CN114551626B - Deep ultraviolet photoelectric detector and preparation method and application thereof - Google Patents
Deep ultraviolet photoelectric detector and preparation method and application thereof Download PDFInfo
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- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/09—Devices sensitive to infrared, visible or ultraviolet radiation
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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
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B82Y40/00—Manufacture or treatment of nanostructures
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- H01L31/0264—Inorganic materials
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Abstract
The invention provides a deep ultraviolet photoelectric detector, a preparation method and application thereof, and belongs to the technical field of photoelectric detection. The invention provides a deep ultraviolet photoelectric detector, which comprises a dielectric insulating substrate, a photosensitive layer arranged on the surface of the dielectric insulating substrate, and two electrodes arranged at two opposite ends of the photosensitive layer; the photosensitive layer comprises a hexagonal boron nitride film and a surface plasmon structure attached to a part of the surface of the hexagonal boron nitride film, the hexagonal boron nitride film is in contact with the dielectric insulating substrate, one electrode is arranged on the surface of the hexagonal boron nitride film without the surface plasmon structure, and the other electrode is arranged on the surface of the hexagonal boron nitride film with the surface plasmon structure; the surface plasmon structure comprises a metal nanoparticle or a semiconductor nanostructure. The dark current of the deep ultraviolet photoelectric detector provided by the invention is extremely low, and the response to deep ultraviolet light is large.
Description
Technical Field
The invention relates to the technical field of photoelectric detection, in particular to a deep ultraviolet photoelectric detector and a preparation method and application thereof.
Background
Photon detection in the deep ultraviolet region (wavelength 200-280 nm) is critical in the fields of flame monitoring and detection, biomedical, chemical and environmental monitoring, ultraviolet astronomy, inter-satellite communication, and the like. The wide forbidden band semiconductor material has excellent physical and chemical characteristics, and has wide prospect in the application fields of high frequency, high temperature, high power and short wavelength. Hexagonal boron nitride is an ultra-wide band-gap semiconductor material, and has proved to be an ideal candidate material for deep ultraviolet photoelectric detectors with solar blindness due to the characteristics of oxidation resistance, radiation resistance, working under high temperature and severe environment and being difficult to react with chemical substances. In addition, the wide bandgap of hexagonal boron nitride (h-BN) greatly simplifies the design of the device by avoiding solar suppression filters and additional cooling systems compared to other conventional wide bandgap semiconductors. The deep ultraviolet photoelectric detector prepared based on the large-area high-quality hexagonal boron nitride two-dimensional atomic crystal film in the current research has good solar blindness, but most of the deep ultraviolet photoelectric detectors based on the hexagonal boron nitride film reported so far still have poor performance, and mainly have the problems of low response to deep ultraviolet light and high dark current.
Disclosure of Invention
The invention aims to provide a deep ultraviolet photoelectric detector, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a deep ultraviolet photoelectric detector, which comprises a dielectric insulating substrate, a photosensitive layer arranged on the surface of the dielectric insulating substrate, and two electrodes arranged at two opposite ends of the photosensitive layer, wherein the photosensitive layer is arranged on the surface of the dielectric insulating substrate;
the photosensitive layer comprises a hexagonal boron nitride film and a surface plasmon structure attached to a part of the surface of the hexagonal boron nitride film, the hexagonal boron nitride film is in contact with the dielectric insulating substrate, one electrode is arranged on the surface of the hexagonal boron nitride film without the surface plasmon structure, and the other electrode is arranged on the surface of the hexagonal boron nitride film with the surface plasmon structure;
the surface plasmon structure comprises a metal nanoparticle or a semiconductor nanostructure.
Preferably, the thickness of the hexagonal boron nitride film is 100-500 nm.
Preferably, the metal nanoparticles are made of gold, aluminum, silver, copper or platinum.
Preferably, the particle size of the metal nano-particles is 1-10 nm, and the distance between adjacent metal nano-particles on the surface of the hexagonal boron nitride film is 25-150 nm.
Preferably, the semiconductor nanostructure comprises hexagonal boron nitride nanoplatelets.
Preferably, the lateral dimension of the hexagonal boron nitride nano-sheet is 1-45 mu m, and the thickness is 0.3-2 mu m; the spacing between adjacent hexagonal boron nitride nano sheets on the surface of the hexagonal boron nitride film is 1-20 mu m.
Preferably, the dielectric insulating substrate includes a sapphire substrate, a quartz glass substrate, or a silicon oxide substrate.
Preferably, the electrode is a metal electrode.
The invention provides a preparation method of the deep ultraviolet photoelectric detector, which comprises the following steps:
depositing a hexagonal boron nitride film on the surface of a dielectric insulating substrate, preparing a surface plasmon structure on part of the surface of the hexagonal boron nitride film, and forming a photosensitive layer on the surface of the dielectric insulating substrate;
two electrodes are arranged at two opposite ends of the photosensitive layer, one electrode is arranged on the surface of the hexagonal boron nitride film without the surface plasmon structure, and the other electrode is arranged on the surface of the hexagonal boron nitride film with the surface plasmon structure, so that the deep ultraviolet photoelectric detector is obtained.
The invention provides application of the deep ultraviolet photoelectric detector in the technical scheme or the deep ultraviolet photoelectric detector prepared by the preparation method in the technical scheme in the fields of chemical environment monitoring, biological environment monitoring, missile plume, radiation detection, astronomical research or satellite communication.
The invention provides a deep ultraviolet photoelectric detector, which comprises a dielectric insulating substrate, a photosensitive layer arranged on the surface of the dielectric insulating substrate, and two electrodes arranged at two opposite ends of the photosensitive layer, wherein the photosensitive layer is arranged on the surface of the dielectric insulating substrate; the photosensitive layer comprises a hexagonal boron nitride film and a surface plasmon structure attached to a part of the surface of the hexagonal boron nitride film, the hexagonal boron nitride film is in contact with the dielectric insulating substrate, one electrode is arranged on the surface of the hexagonal boron nitride film without the surface plasmon structure, and the other electrode is arranged on the surface of the hexagonal boron nitride film with the surface plasmon structure; the surface plasmon structure comprises a metal nanoparticle or a semiconductor nanostructure. The invention adopts metal nano particles or semiconductor nano structures as surface plasmon structures, has the characteristic of extremely strong local field enhancement, combines the surface plasmon structures with hexagonal boron nitride films as photosensitive layers, has extremely low dark current of deep ultraviolet photodetectors based on the photosensitive layers, has high response to deep ultraviolet light (especially 205nm ultraviolet light), and simultaneously has extremely good spectral selectivity to the deep ultraviolet light, obviously enhances light absorption in the wavelength range of the deep ultraviolet light (200-280 nm), has no light absorption in the visible light to near infrared region (400-800 nm), and can solve the problems of high dark current, low light absorption in the deep ultraviolet light region and low response of the traditional hexagonal boron nitride film deep ultraviolet photodetectors. In addition, the surface plasmon structure is only attached to part of the surface of the hexagonal boron nitride film, one electrode is arranged on the surface of the hexagonal boron nitride film without the surface plasmon structure, and the other electrode is arranged on the surface of the hexagonal boron nitride film with the surface plasmon structure, so that an asymmetric vertical structure is formed based on the surface plasmon structure, and the photoelectric characteristic enhancement effect of the detector in a deep ultraviolet region is improved.
The invention adopts the hexagonal boron nitride film as the photosensitive material, and compared with other traditional semiconductor (such as SiC) deep ultraviolet photoelectric detection devices, the device has simplified process and does not need an additional filter plate and a cooling device.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a photosensitive layer in a deep ultraviolet photodetector prepared in example 1;
FIG. 2 is a schematic structural diagram of a deep ultraviolet photodetector prepared in example 1;
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of a photosensitive layer in a deep ultraviolet photodetector prepared in example 2;
FIG. 4 is a schematic structural diagram of a deep ultraviolet photodetector prepared in example 2;
FIG. 5 is an I-V curve of the deep ultraviolet photodetector of example 1 under dark conditions and 205nm ultraviolet irradiation;
FIG. 6 is an I-V curve of the deep ultraviolet photodetector of example 2 under dark conditions and 205nm ultraviolet irradiation;
FIG. 7 is an I-V curve of the deep ultraviolet photodetector of example 1 under dark conditions and 330nm ultraviolet irradiation;
FIG. 8 is an I-V curve of the deep ultraviolet photodetector of example 2 under dark conditions and 330nm ultraviolet irradiation;
FIG. 9 is a histogram of the responsivity of the deep ultraviolet photodetectors prepared in example 1 and comparative example 1 under irradiation of 205nm and 330nm ultraviolet light;
FIG. 10 is a histogram of the responsivity of the deep ultraviolet photodetectors prepared in example 2 and comparative example 1 under irradiation of 205nm and 330nm ultraviolet light;
FIG. 11 is an ultraviolet-visible absorption spectrum at room temperature of the deep ultraviolet photodetectors prepared in examples 1 to 2 and comparative example 1.
Detailed Description
The invention provides a deep ultraviolet photoelectric detector, which comprises a dielectric insulating substrate, a photosensitive layer arranged on the surface of the dielectric insulating substrate, and two electrodes arranged at two opposite ends of the photosensitive layer, wherein the photosensitive layer is arranged on the surface of the dielectric insulating substrate;
the photosensitive layer comprises a hexagonal boron nitride film and a surface plasmon structure attached to a part of the surface of the hexagonal boron nitride film, the hexagonal boron nitride film is in contact with the dielectric insulating substrate, one electrode is arranged on the surface of the hexagonal boron nitride film without the surface plasmon structure, and the other electrode is arranged on the surface of the hexagonal boron nitride film with the surface plasmon structure;
the surface plasmon structure comprises a metal nanoparticle or a semiconductor nanostructure.
The deep ultraviolet photoelectric detector provided by the invention comprises a dielectric insulating substrate. In the present invention, the dielectric insulating substrate preferably includes a sapphire substrate, a quartz glass substrate, or a silicon oxide substrate. In the present invention, the thickness of the dielectric insulating substrate is preferably 300 to 700 μm, more preferably 400 to 500 μm.
The deep ultraviolet photoelectric detector provided by the invention comprises a photosensitive layer arranged on the surface of a dielectric insulating substrate, wherein the photosensitive layer comprises a hexagonal boron nitride film and a surface plasmon structure attached to the surface of a part of the hexagonal boron nitride film, and the hexagonal boron nitride film is in contact with the dielectric insulating substrate. In the present invention, the thickness of the hexagonal boron nitride film is preferably 100 to 500nm, more preferably 100 to 200nm. In the present invention, the surface plasmon structure includes a metal nanoparticle or a semiconductor nanostructure. In the present invention, the metal nanoparticles preferably comprise gold, aluminum, silver, copper or platinum, more preferably gold; the particle diameter of the metal nanoparticle is preferably 1 to 10nm, more preferably 6 to 10nm, and even more preferably 9 to 10nm; the spacing between adjacent metal nanoparticles on the surface of the hexagonal boron nitride film is preferably 25 to 150nm, more preferably 30 to 50nm, and even more preferably 0 to 35nm. In the present invention, the semiconductor nanostructure preferably includes hexagonal boron nitride nanoplatelets having a lateral dimension of preferably 1 to 45 μm, more preferably 1 to 5 μm; the thickness of the hexagonal boron nitride nano-sheet is preferably 0.3-2 μm, more preferably 0.3-1 μm; the spacing between adjacent hexagonal boron nitride nano-sheets on the surface of the hexagonal boron nitride film is preferably 1-20 μm, more preferably 1-10 μm. In the present invention, the area of the hexagonal boron nitride film to which the surface plasmon structure is attached preferably occupies at least 50% of the total area of the hexagonal boron nitride film.
The deep ultraviolet photoelectric detector provided by the invention comprises two electrodes arranged at two opposite ends of the photosensitive layer, wherein one electrode is arranged on the surface of the hexagonal boron nitride film without the surface plasmon structure, and the other electrode is arranged on the surface of the hexagonal boron nitride film with the surface plasmon structure, namely the deep ultraviolet photoelectric detector provided by the invention is of an asymmetric structure. In the present invention, the electrode is preferably a strip electrode. In the present invention, the electrode is preferably a metal electrode; the thickness of the metal electrode is preferably 80-120 nm, more preferably 100-120 nm; the material of the metal electrode preferably comprises one or more of gold, silver, titanium, molybdenum and chromium, and the metal electrode is more preferably a gold/titanium electrode; the gold/titanium electrode preferably comprises a gold layer and a titanium layer which are arranged in a laminated manner, wherein the thickness of the gold layer is 50-100 nm, the thickness of the titanium layer is preferably 10-20 nm, and the titanium layer is in contact with the photosensitive layer.
The invention provides a preparation method of the deep ultraviolet photoelectric detector, which comprises the following steps:
depositing a hexagonal boron nitride film on the surface of a dielectric insulating substrate, preparing a surface plasmon structure on part of the surface of the hexagonal boron nitride film, and forming a photosensitive layer on the surface of the dielectric insulating substrate;
two electrodes are arranged at two opposite ends of the photosensitive layer, one electrode is arranged on the surface of the hexagonal boron nitride film without the surface plasmon structure, and the other electrode is arranged on the surface of the hexagonal boron nitride film with the surface plasmon structure, so that the deep ultraviolet photoelectric detector is obtained.
According to the invention, a hexagonal boron nitride film is deposited on the surface of a dielectric insulating substrate, a surface plasmon structure is prepared on part of the surface of the hexagonal boron nitride film, and a photosensitive layer is formed on the surface of the dielectric insulating substrate. In the present invention, the dielectric insulating substrate is preferably subjected to pretreatment before use, the pretreatment preferably comprising: and sequentially ultrasonically cleaning the dielectric insulating substrate by using acetone and deionized water, then soaking the dielectric insulating substrate in a mixed solution of hydrogen peroxide and sulfuric acid, then taking out the dielectric insulating substrate, sequentially ultrasonically cleaning the dielectric insulating substrate by using deionized water and ethanol, and finally drying the dielectric insulating substrate by using nitrogen. In the invention, the time of each ultrasonic cleaning is independently preferably 5-8 min; the hydrogen peroxide is preferably analytically pure, the sulfuric acid is preferably analytically pure, and the volume ratio of the hydrogen peroxide to the sulfuric acid is preferably 1:3, a step of; the soaking treatment time is preferably 10-15 min.
In the present invention, the preparation method of the hexagonal boron nitride film preferably includes a chemical vapor deposition method, preferably includes a radio frequency plasma chemical vapor deposition method, a microwave plasma enhanced chemical vapor deposition method, or an inductively coupled plasma chemical vapor deposition method, or a physical vapor deposition method, preferably includes a radio frequency magnetron sputtering method, an ion beam assisted sputter deposition method, or a laser deposition method.The hexagonal boron nitride film is preferably prepared by adopting an ion beam assisted sputtering deposition method, and the operation steps of the ion beam assisted sputtering deposition method preferably comprise: and (3) using a double-ion-beam auxiliary sputtering deposition system to perform vacuumizing treatment on the film deposition chamber, heating the dielectric insulation substrate, then introducing a main ion source and an auxiliary ion source, adjusting the film deposition chamber to be at working pressure, then opening the kofmann ion source, adjusting the energy of the main ion source and the energy of the auxiliary ion source, performing deposition, and depositing on the surface of the dielectric insulation substrate to obtain the hexagonal boron nitride film. In the present invention, the evacuation treatment preferably evacuates the vacuum of the thin film deposition chamber to 2X 10 -5 Pa; the heating is preferably to heat the temperature of the dielectric insulating substrate to 300-500 ℃; the main ion source is preferably argon, and the flow rate of the main ion source is preferably 6sccm; the auxiliary ion source is preferably argon and nitrogen, the flow rate of the argon is preferably 2sccm, and the flow rate of the nitrogen is preferably 3sccm; the working pressure of the film deposition chamber is preferably (3-5) x 10 -2 Pa; the energy of the main ion source is preferably 1250eV, and the energy of the auxiliary ion source is preferably 280eV; the deposition time is preferably 2 to 8 hours.
After a hexagonal boron nitride film is obtained by depositing on the surface of a dielectric insulating substrate, a surface plasmon structure is prepared on part of the surface of the hexagonal boron nitride film, and a photosensitive layer is formed on the surface of the dielectric insulating substrate. The invention preferably adopts different preparation methods according to different surface plasmon structures, and particularly, when the surface plasmon structures are metal nano particles, the self-assembled micelle method, nanosphere lithography method, rapid thermal annealing method or hydrothermal method can be adopted for preparation; when the surface plasmon structure is a semiconductor nanostructure, for example, further hexagonal boron nitride nanoplatelets, it may be prepared by a mechanical exfoliation method, preferably including a tape exfoliation method, a ball milling method, a plasma etching method, or a fluid exfoliation method, a chemical exfoliation method, preferably including a liquid-phase ultrasonic exfoliation method, an ion insertion exfoliation method, or a chemical functional exfoliation method, or a synthesis method, preferably including a chemical synthesis method, a hydrothermal synthesis method, or a vapor phase synthesis method. The preparation methods of the gold nanoparticles, the hexagonal boron nitride nanosheets and the photosensitive layer are described in detail below by taking a surface plasmon structure as a gold nanoparticle or a hexagonal boron nitride nanosheet as an example.
In the present invention, when the surface plasmon structure is a gold nanoparticle, the preparation method of the gold nanoparticle and the photosensitive layer preferably includes the steps of:
dispersing a diblock copolymer polystyrene-polyvinylpyridine in toluene to obtain a toluene solution of the polystyrene-polyvinylpyridine; mixing gold-containing inorganic metal salt with the toluene solution of the polystyrene-polyvinyl pyridine to obtain a polystyrene-polyvinyl pyridine reverse micelle solution loaded with gold salt;
and coating the gold salt-loaded polystyrene-polyvinyl pyridine reverse micelle solution on part of the surface of the hexagonal boron nitride film, and reducing the gold salt-loaded polystyrene-polyvinyl pyridine reverse micelle in the gold salt-loaded polystyrene-polyvinyl pyridine reverse micelle solution to generate gold nanoparticles to obtain a photosensitive layer on the surface of the substrate.
The invention disperses the diblock copolymer polystyrene-polyvinylpyridine in toluene to obtain a toluene solution of polystyrene-polyvinylpyridine. In the present invention, the molecular weight of polystyrene in the diblock copolymer polystyrene-polyvinylpyridine is preferably 185000, and the molecular weight of polyvinylpyridine is preferably 90000; in the examples of the present invention, the diblock copolymer polystyrene-polyvinylpyridine had a purity of 99.5% or more, and was purchased from alfa eastern chemical company, ltd. In the toluene solution of the polystyrene-polyvinylpyridine, the concentration of the polystyrene-polyvinylpyridine is preferably 5-25 mg/mL, more preferably 5-10 mg/mL; the dispersing mode is preferably magnetic stirring, and the time of the magnetic stirring is preferably 3-7 days.
After obtaining toluene solution of polystyrene-polyvinyl pyridine, the invention mixes gold-containing inorganic metal salt with the toluene solution of polystyrene-polyvinyl pyridine to obtain polystyrene-polyvinyl pyridine reverse micelle loaded with gold saltA solution. In the present invention, the gold-containing inorganic metal salt is preferably HAuCl 4 The mass ratio of the gold-containing inorganic metal salt to the diblock copolymer polystyrene-polyvinylpyridine is preferably (15-40): 50, more preferably (16 to 27): 50; the mixing mode is preferably magnetic stirring, and the time of the magnetic stirring is preferably 7-14 days.
After obtaining a gold salt-loaded polystyrene-polyvinyl pyridine reverse micelle solution, coating the gold salt-loaded polystyrene-polyvinyl pyridine reverse micelle solution on part of the surface of the hexagonal boron nitride film, reducing the gold salt-loaded polystyrene-polyvinyl pyridine reverse micelle in the gold salt-loaded polystyrene-polyvinyl pyridine reverse micelle solution to generate gold nanoparticles, and obtaining a photosensitive layer on the surface of a substrate; wherein the diblock copolymer polystyrene-polyvinylpyridine contains C, H and N elements, which are reduced to corresponding gases in the reduction process, and do not remain in the photosensitive layer; one end of the diblock copolymer polystyrene-polyvinylpyridine is hydrophilic and the other end is hydrophobic, and the property is utilized to ensure that the polystyrene-polyvinylpyridine reverse micelle solution loaded with gold salt is uniformly distributed on the surface of the substrate in the process of lifting. In the present invention, the coating method preferably includes a pulling method, a spin coating method, or a drop coating method, more preferably a pulling method; in the embodiment of the invention, a part of the square boron nitride film is placed in the polystyrene-polyvinyl pyridine reverse micelle solution loaded with gold salt, and the polystyrene-polyvinyl pyridine reverse micelle solution loaded with gold salt is pulled on a part of the hexagonal boron nitride film; the speed of the pulling is preferably 200 to 300 μm/s, more preferably 234 μm/s. In the present invention, the method of the reduction treatment preferably includes a hydrogen plasma treatment method, a hydrogen reduction method, or a high Wen Tui fire method, more preferably a hydrogen reduction method; the operating conditions of the hydrogen reduction process include: the flow rate of the hydrogen gas is preferably 30 to 50sccm, more preferably 40 to 50sccm; the temperature of the heat treatment is preferably 450 to 550 ℃, more preferably 500 ℃; the heat treatment time is preferably 1 to 3 hours, more preferably 2 hours.
In the present invention, when the surface plasmon structure is a hexagonal boron nitride nanosheet, the preparation method of the hexagonal boron nitride nanosheet and the photosensitive layer preferably includes the steps of:
mixing hexagonal boron nitride powder with potassium permanganate to obtain a solid mixed material; mixing sulfuric acid with phosphoric acid to obtain mixed acid; mixing the solid mixed material with mixed acid, and performing first chemical treatment under heating to obtain a first chemical material; mixing the first chemical material with hydrogen peroxide water solution, and performing second chemical treatment under the ice water bath condition to obtain a second chemical material;
performing low-speed centrifugal separation on the second chemical material to obtain supernatant; carrying out high-speed centrifugal washing on the supernatant by adopting deionized water and ethanol alternately until the pH value is more than 5, and drying the precipitate obtained after the high-speed centrifugal washing to obtain hexagonal boron nitride nanosheets; the rotating speed of the low-speed centrifugal separation is 3000-5000 rpm, and the rotating speed of the high-speed centrifugal washing is 16000-20000 rpm;
dispersing the hexagonal boron nitride nano-sheets in ethanol to obtain hexagonal boron nitride nano-sheet dispersion liquid; and coating the hexagonal boron nitride nanosheet dispersion liquid on part of the surface of the hexagonal boron nitride film, and obtaining a photosensitive layer on the surface of the substrate after the ethanol volatilizes.
The invention mixes hexagonal boron nitride powder with potassium permanganate to obtain solid mixed material. In the present invention, the particle size of the hexagonal boron nitride powder is preferably 1 to 45 μm; the mass ratio of the hexagonal boron nitride powder to the potassium permanganate is preferably 1: (2 to 6), more preferably 1: (5-6). In the embodiment of the invention, the purity of the hexagonal boron nitride powder is more than or equal to 99.5 percent, and the hexagonal boron nitride powder is purchased from alfa elsa (china) chemical company; the potassium permanganate was analytically pure and purchased from beijing chemical reagent company.
The invention mixes sulfuric acid with phosphoric acid to obtain mixed acid. In the present invention, the sulfuric acid is preferably analytically pure, the phosphoric acid is preferably analytically pure, and the volume ratio of sulfuric acid to phosphoric acid is preferably 8: (1-2). In an embodiment of the present invention, the sulfuric acid and phosphoric acid are purchased from Beijing chemical reagent company.
After the solid mixed material and the mixed acid are obtained, the solid mixed material and the mixed acid are mixed, and the first chemical treatment is carried out under the heating condition to obtain the first chemical material. In the present invention, the ratio of the solid mixture to the mixed acid is preferably (3 to 7) g: (135-150) mL, more preferably (6-7) g: (135-140) mL. In the present invention, the temperature of the first chemical treatment is preferably 70 to 78 ℃, more preferably 74 to 75 ℃; the time is preferably 10 to 14 hours, more preferably 12 hours; the first chemical treatment is preferably performed under stirring. In the invention, in the process of the first chemical treatment, potassium permanganate and sulfuric acid react to generate manganese dioxide nano particles, and the manganese dioxide nano particles are inserted between boron nitride layers in hexagonal boron nitride powder (namely massive hexagonal boron nitride), so that the distance between the layers is increased, and the peeling is facilitated through the subsequent second chemical treatment.
After the first chemical material is obtained, the first chemical material is mixed with hydrogen peroxide aqueous solution, and second chemical treatment is carried out under the ice water bath condition to obtain a second chemical material. In the invention, the hydrogen peroxide aqueous solution is preferably obtained by mixing analytically pure hydrogen peroxide with deionized water, and the volume ratio of the analytically pure hydrogen peroxide to the deionized water is preferably 1: (6 to 20), more preferably 1: (6-8). In an embodiment of the invention, the analytically pure hydrogen peroxide is purchased from beijing chemical reagent company. In the present invention, the aqueous hydrogen peroxide solution is preferably subjected to a refrigeration treatment before use, and the temperature of the refrigeration is preferably-5 to 5 ℃, more preferably-5 to 0 ℃; the time is preferably 12 to 24 hours, more preferably 12 to 15 hours. In the present invention, the time of the second chemical treatment is preferably 1.5 to 2 hours, and the second chemical treatment is preferably performed under stirring. After the second chemical treatment, the present invention preferably naturally cools the resulting suspension to room temperature (25 ℃) to provide a second chemical material. In the invention, in the second chemical treatment process, the manganese dioxide nano particles react with hydrogen peroxide to generate oxygen, and release of the oxygen can realize stripping of hexagonal boron nitride powder (namely massive hexagonal boron nitride), so that the hexagonal boron nitride nano sheets are obtained.
Performing low-speed centrifugal separation on the second chemical material to obtain supernatant; carrying out high-speed centrifugal washing on the supernatant by adopting deionized water and ethanol alternately until the pH value is more than 5, and drying the precipitate obtained after the high-speed centrifugal washing to obtain hexagonal boron nitride nanosheets; the rotation speed of the low-speed centrifugal separation is 3000-5000 rpm, and the rotation speed of the high-speed centrifugal washing is 16000-20000 rpm. In the present invention, the time for the low-speed centrifugal separation is preferably 10 to 15 minutes, and the time for each high-speed centrifugal washing is preferably 10 to 15 minutes.
After hexagonal boron nitride nanosheets are obtained, the hexagonal boron nitride nanosheets are dispersed in ethanol to obtain hexagonal boron nitride nanosheet dispersion liquid; and coating the hexagonal boron nitride nanosheet dispersion liquid on part of the surface of the hexagonal boron nitride film, and obtaining a photosensitive layer on the surface of the substrate after the ethanol volatilizes. In the present invention, the concentration of the hexagonal boron nitride nanosheet dispersion is preferably 0.01 to 0.05mg/mL, more preferably 0.01 to 0.03mg/mL. In the present invention, the coating method preferably includes a pulling method, a spin coating method, or a drop coating method, more preferably a pulling method; in the embodiment of the invention, a part of square boron nitride film is placed in the hexagonal boron nitride nano-sheet dispersion liquid, and the hexagonal boron nitride nano-sheet dispersion liquid is lifted on a part of the hexagonal boron nitride film; the pulling speed is preferably 10 to 50. Mu.m/s, more preferably 15 to 20. Mu.m/s.
After the photosensitive layer is obtained, two electrodes are arranged at two opposite ends of the photosensitive layer, one electrode is arranged on the surface of the hexagonal boron nitride film without the surface plasmon structure, and the other electrode is arranged on the surface of the hexagonal boron nitride film with the surface plasmon structure, so that the deep ultraviolet photoelectric detector is obtained. The electrode is preferably prepared by a magnetron sputtering method or an evaporation coating method; the specific operation conditions of the magnetron sputtering method and the evaporation coating method are not particularly limited, and the specific operation conditions are selected according to the material and thickness of the electrode.
The preparation process of the deep ultraviolet photoelectric detector provided by the invention is simple, has low cost and is suitable for large-scale production.
The invention provides application of the deep ultraviolet photoelectric detector in the technical scheme or the deep ultraviolet photoelectric detector prepared by the preparation method in the technical scheme in the fields of chemical environment monitoring, biological environment monitoring, missile plume, radiation detection, astronomical research or satellite communication.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Adding a mixture of bulk hexagonal boron nitride powder (granularity of 1-45 μm, purity of not less than 99.5%, alfa aegasa, 1 g) and potassium permanganate (analytically pure, beijing reagent, 6 g) to an acidic mixture of sulfuric acid (analytically pure, beijing reagent, 120 mL) and phosphoric acid (analytically pure, beijing reagent, 15 mL), and stirring the obtained mixture at 75 ℃ for 12h to obtain a first chemical material; mixing hydrogen peroxide (analytically pure, beijing reagent, 18 mL) and deionized water (120 mL), refrigerating at-5 ℃ for 12h, mixing the obtained refrigerating solution with the first chemical material, stirring for 1.5h under the ice water bath condition, removing the ice water bath, and naturally cooling to room temperature (25 ℃), thus obtaining a second chemical material; and (3) carrying out centrifugal separation on the second chemical material for 15min at 3000rpm, carrying out high-speed centrifugal washing on the obtained supernatant by alternately adopting deionized water and ethanol at 20000rpm, wherein the time of each centrifugal washing is 15min until the pH value is more than 5, and then drying the precipitate material obtained after the high-speed centrifugal washing to obtain hexagonal boron nitride nano-sheets (BNSs), wherein the transverse dimension is 1-5 mu m, and the thickness is 0.3-1 mu m.
(2) Taking a quartz glass substrate (with the thickness of 400 nm) as a dielectric insulating substrate, sequentially using acetone and deionized water to ultrasonically clean the quartz glass substrate for 5min, then soaking the quartz glass substrate in a mixed solution of hydrogen peroxide and sulfuric acid (the volume ratio of the hydrogen peroxide to the sulfuric acid is 1:3) for 10min, then taking out the quartz glass substrate, sequentially using deionized water and ethanol to ultrasonically clean the quartz glass substrate for 5min, finally drying the quartz glass substrate by nitrogen to obtain a pretreated substrate, and drying and preserving the pretreated substrate;
vacuum pumping the film depositing chamber to 2 x 10 with double ion beam assisted sputtering depositing system -5 Pa, heating the pretreated substrate to 500 ℃, then introducing argon gas serving as a main ion source into the substrate at 6sccm, argon gas serving as an auxiliary ion source into the substrate at 2sccm, nitrogen gas serving as an auxiliary ion source into the substrate at 3sccm, and adjusting the working pressure of the thin film deposition chamber to 3X 10 -2 Pa, then turning on the kofmann ion source, adjusting the energy of the main ion source to 1250eV, depositing with the energy of the auxiliary ion source to 280eV for 2h, and depositing on the surface of the substrate to obtain the hexagonal boron nitride film with the thickness of 200nm.
(3) Uniformly dispersing the hexagonal boron nitride nano-sheets into ethanol to ensure that the concentration of the hexagonal boron nitride nano-sheets is 0.01mg/mL, thereby obtaining hexagonal boron nitride nano-sheet dispersion liquid; and placing a substrate with a part of hexagonal boron nitride film deposited in the hexagonal boron nitride nano-sheet dispersion liquid, lifting the hexagonal boron nitride nano-sheet dispersion liquid on a part of hexagonal boron nitride film at a speed of 15 mu m/s, and obtaining a photosensitive layer on the surface of the substrate after ethanol is volatilized completely, wherein the photosensitive layer comprises the hexagonal boron nitride film and hexagonal boron nitride nano-sheets attached to the surface of the hexagonal boron nitride film part, the spacing distance between adjacent hexagonal boron nitride nano-sheets is 1-10 mu m, and the area of the hexagonal boron nitride film attached with the hexagonal boron nitride nano-sheets accounts for 50% of the total area of the hexagonal boron nitride film.
(4) And depositing two strip-shaped gold/titanium electrodes at two opposite ends of the surface of the photosensitive layer by adopting a magnetron sputtering method, wherein one strip-shaped gold/titanium electrode is deposited on the surface of the hexagonal boron nitride film without the hexagonal boron nitride nano-sheet, the other strip-shaped gold/titanium electrode is deposited on the surface of the hexagonal boron nitride film with the hexagonal boron nitride nano-sheet, the gold/titanium electrode comprises a gold layer and a titanium layer which are arranged in a laminated manner, the thickness of the gold layer is 100nm, the thickness of the titanium layer is 20nm, and the titanium layer is in contact with the photosensitive layer to obtain the deep ultraviolet photoelectric detector (h-BN/BNSs).
Fig. 1 is a Scanning Electron Microscope (SEM) photograph of a photosensitive layer in a deep ultraviolet photodetector prepared in example 1, and it can be seen that hexagonal boron nitride nanoplatelets have been compounded on a hexagonal boron nitride thin film.
Fig. 2 is a schematic structural diagram of a deep ultraviolet photodetector prepared in embodiment 1, which comprises a substrate, a photosensitive layer disposed on the surface of the substrate, and two strip-shaped gold/titanium electrodes disposed at two opposite ends of the photosensitive layer, wherein the photosensitive layer comprises a hexagonal boron nitride film and hexagonal boron nitride nanoplatelets attached to a part of the surface of the hexagonal boron nitride film, one strip-shaped gold/titanium electrode is disposed on the surface of the hexagonal boron nitride film, to which the hexagonal boron nitride nanoplatelets are not attached, and the other strip-shaped gold/titanium electrode is disposed on the surface of the hexagonal boron nitride film, to which the hexagonal boron nitride nanoplatelets are attached, i.e., the deep ultraviolet photodetector provided in the invention is of an asymmetric structure.
Example 2
(1) 50mg of diblock copolymer polystyrene-polyvinylpyridine (the purity is more than or equal to 99.95 percent, the alfa is, the molecular weight of polystyrene in the diblock copolymer polystyrene-polyvinylpyridine is 185000, the molecular weight of polyvinylpyridine is 90000) is dispersed in 10mL of toluene, and the mixture is magnetically stirred for 7 days to completely dissolve the polystyrene-polyvinylpyridine, so as to obtain a toluene solution of the polystyrene-polyvinylpyridine; 26mg of HAuCl 4 Adding the mixture into a toluene solution of polystyrene-polyvinyl pyridine, and magnetically stirring the mixture for 7 days to obtain a polystyrene-polyvinyl pyridine reverse micelle solution loaded with gold salt.
(2) The quartz glass substrate was pretreated in the same manner as in step (2) of example 1, and then a hexagonal boron nitride film having a thickness of 200nm was deposited on the surface of the substrate.
(3) Placing a substrate with a part of the hexagonal boron nitride film deposited in the polystyrene-polyvinyl pyridine reverse micelle solution loaded with gold salt, lifting the polystyrene-polyvinyl pyridine reverse micelle solution loaded with gold salt at the speed of 234 mu m/s on the part of the hexagonal boron nitride film, heating for 2 hours in a 50sccm hydrogen environment at 500 ℃, reducing the polystyrene-polyvinyl pyridine reverse micelle loaded with gold salt on the hexagonal boron nitride film to generate gold nano particles (AuNPs), and obtaining a photosensitive layer on the surface of the substrate, wherein the photosensitive layer comprises the hexagonal boron nitride film and the gold nano particles attached to the part of the hexagonal boron nitride film, the particle size of the gold nano particles is 9-10 nm, the spacing distance between adjacent gold nano particles is 30-35 nm, and the area of the hexagonal boron nitride film attached with the gold nano particles accounts for 50% of the total area of the hexagonal boron nitride film.
(4) And depositing two strip-shaped gold/titanium electrodes at two opposite ends of the surface of the photosensitive layer by adopting a magnetron sputtering method, wherein one strip-shaped gold/titanium electrode is deposited on the surface of the hexagonal boron nitride film without the attached gold nanoparticles, the other strip-shaped gold/titanium electrode is deposited on the surface of the hexagonal boron nitride film with the attached gold nanoparticles, the gold/titanium electrode comprises a gold layer and a titanium layer which are arranged in a laminated manner, the thickness of the gold layer is 100nm, the thickness of the titanium layer is 20nm, and the titanium layer is in contact with the photosensitive layer to obtain the deep ultraviolet photoelectric detector (h-BN/AuNPs).
Fig. 3 is a Scanning Electron Microscope (SEM) photograph of a photosensitive layer in the deep ultraviolet photodetector prepared in example 2, and it can be seen that gold nanoparticles are uniformly compounded on a hexagonal boron nitride thin film.
Fig. 4 is a schematic structural diagram of a deep ultraviolet photodetector prepared in example 2, which includes a substrate, a photosensitive layer disposed on a surface of the substrate, and two strip-shaped gold/titanium electrodes disposed at two opposite ends of the photosensitive layer, wherein the photosensitive layer includes a hexagonal boron nitride film and gold nanoparticles attached to a portion of the surface of the hexagonal boron nitride film, one of the strip-shaped gold/titanium electrodes is disposed on the surface of the hexagonal boron nitride film to which no gold nanoparticles are attached, and the other strip-shaped gold/titanium electrode is disposed on the surface of the hexagonal boron nitride film to which gold nanoparticles are attached, i.e., the deep ultraviolet photodetector provided in the invention is of an asymmetric structure.
Comparative example 1
Pretreating a quartz glass substrate according to the method of the step (2) in the example 1, and then depositing a hexagonal boron nitride film with the thickness of 200nm on the surface of the substrate;
and depositing two strip-shaped gold/titanium electrodes at two opposite ends of the surface of the hexagonal boron nitride film by adopting a magnetron sputtering method, wherein the gold/titanium electrodes comprise gold layers and titanium layers which are arranged in a laminated manner, the thickness of the gold layers is 100nm, the thickness of the titanium layers is 20nm, and the titanium layers are in contact with the hexagonal boron nitride film to obtain the deep ultraviolet photoelectric detector.
Performance test:
1. the performances of the deep ultraviolet photodetectors prepared in examples 1 to 2 were tested under dark conditions and 205nm ultraviolet irradiation, respectively, using a digital source meter of Ji Shi Li 2450 under a voltage condition of.+ -.35V, and the resulting I-V curves are shown in FIGS. 5 and 6. FIG. 5 is an I-V curve of the deep ultraviolet photodetector of example 1 under dark conditions and 205nm ultraviolet irradiation, showing that the device has very little photo-response when a forward voltage is applied; when negative voltage is applied, the light response of the device increases with the increase of the voltage, and when-35V voltage is applied, the dark current of the device is-8.87×10 -8 Amperes, current under 205nm light excitation of-1.47×10 -7 Amperes indicate that the device has good light response characteristics. FIG. 6 is an I-V curve of the deep ultraviolet photodetector of example 2 under dark conditions and 205nm ultraviolet irradiation, showing that the device has very little photoresponse when negative voltage is applied; when a forward voltage is applied, the photoresponse of the device increases with the increase of the voltage, and when a +35V voltage is applied, the dark current of the device is +7.06X10 -8 Amperes, current under 205nm light excitation of +1.7X10 -7 Amperes indicate that the device has good light response characteristics.
2. The performances of the deep ultraviolet photodetectors prepared in examples 1 to 2 were tested under dark conditions and 330nm ultraviolet irradiation, respectively, using a digital source meter of Ji Shi Li 2450 under a voltage condition of.+ -.35V, and the resulting I-V curves are shown in FIG. 7 and FIG. 8. FIG. 7 is an I-V curve of the deep ultraviolet photodetector of example 1 under dark conditions and 330nm ultraviolet irradiation, showing that the device has very little photo-response when a forward voltage is applied; when negative voltage is applied, the light response of the device increases with the increase of the voltage, and when-35V voltage is applied, the dark current of the device is-8.87×10 -8 Ampere, current under 330nm light excitation is-1.55X10 -7 Amperes, indicating that the device hasGood light response characteristics. FIG. 8 is an I-V curve of the deep ultraviolet photodetector of example 2 under dark conditions and 330nm ultraviolet irradiation, showing that the device has very little photoresponse when negative voltage is applied; when a forward voltage is applied, the photoresponse of the device increases with the increase of the voltage, and when a +35V voltage is applied, the dark current of the device is +7.06X10 -8 Amperes, current under 330nm light excitation of +1.19X10 -7 Amperes indicate that the device has good light response characteristics.
3. The performance of the deep ultraviolet photodetectors prepared in examples 1-2 and comparative example 1 were tested under ultraviolet irradiation conditions of applied voltage of.+ -.35V, light area of 0.25 square cm at 205nm (power density of 0.019 watts per square cm) and 330nm (power density of 0.044 watts per square cm) using a digital source meter of Ji Shi Li 2450, and the resulting responsivity bar charts are shown in FIGS. 9 and 10. FIG. 9 is a histogram of the responsivity of the deep ultraviolet photodetectors prepared in example 1 and comparative example 1 under irradiation of 205nm and 330nm ultraviolet light, and the specific data are shown in Table 1. The results show that the device prepared in example 1 has a photo-response intensity of 1.24X10 under 205nm UV irradiation -5 An ampere/watt, which is much higher than the light response intensity of the device of comparative example 1 (3.86X 10 -7 An/watt). The device prepared in example 1 had a photo-response intensity of 6.00X 10 under 330nm UV irradiation -6 An ampere/watt which is smaller than the light response intensity under the irradiation of 205nm ultraviolet light, which indicates that the response wave band of the device is in the deep ultraviolet region; also, at an excitation wavelength of 330nm, the light response intensity of the device in example 1 was still much higher than that of the device in comparative example 1 (8.49×10 -7 An/watt). FIG. 10 is a histogram of the responsivity of the deep ultraviolet photodetectors prepared in example 2 and comparative example 1 under irradiation of 205nm and 330nm ultraviolet light, and the specific data are shown in Table 1. The results show that the device prepared in example 2 has a photo-response intensity of 2.24X10 under 205nm UV irradiation -5 An ampere/watt, which is much higher than the light response intensity of the device of comparative example 1 (3.86X 10 -7 An/watt). The device prepared in example 2 had a photo-response intensity of 4.35X10 under 330nm UV irradiation -6 An ampere/watt less than the light response intensity under 205nm ultraviolet light, indicating thatThe response wave band of the device is in the deep ultraviolet region; also, at an excitation wavelength of 330nm, the light response intensity of the device in example 2 was still much higher than that of the device in comparative example 1 (8.49×10 -7 An/watt).
TABLE 1 light response intensities of devices of examples 1-2 and comparative example 1 at different excitation wavelengths
As can be seen from the combination of fig. 9 and 10 and table 1, the dark current of the deep ultraviolet photodetector without adding metal nanoparticles and boron nitride nanosheets as surface plasmon structure is large, and the responsivity to ultraviolet light is extremely low; dark current of the deep ultraviolet photoelectric detector with the metal nano particles and the boron nitride nano sheets as surface plasmon structures is reduced, and responsiveness is greatly improved.
4. The performance of the deep ultraviolet photodetectors prepared in examples 1 to 2 and comparative example 1 was tested at room temperature using a UNICO UV-2802S UV-vis absorption spectrometer, and fig. 11 is a UV-vis absorption spectrum of the deep ultraviolet photodetectors prepared in examples 1 to 2 and comparative example 1 at room temperature, and as can be seen from fig. 11, the deep ultraviolet photodetectors prepared in examples 1 to 2 and comparative example 1 have excellent spectral selectivity to deep ultraviolet light and no light absorption in the visible to near infrared region (400 to 800 nm). Meanwhile, the deep ultraviolet photoelectric detector prepared in the embodiment 2 has obviously enhanced light absorption in the deep ultraviolet light wavelength (200-280 nm) range.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. A deep ultraviolet photoelectric detector comprises a dielectric insulating substrate, a photosensitive layer arranged on the surface of the dielectric insulating substrate, and two electrodes arranged at two opposite ends of the photosensitive layer;
the photosensitive layer comprises a hexagonal boron nitride film and a surface plasmon structure attached to a part of the surface of the hexagonal boron nitride film, the hexagonal boron nitride film is in contact with the dielectric insulating substrate, one electrode is arranged on the surface of the hexagonal boron nitride film without the surface plasmon structure, and the other electrode is arranged on the surface of the hexagonal boron nitride film with the surface plasmon structure;
the surface plasmon structure comprises a metal nanoparticle or a semiconductor nanostructure;
the particle size of the metal nano particles is 1-10 nm, and the distance between adjacent metal nano particles on the surface of the hexagonal boron nitride film is 25-150 nm;
the semiconductor nano structure is a hexagonal boron nitride nano sheet, the transverse dimension of the hexagonal boron nitride nano sheet is 1-45 mu m, and the thickness of the hexagonal boron nitride nano sheet is 0.3-2 mu m; the distance between adjacent hexagonal boron nitride nano sheets on the surface of the hexagonal boron nitride film is 1-20 mu m;
the thickness of the hexagonal boron nitride film is 100-500 nm;
the dielectric insulating substrate includes a sapphire substrate, a quartz glass substrate, or a silicon oxide substrate.
2. The deep ultraviolet photodetector of claim 1, wherein the metal nanoparticles comprise gold, aluminum, silver, copper, or platinum.
3. The deep ultraviolet photodetector of claim 1, wherein said electrode is a metal electrode.
4. A method of manufacturing a deep ultraviolet photodetector as defined in any one of claims 1 to 3, comprising the steps of:
depositing a hexagonal boron nitride film on the surface of a dielectric insulating substrate, preparing a surface plasmon structure on part of the surface of the hexagonal boron nitride film, and forming a photosensitive layer on the surface of the dielectric insulating substrate;
two electrodes are arranged at two opposite ends of the photosensitive layer, one electrode is arranged on the surface of the hexagonal boron nitride film without the surface plasmon structure, and the other electrode is arranged on the surface of the hexagonal boron nitride film with the surface plasmon structure, so that the deep ultraviolet photoelectric detector is obtained.
5. Use of a deep ultraviolet photodetector according to any one of claims 1 to 3 or prepared by the preparation method according to claim 4 in the fields of chemical environmental monitoring, biological environmental monitoring, missile plume, radiation detection, astronomical research or satellite communication.
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