WO2019153698A1 - Optical detector and manufacturing method therefor - Google Patents

Optical detector and manufacturing method therefor Download PDF

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Publication number
WO2019153698A1
WO2019153698A1 PCT/CN2018/100580 CN2018100580W WO2019153698A1 WO 2019153698 A1 WO2019153698 A1 WO 2019153698A1 CN 2018100580 W CN2018100580 W CN 2018100580W WO 2019153698 A1 WO2019153698 A1 WO 2019153698A1
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dimensional
nanosheet
photodetector
tantalum
working electrode
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PCT/CN2018/100580
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French (fr)
Chinese (zh)
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张晗
谢中建
邢晨阳
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深圳大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—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
    • H01L31/0248—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 characterised by their semiconductor bodies
    • H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—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
    • H01L31/0248—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 characterised by their semiconductor bodies
    • H01L31/0352—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H01L31/035272—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—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
    • 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
    • H01L31/10—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 characterised by potential barriers, e.g. phototransistors
    • H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
    • H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
    • H01L31/108—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the Schottky type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors

Definitions

  • the invention relates to the field of optoelectronics, in particular to a photodetector and a preparation method thereof.
  • the photodetector is a sensor that can realize photoelectric conversion by using a material having a photoelectric effect, and its function is to realize photoelectric conversion.
  • the mechanism is that the guided beam incident on the detector causes an excited transition of the electron from the valence band to the conduction band, producing photogenerated carriers (electrons and holes). These carriers are collected by a PN junction or a Schottky barrier and ultimately appear as a photovoltage or photocurrent.
  • photodetectors based on two-dimensional nanomaterials such as black phosphorus are considered to be an effective alternative to current commercial photodetectors.
  • a photodetector has the following disadvantages: (1) The photodetector based on the wide bandgap semiconductor has a short detection band due to a large band gap; (2) the existing two-dimensional nanomaterial has poor stability, resulting in light detection. The performance of the device is poor; (3) The photodetector of the solid module is exposed to the air and has the disadvantage of being easily oxidized.
  • the present invention proposes a novel photoelectrochemical based photodetector.
  • the present invention provides a photodetector comprising a novel two-dimensional functional material-two-dimensional germanium nanosheet, the two-dimensional germanium nanosheet having good environmental stability and simultaneous Has a good photodetection function.
  • a first aspect of the present invention provides a photodetector including a working electrode, a counter electrode, and an electrolyte disposed between the working electrode and the counter electrode, the working electrode including a conductive substrate and disposed on the conductive A semiconductor layer on the substrate, the material of the semiconductor layer comprising a two-dimensional germanium nanosheet.
  • the two-dimensional tantalum nanosheet has a thickness of 1-50 nm.
  • the two-dimensional tantalum nanosheet has a thickness of 1-5 nm.
  • the two-dimensional tantalum nanosheet has a thickness of 5-10 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 10-200 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 10-50 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 50-100 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 100-200 nm.
  • the semiconductor layer further includes a polymer material, and the polymer material and the two-dimensional germanium nanosheet are uniformly distributed in the semiconductor layer.
  • the polymer material comprises at least one of polyvinylidene fluoride and cellulose.
  • the mass ratio of the polymer material to the two-dimensional cerium nanosheet is 1:10-1:100.
  • the mass ratio of the polymer material to the two-dimensional cerium nanosheet is 1:10 to 1:50.
  • the electrolyte comprises an alkaline electrolyte or a neutral electrolyte
  • the alkaline electrolyte comprises an alkali solution
  • the neutral electrolyte comprises a neutral salt solution.
  • the alkali solution comprises at least one of a potassium hydroxide solution and a sodium hydroxide solution
  • the salt solution includes at least one of a sodium sulfate solution, a potassium sulfate solution, a sodium chloride solution, and a potassium chloride solution.
  • the concentration of the electrolyte is from 0.1 mol/L to 10 mol/L.
  • concentration of the electrolyte is from 0.1 mol/L to 1 mol/L.
  • the semiconductor layer has a thickness of 100 nm to 500 nm.
  • the semiconductor material of the photodetector comprises a two-dimensional germanium nanosheet, the two-dimensional germanium nanosheet has a narrow band gap, a wide response spectrum, and good stability. Excellent photodetection performance, the photodetector containing the two-dimensional germanium nanosheet has good stability and long service life.
  • a second aspect of the present invention provides a method of fabricating a photodetector, comprising the steps of:
  • a counter electrode is provided, an electrolyte is injected between the working electrode and the counter electrode, and a photodetector is obtained after being packaged.
  • the method for liquid phase stripping specifically comprises the following operations:
  • the bismuth raw material is added to the stripping solvent, and the probe is ultrasonicated for 8-15 hours in an ice bath environment; after the probe is ultrasonicated, the water bath ultrasonication is continued, and the ultrasonic bath time is 3-10 h, the temperature of the water bath Maintain 5-15 ° C; after sonication, centrifuge and dry to obtain two-dimensional tantalum nanosheets.
  • the specific preparation method of the working electrode includes:
  • the two-dimensional tantalum nanosheet dispersion is uniformly coated on the conductive substrate to form a semiconductor layer, and dried to obtain the working electrode.
  • the method for preparing a photodetector provided by the second aspect of the invention is simple and easy to operate, and the obtained photodetector has good photoelectric detection performance.
  • the photodetector provided by the present invention wherein the semiconductor material of the photodetector comprises a two-dimensional germanium nanosheet, the two-dimensional germanium nanosheet has a narrow band gap, a wide response spectrum, and good stability, and is excellent. Photodetection performance, the photodetector containing the two-dimensional germanium nanosheet has good stability and long service life;
  • the method for preparing the photodetector provided by the invention is simple and easy to operate, and the obtained photodetector has good photoelectric detection performance.
  • FIG. 1 is a schematic structural view of a photodetector according to an embodiment of the present invention.
  • Example 2 is a transmission electron micrograph of a two-dimensional tantalum nanosheet prepared in Example 1;
  • Example 3 is an atomic force micrograph of a two-dimensional tantalum nanosheet prepared in Example 1;
  • Example 4 is an absorption spectrum diagram of a liquid phase stripping process of a two-dimensional tantalum nanosheet in Example 1;
  • Figure 6 shows the photodetector produced in Example 4 at different light intensities (dark, I, II, III, IV, and VI) and different applied voltages (0, 0.1, 0.2, 0.3, 0.4, 0.5, and 0.6 V). signal of.
  • two-dimensional tantalum nanosheet or " ⁇ " referred to in the present invention, unless otherwise specified, refers to elemental germanium.
  • FIG. 1 is a schematic structural diagram of a photodetector according to an embodiment of the present invention.
  • the embodiment of the present invention provides a photodetector 10 including a working electrode 1, a counter electrode 2, and a working electrode. 1 and an electrolyte 3 between the counter electrode 2, the working electrode 1 comprising a conductive substrate 11 and a semiconductor layer 12 disposed on the conductive substrate 11, the material of the semiconductor layer 12 comprising two-dimensional germanium nanosheets .
  • the two-dimensional tantalum nanosheet has a thickness of 1-50 nm.
  • the two-dimensional tantalum nanosheet has a thickness of 1-5 nm.
  • the two-dimensional tantalum nanosheet has a thickness of 5-10 nm.
  • the two-dimensional tantalum nanosheet has a thickness of 10-50 nm.
  • the two-dimensional tantalum nanosheet has a thickness of 1 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm or 50 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 10 to 200 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 10-50 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 50-100 nm.
  • the two-dimensional germanium nanosheet has a length to width dimension of 100-200 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 30-40 nm.
  • the two-dimensional tantalum nanosheet has a length to width dimension of 10-30 nm.
  • the two-dimensional ⁇ nanosheet has a length and width dimension of 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm. , 180 nm, 190 nm or 200 nm.
  • the semiconductor layer further includes a polymer material, and the polymer material and the two-dimensional germanium nanosheet are uniformly distributed in the semiconductor layer.
  • the polymer material comprises at least one of polyvinylidene fluoride and cellulose. The polymer material facilitates adhesion of the two-dimensional tantalum nanosheet to the conductive substrate.
  • the mass ratio of the polymer material to the two-dimensional tantalum nanosheet is 1:10-1:100. Further optionally, the mass ratio of the polymer material to the two-dimensional tantalum nanosheet is 1:10 to 1:50. Further optionally, the mass ratio of the polymer material to the two-dimensional cerium nanosheet is 1:50-1:100. Further, the mass ratio of the polymer material to the two-dimensional cerium nanosheet is 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90 or 1:100.
  • the two-dimensional germanium nanosheet has a light response wavelength range of 500 nm or less.
  • the semiconductor layer is formed by uniformly coating a dispersion containing a two-dimensional germanium nanosheet on a conductive substrate.
  • the thickness of the semiconductor layer may be specifically selected according to actual needs, such as nanometer scale, and specifically may be 100 nm to 500 nm.
  • the conductive substrate comprises ITO transparent conductive glass (indium tin oxide transparent conductive glass) or FTO transparent conductive glass (fluorine-doped SnO 2 transparent conductive glass).
  • the conductive substrate has a sheet resistance of about 10 ⁇ .
  • the counter electrode comprises a platinum electrode or a carbon electrode.
  • the counter electrode is an electrode obtained by disposing platinum particles on the conductive substrate or the counter electrode is a platinum plate.
  • the photodetector further comprises a reference electrode, the reference electrode serving as a reference, the potential of which is fixed and known.
  • the reference electrode described herein can be selected from conventional reference electrodes.
  • a power source is connected between the working electrode and the counter electrode.
  • the electrolyte 3 is filled in a sealed space between the working electrode 1 and the counter electrode 2.
  • the electrolyte 3 comprises an alkaline electrolyte or a neutral electrolyte, the alkaline electrolyte comprising an alkali solution, the neutral electrolyte comprising a neutral salt solution.
  • the lye comprises at least one of a potassium hydroxide solution and a sodium hydroxide solution; the salt solution includes at least at least a sodium sulfate solution, a potassium sulfate solution, a sodium chloride solution, and a potassium chloride solution; One.
  • the concentration of the electrolyte is 0.1-10 mol/L, that is, the electrolyte concentration in the electrolyte is 0.1-10 mol/L. Further optionally, the concentration of the electrolyte is from 0.1 mol/L to 1 mol/L.
  • the photodetector further includes an encapsulation material that encapsulates the working electrode, the counter electrode, and the electrolyte.
  • the encapsulation material 4 is as shown in FIG.
  • the encapsulating material 4 comprises a fiberglass membrane.
  • the assembly of the working electrode, the counter electrode, and the electrolyte may be set according to actual conditions.
  • the semiconductor material of the photodetector comprises a two-dimensional germanium nanosheet, the two-dimensional germanium nanosheet has a narrow band gap, and thus can respond to a range from ultraviolet light to visible light. Secondly, it has better time stability and stability of the light probe cycle. Two-dimensional bismuth nanosheets can achieve better photometric stability within 2 weeks. In the 10h photodetection cycle test, the light probe signal showed only a slight attenuation.
  • the photodetector provided by the present invention is a photoelectrochemical (PEC) type photodetector, and the photoelectrochemical detector can protect the two-dimensional material in the electrolyte to prevent oxidation in the air. Therefore, stability and service life can be improved. Therefore, the photodetector provided by the invention has a wide response spectrum range, good stability, long service life and good performance.
  • a second aspect of the present invention provides a method of fabricating a photodetector, comprising the steps of:
  • the crucible raw material is a two-dimensional non-layered metal crucible, and may be a crucible powder or a crucible, and the size and shape thereof are not particularly limited. For example, it can be a micron or millimeter block.
  • the bismuth raw material can be obtained by purchase.
  • the band gap of the tantalum raw material is about 0.3 eV, and the band gap of the two-dimensional tantalum nanosheet obtained after peeling is also narrow, and can be used for detecting light with a long wavelength.
  • the method for liquid phase stripping specifically includes the following operations:
  • the bismuth raw material is added to the stripping solvent, and the probe is ultrasonicated for 8-15 hours in an ice bath environment; after the probe is ultrasonicated, the water bath ultrasonication is continued, and the ultrasonic bath time is 3-10 h, the temperature of the water bath Maintain 5-15 ° C; after sonication, centrifuge and dry to obtain two-dimensional tantalum nanosheets.
  • the stripping solvent comprises at least one of isopropanol, ethanol, acetone, water, and methylpyrrolidone (ie, N-methylpyrrolidone, NMP).
  • the concentration of the rhodium material in the solvent is from 1 to 7 mg/mL.
  • the probe has an ultrasonic power of 200-250W. Further optionally, the ultrasonic power of the probe is 240W.
  • the probe is sonicated for 10 hours.
  • the probe ultrasound is non-continuous ultrasound
  • the ultrasonic on/off time is selected to be 2/4 s, that is, ultrasonic for 2 s, then the ultrasonic probe is turned off for 4 s, the ultrasound is continued for 2 s, and so on.
  • the water bath has an ultrasonic power of 300-380 W. Further optionally, the water bath has an ultrasonic power of 360W.
  • the time of the water bath ultrasound is 8 h.
  • the water bath temperature is maintained at 10 °C.
  • the centrifuging operation comprises: firstly using a centrifugal force of 0.5-6 kg, centrifuging for 20-35 min, taking the supernatant; then, the supernatant is continuously centrifuged with a centrifugal force of 10-15 kg. At 25-35 min, a precipitate is obtained as a two-dimensional tantalum nanosheet.
  • the supernatant is taken; then the supernatant is centrifuged for 30 min with a centrifugal force of 12 kg to obtain a precipitate, and the obtained precipitate is dried to obtain a two-dimensional tantalum nanosheet.
  • the manner of drying is not limited, and may be, for example, vacuum drying.
  • the prior art generally employs a liquid phase lift-off method for stripping a two-dimensional layered material.
  • the present invention firstly uses a liquid phase stripping method to strip a two-dimensional non-layered elemental germanium material to obtain a two-dimensional tantalum nanosheet, and is successful, and the preparation method is simple and easy to operate.
  • step S02 the specific preparation method of the working electrode includes:
  • the two-dimensional cerium nanosheet dispersion is uniformly coated on the conductive substrate to form a semiconductor layer, and the working electrode is obtained after drying.
  • the polymer material is mixed with a two-dimensional tantalum nanosheet and uniformly coated on the conductive substrate, and the polymer material can improve the adhesion of the two-dimensional tantalum nanosheet on the conductive substrate. It helps the two-dimensional tantalum nanosheet to adhere closely to the conductive substrate.
  • the organic solvent comprises at least one of methylpyrrolidone and an alcohol solvent.
  • the alcohol solvent comprises at least one of methanol, ethanol, benzyl alcohol, and ethylene glycol.
  • the two-dimensional tantalum nanosheet dispersion is uniformly coated over the entire conductive substrate to form a semiconductor layer.
  • the concentration of the two-dimensional tantalum nanosheet in the two-dimensional tantalum nanosheet dispersion is greater than 1 mg/mL to ensure that the entire conductive substrate can be covered.
  • agitation may be carried out during the dispersion.
  • the polymer material comprises at least one of polyvinylidene fluoride and cellulose.
  • the cellulose has a molecular weight of from 50,000 to 250,000. The molecular weight can be specifically selected according to actual conditions.
  • the mass ratio of the polymer material to the two-dimensional tantalum nanosheet is 1:10-1:100. Further optionally, the mass ratio of the polymer material to the two-dimensional tantalum nanosheet is 1:10 to 1:50. Further optionally, the mass ratio of the polymer material to the two-dimensional cerium nanosheet is 1:50-1:100. Further, the mass ratio of the polymer material to the two-dimensional cerium nanosheet is 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90 or 1:100.
  • the working electrode, the counter electrode, and the electrolyte solution are encapsulated by a packaging material.
  • the encapsulating material comprises a fiberglass membrane.
  • the method for preparing a photodetector provided by the second aspect of the invention is simple and easy to operate, and the obtained photodetector has good photoelectric detection performance.
  • a method for preparing a two-dimensional tantalum nanosheet comprises the following steps:
  • the required two-dimensional bismuth nanosheets are obtained by centrifugation. First, the centrifugal force of 2000g was used and centrifuged for 30 minutes. The supernatant was taken, and then the supernatant was centrifuged for 30 min at 12000 g to obtain a precipitate, which was vacuum dried to obtain a two-dimensional tantalum nanosheet.
  • FIG. 2 it is an electron microscopic topography of a two-dimensional metal elemental tantalum nanosheet. Its size is less than 100 nm.
  • Figure 3 shows an atomic force micrograph. As can be seen from the figure, the thickness of the two-dimensional tantalum nanosheet is about 4 nm. Therefore, by observation by transmission electron microscopy and atomic force microscopy, two-dimensional elemental germanium nanosheets can be peeled off by liquid phase stripping.
  • Figure 5a is an absorption spectrum of two-dimensional tantalum nanosheets of different sizes under different centrifugal forces (rotational speeds).
  • Figure 5b shows different bandgap plots for tantalum nanosheets at different speeds.
  • the dimensions of the two-dimensional tantalum nanosheets corresponding to the first centrifugal speed of 0.5-1 kg, 1-3 kg and 3-6 kg are about 200 nm, about 100 nm and about 50 nm, respectively.
  • the absorption spectrum was measured using an ultraviolet-spectrophotometer. Different sizes of cerium nanosheet dispersions were placed in a quartz cuvette and placed in an ultraviolet spectrophotometer card slot to measure absorbance.
  • band gaps of the yttrium nanosheets corresponding to the rotational speeds of 0.5-1 kg, 1-3 kg and 3-6 kg were 1.63 eV, 1.72 eV and 1.90 eV, respectively.
  • Larger size two-dimensional germanium nanosheets have smaller band gaps and can achieve longer wavelength response. Smaller size two-dimensional germanium nanosheets can achieve higher photodetection signals due to their larger surface area.
  • a method for preparing a two-dimensional tantalum nanosheet comprises the following steps:
  • the required two-dimensional bismuth nanosheets are obtained by centrifugation. First, centrifugal force of 1800 g was used and centrifuged for 35 min. The supernatant was taken, and then the supernatant was centrifuged at 15000 g for 25 min to obtain a precipitate, which was vacuum dried to obtain a two-dimensional tantalum nanosheet.
  • a method for preparing a two-dimensional tantalum nanosheet comprises the following steps:
  • (1) 500 mg of a mash block was added to 100 ml of isopropyl alcohol. Then select the probe ultrasound 250W, ultrasound for 8h. The ultrasound on/off time was chosen to be 2/4 s and ultrasound was performed in an ice bath environment. After the probe is ultrasonicated, it is then ultrasonically probed in a water bath. The water bath ultrasonic power is 380W. The ultrasound time was 3 h. The bath temperature is maintained at 5 ° C;
  • the required two-dimensional bismuth nanosheets are obtained by centrifugation.
  • the centrifugal force of 2200 g was used and centrifuged for 20 min. The supernatant was taken, and then the supernatant was centrifuged for 35 min using 10000 g to obtain a precipitate, which was vacuum dried to obtain a two-dimensional tantalum nanosheet.
  • a method of preparing a photodetector includes the following steps:
  • Two-dimensional ⁇ nanosheets at a certain speed such as two-dimensional ⁇ nanosheets with a centrifugal force of 1-3kg at the first centrifugation.
  • the two-dimensional tantalum nanosheet prepared in Example 1 is used;
  • the polyvinylidene fluoride is taken, the polyvinylidene fluoride is dissolved in the methylpyrrolidone, and then the two-dimensional tantalum nanosheet prepared in the first embodiment is added to form a two-dimensional tantalum nanosheet dispersion, and the two-dimensional tantalum nanosheet dispersion is two-dimensionally
  • concentration of the nanosheet is 5 mg/mL, and the mass ratio of the polyvinylidene fluoride to the two-dimensional tantalum nanosheet is 1:10;
  • the two-dimensional cerium nanosheet dispersion is uniformly coated on the ITO glass, and dried to obtain a working electrode;
  • a platinum electrode is provided, and an electrolyte is injected between the working electrode and the platinum electrode, and the electrolyte is a 1 mol/L KOH solution, and a photodetector is obtained after being packaged.
  • the photodetector prepared in Example 4 was subjected to signals of different light intensities (dark, I, II, III, IV, and VI) and different applied voltages (0, 0.1, 0.2, 0.3, 0.4, 0.5, and 0.6 V). .
  • the light intensities of I, II, III, IV and VI of the white light source correspond to 26.2, 53.0, 83.1, 118.0, and 122.0 mW/cm 2 , respectively .
  • the test results are shown in Figure 6. As shown in FIG. 6, as the applied voltage increases, the light intensity increases, and the photoelectric signal also increases. In addition, it can be seen that in the photoelectric detection of up to 600 s, the photoelectric signal is not attenuated, indicating that the two-dimensional ⁇ nanosheet and the photodetector have good stability.
  • a method of preparing a photodetector includes the following steps:
  • the two-dimensional cerium nanosheet dispersion is uniformly coated on the ITO glass, and dried to obtain a working electrode;
  • a platinum electrode is provided, and an electrolyte is injected between the working electrode and the platinum electrode, and the electrolyte is a 10 mol/L sodium chloride solution, and a photodetector is obtained after being packaged.
  • a method of preparing a photodetector includes the following steps:
  • Polyvinylidene fluoride was taken, polyvinylidene fluoride was dissolved in methylpyrrolidone, and then two-dimensional cerium nanosheets prepared in Example 3 were added to form a two-dimensional cerium nanosheet dispersion, two-dimensional bismuth nanosheet dispersion in two-dimensional
  • concentration of the nanosheet is 8 mg/mL
  • mass ratio of the polyvinylidene fluoride to the two-dimensional tantalum nanosheet is 1:50;
  • the two-dimensional cerium nanosheet dispersion is uniformly coated on the ITO glass, and dried to obtain a working electrode;
  • a platinum electrode is provided, and an electrolyte is injected between the working electrode and the platinum electrode, and the electrolyte is a 5 mol/L potassium sulfate solution, and a photodetector is obtained after being packaged.

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Abstract

Provided in the present invention is an optical detector, comprising a working electrode, a counter electrode, and an electrolytic solution provided between the working electrode and the counter electrode, the working electrode comprising a conductive substrate and a semiconductor layer provided on the conductive substrate, and the material of the semiconductor layer comprising two-dimensional tellurium nanosheets. The optical detector provided in the present invention has good performance. Further provided in the present invention is a manufacturing method for an optical detector, comprising the following steps: providing a tellurium raw material, and exfoliating the tellurium raw material with a liquid phase exfoliation method to obtain two-dimensional tellurium nanosheets; dispersing the two-dimensional tellurium nanosheets into a solvent to form a two-dimensional tellurium nanosheet dispersion, uniformly coating the two-dimensional tellurium nanosheet dispersion onto a conductive substrate, and obtaining a working electrode after drying; and providing a counter electrode, filling an electrolytic solution between the working electrode and the counter electrode, and obtaining an optical detector after encapsulation. The manufacturing method provided in the present invention is simple and easy to operate.

Description

光探测器及其制备方法Photodetector and preparation method thereof
本发明要求于2018年02月09日递交的申请号为201810135379.5，发明名称为“光探测器及其制备方法”的在先申请的优先权，上述在先申请的内容以引入的方式并入本文本中。The present invention claims the priority of the prior application filed on February 9, 2018, the number of which is incorporated herein by reference. This.
技术领域Technical field
本发明涉及光电领域，具体涉及一种光探测器及其制备方法。The invention relates to the field of optoelectronics, in particular to a photodetector and a preparation method thereof.
背景技术Background technique
光探测器是利用具有光电效应的材料制成的能够实现光电转换的传感器，其作用是实现光电变换。其机理是由射入探测器的导波光束引起电子从价带到导带的受激跃迁，产生光生载流子(电子和空穴)。并由PN结或肖特基势垒将这些载流子收集起来，最终表现为光电压或光电流。The photodetector is a sensor that can realize photoelectric conversion by using a material having a photoelectric effect, and its function is to realize photoelectric conversion. The mechanism is that the guided beam incident on the detector causes an excited transition of the electron from the valence band to the conduction band, producing photogenerated carriers (electrons and holes). These carriers are collected by a PN junction or a Schottky barrier and ultimately appear as a photovoltage or photocurrent.
目前，基于二维纳米材料如黑磷的光探测器被认为是当前商用光探测器的有效替代产品。但是这种光探测器具有以下缺点：(1)基于宽带隙半导体的光探测器由于带隙较大导致探测波长过短；(2)现有的二维纳米材料稳定性较差，导致光探测器的使用性能较差；(3)固体模块的光探测器暴露在空气中，具有容易被氧化的缺点。Currently, photodetectors based on two-dimensional nanomaterials such as black phosphorus are considered to be an effective alternative to current commercial photodetectors. However, such a photodetector has the following disadvantages: (1) The photodetector based on the wide bandgap semiconductor has a short detection band due to a large band gap; (2) the existing two-dimensional nanomaterial has poor stability, resulting in light detection. The performance of the device is poor; (3) The photodetector of the solid module is exposed to the air and has the disadvantage of being easily oxidized.
鉴于传统的光探测器的缺陷，本发明提出了一种全新的基于光电化学型光探测器。In view of the drawbacks of conventional photodetectors, the present invention proposes a novel photoelectrochemical based photodetector.
发明内容Summary of the invention
为解决上述问题，本发明提供了一种光探测器，所述光探测器包括一种新型的二维功能材料-二维碲纳米片，所述二维碲纳米片环境稳定性较好，同时具有良好的光电探测功能。In order to solve the above problems, the present invention provides a photodetector comprising a novel two-dimensional functional material-two-dimensional germanium nanosheet, the two-dimensional germanium nanosheet having good environmental stability and simultaneous Has a good photodetection function.
本发明第一方面提供了一种光探测器，包括工作电极、对电极以及设于所述工作电极和所述对电极之间的电解液，所述工作电极包括导电基底和设置在所述导电基底上的半导体层，所述半导体层的材料包括二维碲纳米片。A first aspect of the present invention provides a photodetector including a working electrode, a counter electrode, and an electrolyte disposed between the working electrode and the counter electrode, the working electrode including a conductive substrate and disposed on the conductive A semiconductor layer on the substrate, the material of the semiconductor layer comprising a two-dimensional germanium nanosheet.
其中，所述二维碲纳米片的厚度为1-50nm。Wherein, the two-dimensional tantalum nanosheet has a thickness of 1-50 nm.
其中，所述二维碲纳米片的厚度为1-5nm。Wherein, the two-dimensional tantalum nanosheet has a thickness of 1-5 nm.
所述二维碲纳米片的厚度为5-10nm。The two-dimensional tantalum nanosheet has a thickness of 5-10 nm.
其中，所述二维碲纳米片的长宽尺寸为10-200nm。Wherein, the two-dimensional tantalum nanosheet has a length to width dimension of 10-200 nm.
其中，所述二维碲纳米片的长宽尺寸为10-50nm。Wherein, the two-dimensional tantalum nanosheet has a length to width dimension of 10-50 nm.
其中，所述二维碲纳米片的长宽尺寸为50-100nm。Wherein, the two-dimensional tantalum nanosheet has a length to width dimension of 50-100 nm.
其中，所述二维碲纳米片的长宽尺寸为100-200nm。Wherein, the two-dimensional tantalum nanosheet has a length to width dimension of 100-200 nm.
其中，所述半导体层还包括高分子材料，所述高分子材料与所述二维碲纳米片均匀分布在所述半导体层中。The semiconductor layer further includes a polymer material, and the polymer material and the two-dimensional germanium nanosheet are uniformly distributed in the semiconductor layer.
其中，所述高分子材料包括聚偏氟乙烯和纤维素中的至少一种。Wherein, the polymer material comprises at least one of polyvinylidene fluoride and cellulose.
其中，所述高分子材料与所述二维碲纳米片的质量比为1∶10-1∶100。Wherein, the mass ratio of the polymer material to the two-dimensional cerium nanosheet is 1:10-1:100.
其中，所述高分子材料与所述二维碲纳米片的质量比为1∶10-1∶50。The mass ratio of the polymer material to the two-dimensional cerium nanosheet is 1:10 to 1:50.
其中，所述电解液包括碱性电解液或中性电解液，所述碱性电解液包括碱液，所述中性电解液包括中性盐溶液。Wherein, the electrolyte comprises an alkaline electrolyte or a neutral electrolyte, the alkaline electrolyte comprises an alkali solution, and the neutral electrolyte comprises a neutral salt solution.
其中，所述碱液包括氢氧化钾溶液和氢氧化钠溶液中的至少一种；所述盐溶液包括硫酸钠溶液、硫酸钾溶液、氯化钠溶液和氯化钾溶液中的至少一种。Wherein the alkali solution comprises at least one of a potassium hydroxide solution and a sodium hydroxide solution; the salt solution includes at least one of a sodium sulfate solution, a potassium sulfate solution, a sodium chloride solution, and a potassium chloride solution.
其中，所述电解液的浓度为0.1mol/L-10mol/L。Wherein, the concentration of the electrolyte is from 0.1 mol/L to 10 mol/L.
其中，所述电解液的浓度为0.1mol/L-1mol/L。Wherein the concentration of the electrolyte is from 0.1 mol/L to 1 mol/L.
其中，所述半导体层的厚度为100nm-500nm。Wherein, the semiconductor layer has a thickness of 100 nm to 500 nm.
本发明第一方面提供的光探测器，所述光探测器的半导体材料包括二维碲纳米片，所述二维碲纳米片带隙较窄，响应光谱较宽，同时稳定性较好，具有优良的光电探测性能，含有所述二维碲纳米片的光探测器稳定性较好，使用寿命较长。In the photodetector provided by the first aspect of the present invention, the semiconductor material of the photodetector comprises a two-dimensional germanium nanosheet, the two-dimensional germanium nanosheet has a narrow band gap, a wide response spectrum, and good stability. Excellent photodetection performance, the photodetector containing the two-dimensional germanium nanosheet has good stability and long service life.
本发明第二方面提供了一种光探测器的制备方法，包括以下步骤：A second aspect of the present invention provides a method of fabricating a photodetector, comprising the steps of:
提供碲原料，采用液相剥离的方法对所述碲原料进行剥离，得到二维碲纳米片；Providing a bismuth raw material, and stripping the bismuth raw material by a liquid phase stripping method to obtain a two-dimensional bismuth nanosheet;
将所述二维碲纳米片分散在有机溶剂中形成二维碲纳米片分散液，将所述二维碲纳米片分散液均匀涂布在导电基底上，干燥后得到工作电极；Dispersing the two-dimensional cerium nanosheet in an organic solvent to form a two-dimensional cerium nanosheet dispersion, uniformly coating the two-dimensional cerium nanosheet dispersion on a conductive substrate, and drying to obtain a working electrode;
提供对电极，在所述工作电极和所述对电极之间注入电解液，经封装后得到光探测器。A counter electrode is provided, an electrolyte is injected between the working electrode and the counter electrode, and a photodetector is obtained after being packaged.
其中，所述液相剥离的方法具体包括以下操作：Wherein, the method for liquid phase stripping specifically comprises the following operations:
将所述碲原料加入至剥离溶剂中，在冰浴环境下采用探头超声8-15h；所述探头超声结束后，继续采用水浴超声，所述水浴超声时间为3-10h，所述水浴的温度保持5-15℃；超声后，进行离心和干燥得到二维碲纳米片。The bismuth raw material is added to the stripping solvent, and the probe is ultrasonicated for 8-15 hours in an ice bath environment; after the probe is ultrasonicated, the water bath ultrasonication is continued, and the ultrasonic bath time is 3-10 h, the temperature of the water bath Maintain 5-15 ° C; after sonication, centrifuge and dry to obtain two-dimensional tantalum nanosheets.
其中，所述工作电极的具体制备方法包括：The specific preparation method of the working electrode includes:
提供高分子材料，将所述高分子材料溶解在有机溶剂中，然后将所述二维碲纳米片分散在含有所述高分子材料的所述有机溶剂中，形成二维碲纳米片分散液，将所述二维碲纳米片分散液均匀涂布在所述导电基底上形成半导体层， 干燥后得到所述工作电极。Providing a polymer material, dissolving the polymer material in an organic solvent, and then dispersing the two-dimensional tantalum nanosheet in the organic solvent containing the polymer material to form a two-dimensional tantalum nanosheet dispersion. The two-dimensional tantalum nanosheet dispersion is uniformly coated on the conductive substrate to form a semiconductor layer, and dried to obtain the working electrode.
本发明第二方面提供的光探测器的制备方法，方法简单易操作，制得的光探测器具有良好光电探测性能。The method for preparing a photodetector provided by the second aspect of the invention is simple and easy to operate, and the obtained photodetector has good photoelectric detection performance.
综上，本发明有益效果包括以下几个方面：In summary, the beneficial effects of the present invention include the following aspects:
1、本发明提供的光探测器，所述光探测器的半导体材料包括二维碲纳米片，所述二维碲纳米片带隙较窄，响应光谱较宽，同时稳定性较好，具有优良的光电探测性能，含有所述二维碲纳米片的光探测器稳定性较好，使用寿命较长；1. The photodetector provided by the present invention, wherein the semiconductor material of the photodetector comprises a two-dimensional germanium nanosheet, the two-dimensional germanium nanosheet has a narrow band gap, a wide response spectrum, and good stability, and is excellent. Photodetection performance, the photodetector containing the two-dimensional germanium nanosheet has good stability and long service life;
2、本发明提供的光探测器的制备方法，方法简单易操作，制得的光探测器具有良好光电探测性能。2. The method for preparing the photodetector provided by the invention is simple and easy to operate, and the obtained photodetector has good photoelectric detection performance.
附图说明DRAWINGS
图1为本发明一实施方式提供的光探测器的结构示意图；1 is a schematic structural view of a photodetector according to an embodiment of the present invention;
图2为实施例1制得的二维碲纳米片的透射电镜图片；2 is a transmission electron micrograph of a two-dimensional tantalum nanosheet prepared in Example 1;
图3为实施例1制得的二维碲纳米片的原子力显微图片；3 is an atomic force micrograph of a two-dimensional tantalum nanosheet prepared in Example 1;
图4为实施例1中二维碲纳米片的液相剥离过程的吸收光谱图；4 is an absorption spectrum diagram of a liquid phase stripping process of a two-dimensional tantalum nanosheet in Example 1;
图5为不同尺寸的二维碲纳米片水分散液的吸收光谱图和带隙图；5 is an absorption spectrum diagram and a band gap diagram of two-dimensional bismuth nanosheet aqueous dispersions of different sizes;
图6为实施例4制得的光探测器在不同光强(黑暗，I，II，III，IV以及VI)以及不同施加电压下(0，0.1，0.2，0.3，0.4，0.5以及0.6V)的信号。Figure 6 shows the photodetector produced in Example 4 at different light intensities (dark, I, II, III, IV, and VI) and different applied voltages (0, 0.1, 0.2, 0.3, 0.4, 0.5, and 0.6 V). signal of.
具体实施方式Detailed ways
以下所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明的保护范围。The following is a preferred embodiment of the present invention, and it should be noted that those skilled in the art can also make several improvements and retouchings without departing from the principles of the present invention. It is the scope of protection of the present invention.
本发明提到的“二维碲纳米片”或“碲”，除特殊说明，均指的是单质碲。The "two-dimensional tantalum nanosheet" or "碲" referred to in the present invention, unless otherwise specified, refers to elemental germanium.
请参照图1，图1为本发明一实施方式提供的光探测器的结构示意图；本发明实施方式提供了一种光探测器10，包括工作电极1、对电极2以及设于所述工作电极1和所述对电极2之间的电解液3，所述工作电极1包括导电基底11和设置在所述导电基底11上的半导体层12，所述半导体层12的材料包括二维碲纳米片。1 is a schematic structural diagram of a photodetector according to an embodiment of the present invention. The embodiment of the present invention provides a photodetector 10 including a working electrode 1, a counter electrode 2, and a working electrode. 1 and an electrolyte 3 between the counter electrode 2, the working electrode 1 comprising a conductive substrate 11 and a semiconductor layer 12 disposed on the conductive substrate 11, the material of the semiconductor layer 12 comprising two-dimensional germanium nanosheets .
本发明实施方式中，所述二维碲纳米片的厚度为1-50nm。可选地，所述二维碲纳米片的厚度为1-5nm。可选地，所述二维碲纳米片的厚度为5-10nm。可选地，所述二维碲纳米片的厚度为10-50nm。进一步可选地，所述二维碲纳米片的厚度为1nm、5nm、10nm、15nm、20nm、25nm、30nm、35nm、40nm、45nm或50nm。In an embodiment of the invention, the two-dimensional tantalum nanosheet has a thickness of 1-50 nm. Optionally, the two-dimensional tantalum nanosheet has a thickness of 1-5 nm. Optionally, the two-dimensional tantalum nanosheet has a thickness of 5-10 nm. Optionally, the two-dimensional tantalum nanosheet has a thickness of 10-50 nm. Further optionally, the two-dimensional tantalum nanosheet has a thickness of 1 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm or 50 nm.
本发明实施方式中，所述二维碲纳米片的长宽尺寸为10-200nm。可选地，所述二维碲纳米片的长宽尺寸为10-50nm。可选地，所述二维碲纳米片的长宽尺寸为50-100nm。可选地，所述二维碲纳米片的长宽尺寸为100-200nm。进一步可选地，所述二维碲纳米片的长宽尺寸为30-40nm。进一步可选地，所述二维碲纳米片的长宽尺寸为10-30nm。进一步可选地，所述二维碲纳米片的长宽尺寸为10nm、20nm、30nm、40nm、50nm、60nm、70nm、80nm、90nm、100nm、110nm、120nm、130nm、140nm、150nm、160nm、170nm、180nm、190nm或200nm。In an embodiment of the invention, the two-dimensional tantalum nanosheet has a length to width dimension of 10 to 200 nm. Optionally, the two-dimensional tantalum nanosheet has a length to width dimension of 10-50 nm. Optionally, the two-dimensional tantalum nanosheet has a length to width dimension of 50-100 nm. Optionally, the two-dimensional germanium nanosheet has a length to width dimension of 100-200 nm. Further optionally, the two-dimensional tantalum nanosheet has a length to width dimension of 30-40 nm. Further optionally, the two-dimensional tantalum nanosheet has a length to width dimension of 10-30 nm. Further optionally, the two-dimensional 碲 nanosheet has a length and width dimension of 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm. , 180 nm, 190 nm or 200 nm.
本发明实施方式中，所述半导体层还包括高分子材料，所述高分子材料与所述二维碲纳米片均匀分布在所述半导体层中。可选地，所述高分子材料包括聚偏氟乙烯和纤维素中的至少一种。所述高分子材料有助于二维碲纳米片紧密粘附在所述导电基底上。In an embodiment of the invention, the semiconductor layer further includes a polymer material, and the polymer material and the two-dimensional germanium nanosheet are uniformly distributed in the semiconductor layer. Optionally, the polymer material comprises at least one of polyvinylidene fluoride and cellulose. The polymer material facilitates adhesion of the two-dimensional tantalum nanosheet to the conductive substrate.
可选地，所述高分子材料与所述二维碲纳米片的质量比为1∶10-1∶100。进一步可选地，所述高分子材料与所述二维碲纳米片的质量比为1∶10-1∶50。进一步可选地，所述高分子材料与所述二维碲纳米片的质量比为1∶50-1∶100。进一步可选地，所述高分子材料与所述二维碲纳米片的质量比为1∶10、1∶20、1∶30、1∶40、1∶50、1∶60、1∶70、1∶80、1∶90或1∶100。Optionally, the mass ratio of the polymer material to the two-dimensional tantalum nanosheet is 1:10-1:100. Further optionally, the mass ratio of the polymer material to the two-dimensional tantalum nanosheet is 1:10 to 1:50. Further optionally, the mass ratio of the polymer material to the two-dimensional cerium nanosheet is 1:50-1:100. Further, the mass ratio of the polymer material to the two-dimensional cerium nanosheet is 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90 or 1:100.
本发明实施方式中，所述二维碲纳米片的光响应波长范围为500nm以下。In an embodiment of the invention, the two-dimensional germanium nanosheet has a light response wavelength range of 500 nm or less.
本发明实施方式中，所述半导体层为将含有二维碲纳米片的分散液均匀涂布在导电基底形成的。所述半导体层的厚度可根据实际需要进行具体选择，如可为纳米级，如具体可为100nm-500nm。In an embodiment of the invention, the semiconductor layer is formed by uniformly coating a dispersion containing a two-dimensional germanium nanosheet on a conductive substrate. The thickness of the semiconductor layer may be specifically selected according to actual needs, such as nanometer scale, and specifically may be 100 nm to 500 nm.
本发明实施方式中，所述导电基底包括的ITO透明导电玻璃(铟锡氧化物透明导电玻璃)或FTO透明导电玻璃(掺杂氟的SnO 2透明导电玻璃)。可选地，所述导电基底的方块电阻为10Ω左右。 In an embodiment of the invention, the conductive substrate comprises ITO transparent conductive glass (indium tin oxide transparent conductive glass) or FTO transparent conductive glass (fluorine-doped SnO 2 transparent conductive glass). Optionally, the conductive substrate has a sheet resistance of about 10 Ω.
本发明实施方式中，所述对电极包括铂电极或碳电极。可选地，所述对电极为由在所述导电基底上设置铂颗粒得到的电极或者所述对电极为铂片。In an embodiment of the invention, the counter electrode comprises a platinum electrode or a carbon electrode. Optionally, the counter electrode is an electrode obtained by disposing platinum particles on the conductive substrate or the counter electrode is a platinum plate.
本发明实施方式中，所述光探测器还包括参比电极，所述参比电极起到参考的作用，其电势是固定且已知的。这里所述的参比电极可选择常规的参比电极。In an embodiment of the invention, the photodetector further comprises a reference electrode, the reference electrode serving as a reference, the potential of which is fixed and known. The reference electrode described herein can be selected from conventional reference electrodes.
本发明实施方式中，所述工作电极和所述对电极之间连接电源。In an embodiment of the invention, a power source is connected between the working electrode and the counter electrode.
本发明实施方式中，所述电解液3填充在工作电极1和对电极2之间的密封空间内。可选地，所述电解液3包括碱性电解液或中性电解液，所述碱性电解液包括碱液，所述中性电解液包括中性盐溶液。进一步可选地，所述碱液包括氢氧化钾溶液和氢氧化钠溶液中的至少一种；所述盐溶液包括硫酸钠溶液、硫酸钾溶液、氯化钠溶液和氯化钾溶液中的至少一种。可选地，所述电解液的浓度为0.1-10mol/L，即所述电解液中的电解质浓度为0.1-10mol/L。进一步可选地，所述电解液的浓度为0.1mol/L-1mol/L。In an embodiment of the invention, the electrolyte 3 is filled in a sealed space between the working electrode 1 and the counter electrode 2. Optionally, the electrolyte 3 comprises an alkaline electrolyte or a neutral electrolyte, the alkaline electrolyte comprising an alkali solution, the neutral electrolyte comprising a neutral salt solution. Further optionally, the lye comprises at least one of a potassium hydroxide solution and a sodium hydroxide solution; the salt solution includes at least at least a sodium sulfate solution, a potassium sulfate solution, a sodium chloride solution, and a potassium chloride solution; One. Optionally, the concentration of the electrolyte is 0.1-10 mol/L, that is, the electrolyte concentration in the electrolyte is 0.1-10 mol/L. Further optionally, the concentration of the electrolyte is from 0.1 mol/L to 1 mol/L.
本发明实施方式中，所述光探测器还包括将所述工作电极、对电极和电解液封装的封装材料。如图5中示出的封装材料4。可选地，所述封装材料4包括玻璃纤维膜。具体所述工作电极、对电极以及电解液的组装可根据实际情况进行设置。In an embodiment of the invention, the photodetector further includes an encapsulation material that encapsulates the working electrode, the counter electrode, and the electrolyte. The encapsulation material 4 is as shown in FIG. Optionally, the encapsulating material 4 comprises a fiberglass membrane. Specifically, the assembly of the working electrode, the counter electrode, and the electrolyte may be set according to actual conditions.
本发明第一方面提供的光探测器，所述光探测器的半导体材料包括二维碲纳米片，所述二维碲纳米片具有较窄的带隙，因此可以响应从紫外光到可见光的范围；其次具有较好的时间稳定性和光探循环稳定性。二维碲纳米片可以实现2周内较好的光探稳定性。在10h的光探循环测试中，光探信号只出现了轻微的衰减。此外，本发明提供的光探测器为光电化学(PEC)型的光探测器，光电化学探测器可以将二维材料保护在电解液中，以防暴露在空气中被氧化。因此可以提高稳定性和使用寿命。因此，本发明提供的光探测器响应光谱范围较宽，稳定性较好，使用寿命较长，性能较好。The photodetector provided by the first aspect of the invention, the semiconductor material of the photodetector comprises a two-dimensional germanium nanosheet, the two-dimensional germanium nanosheet has a narrow band gap, and thus can respond to a range from ultraviolet light to visible light. Secondly, it has better time stability and stability of the light probe cycle. Two-dimensional bismuth nanosheets can achieve better photometric stability within 2 weeks. In the 10h photodetection cycle test, the light probe signal showed only a slight attenuation. In addition, the photodetector provided by the present invention is a photoelectrochemical (PEC) type photodetector, and the photoelectrochemical detector can protect the two-dimensional material in the electrolyte to prevent oxidation in the air. Therefore, stability and service life can be improved. Therefore, the photodetector provided by the invention has a wide response spectrum range, good stability, long service life and good performance.
本发明第二方面提供了一种光探测器的制备方法，包括以下步骤：A second aspect of the present invention provides a method of fabricating a photodetector, comprising the steps of:
S01，提供碲原料，采用液相剥离的方法对所述碲原料进行剥离，得到二维碲纳米片；S01, providing a bismuth raw material, and stripping the bismuth raw material by a liquid phase stripping method to obtain a two-dimensional bismuth nanosheet;
S02，将所述二维碲纳米片分散在有机溶剂中形成二维碲纳米片分散液，将所述二维碲纳米片分散液均匀涂布在导电基底上，干燥后得到工作电极；S02, dispersing the two-dimensional tantalum nanosheet in an organic solvent to form a two-dimensional tantalum nanosheet dispersion, uniformly coating the two-dimensional tantalum nanosheet dispersion on a conductive substrate, and drying to obtain a working electrode;
S03，提供对电极，在所述工作电极和所述对电极之间注入电解液，经封装后得到光探测器。S03, providing a counter electrode, injecting an electrolyte between the working electrode and the counter electrode, and obtaining a photodetector after being packaged.
本发明实施方式中，步骤S01中，所述碲原料为二维非层状的金属碲单质，如可以为碲粉，也可以为碲块，对其大小和形状没有特殊限定。如可以为微米级或毫米级的块体。所述碲原料可通过购买得到。所述碲原料的带隙较窄为0.3eV左右，经剥离后得到的二维碲纳米片的带隙也较窄，可用于探测波长较长的光。In the embodiment of the present invention, in the step S01, the crucible raw material is a two-dimensional non-layered metal crucible, and may be a crucible powder or a crucible, and the size and shape thereof are not particularly limited. For example, it can be a micron or millimeter block. The bismuth raw material can be obtained by purchase. The band gap of the tantalum raw material is about 0.3 eV, and the band gap of the two-dimensional tantalum nanosheet obtained after peeling is also narrow, and can be used for detecting light with a long wavelength.
本发明实施方式中，所述液相剥离的方法具体包括以下操作：In the embodiment of the present invention, the method for liquid phase stripping specifically includes the following operations:
将所述碲原料加入至剥离溶剂中，在冰浴环境下采用探头超声8-15h；所述探头超声结束后，继续采用水浴超声，所述水浴超声时间为3-10h，所述水浴的温度保持5-15℃；超声后，进行离心和干燥得到二维碲纳米片。The bismuth raw material is added to the stripping solvent, and the probe is ultrasonicated for 8-15 hours in an ice bath environment; after the probe is ultrasonicated, the water bath ultrasonication is continued, and the ultrasonic bath time is 3-10 h, the temperature of the water bath Maintain 5-15 ° C; after sonication, centrifuge and dry to obtain two-dimensional tantalum nanosheets.
可选地，所述剥离溶剂包括异丙醇、乙醇、丙酮、水和甲基吡咯烷酮(即N-甲基吡咯烷酮，NMP)中的至少一种。Optionally, the stripping solvent comprises at least one of isopropanol, ethanol, acetone, water, and methylpyrrolidone (ie, N-methylpyrrolidone, NMP).
可选地，所述碲原料在所述溶剂中的浓度为1-7mg/mL。Optionally, the concentration of the rhodium material in the solvent is from 1 to 7 mg/mL.
可选地，所述探头超声的功率为200-250W。进一步可选地，所述探头超声的功率为240W。Optionally, the probe has an ultrasonic power of 200-250W. Further optionally, the ultrasonic power of the probe is 240W.
可选地，所述探头超声的时间为10h。Optionally, the probe is sonicated for 10 hours.
可选地，所述探头超声是非连续超声，选择超声开/关时间为2/4s，即先超声2s，然后关闭超声探头保持4s，再继续超声2s，以此类推。Optionally, the probe ultrasound is non-continuous ultrasound, and the ultrasonic on/off time is selected to be 2/4 s, that is, ultrasonic for 2 s, then the ultrasonic probe is turned off for 4 s, the ultrasound is continued for 2 s, and so on.
可选地，所述水浴超声功率为300-380W。进一步可选地，所述水浴超声 功率为360W。Optionally, the water bath has an ultrasonic power of 300-380 W. Further optionally, the water bath has an ultrasonic power of 360W.
可选地，所述水浴超声的时间为8h。Optionally, the time of the water bath ultrasound is 8 h.
可选地，所述水浴温度保持10℃。Optionally, the water bath temperature is maintained at 10 °C.
可选地，超声后，进行离心，所述离心的操作包括：首先采用0.5-6kg的离心力，离心20-35min，取上清液；然后将所述上清液采用10-15kg的离心力继续离心25-35min，得到沉淀即为二维碲纳米片。进一步可选地，首先采用2kg的离心力，离心30min，取上清液；然后将所述上清液采用12kg的离心力继续离心30min，得到沉淀，将所得沉淀干燥后即得二维碲纳米片。可选地，所述干燥的方式不限，例如可为真空干燥。Optionally, after the ultrasonication, performing centrifugation, the centrifuging operation comprises: firstly using a centrifugal force of 0.5-6 kg, centrifuging for 20-35 min, taking the supernatant; then, the supernatant is continuously centrifuged with a centrifugal force of 10-15 kg. At 25-35 min, a precipitate is obtained as a two-dimensional tantalum nanosheet. Further optionally, firstly, using a centrifugal force of 2 kg, centrifuging for 30 min, the supernatant is taken; then the supernatant is centrifuged for 30 min with a centrifugal force of 12 kg to obtain a precipitate, and the obtained precipitate is dried to obtain a two-dimensional tantalum nanosheet. Optionally, the manner of drying is not limited, and may be, for example, vacuum drying.
现有技术通常采用液相剥离法用来剥离二维层状材料。而本发明首次采用液相剥离法剥离二维非层状单质碲材料从而制得二维碲纳米片，并取得成功，制备方法简单易操作。The prior art generally employs a liquid phase lift-off method for stripping a two-dimensional layered material. However, the present invention firstly uses a liquid phase stripping method to strip a two-dimensional non-layered elemental germanium material to obtain a two-dimensional tantalum nanosheet, and is successful, and the preparation method is simple and easy to operate.
本发明实施方式中，步骤S02中，所述工作电极的具体制备方法包括：In the embodiment of the present invention, in step S02, the specific preparation method of the working electrode includes:
提供高分子材料，将所述高分子材料溶解在有机溶剂中，然后将所述二维碲纳米片分散在含有所述高分子材料的所述有机溶剂中，形成二维碲纳米片分散液，将所述二维碲纳米片分散液均匀涂布在所述导电基底上形成半导体层，干燥后得到所述工作电极。Providing a polymer material, dissolving the polymer material in an organic solvent, and then dispersing the two-dimensional tantalum nanosheet in the organic solvent containing the polymer material to form a two-dimensional tantalum nanosheet dispersion. The two-dimensional cerium nanosheet dispersion is uniformly coated on the conductive substrate to form a semiconductor layer, and the working electrode is obtained after drying.
本发明实施方式中，将所述高分子材料与二维碲纳米片混合并一起均匀地涂布在所述导电基底上，高分子材料可以提高二维碲纳米片在所述导电基底的粘附性，有助于二维碲纳米片紧密粘附在所述导电基底上。In the embodiment of the present invention, the polymer material is mixed with a two-dimensional tantalum nanosheet and uniformly coated on the conductive substrate, and the polymer material can improve the adhesion of the two-dimensional tantalum nanosheet on the conductive substrate. It helps the two-dimensional tantalum nanosheet to adhere closely to the conductive substrate.
可选地，所述有机溶剂包括甲基吡咯烷酮和醇类溶剂中的至少一种。可选地，所述醇类溶剂包括甲醇、乙醇、苯甲醇和乙二醇中的至少一种。Optionally, the organic solvent comprises at least one of methylpyrrolidone and an alcohol solvent. Optionally, the alcohol solvent comprises at least one of methanol, ethanol, benzyl alcohol, and ethylene glycol.
可选地，将所述二维碲纳米片分散液均匀地涂满整个导电基底形成半导体层。Optionally, the two-dimensional tantalum nanosheet dispersion is uniformly coated over the entire conductive substrate to form a semiconductor layer.
可选地，所述二维碲纳米片分散液中二维碲纳米片的浓度大于1mg/mL，以保证能够将整个导电基底覆盖住。Optionally, the concentration of the two-dimensional tantalum nanosheet in the two-dimensional tantalum nanosheet dispersion is greater than 1 mg/mL to ensure that the entire conductive substrate can be covered.
可选地，所述分散过程中可进行搅拌。Alternatively, agitation may be carried out during the dispersion.
可选地，所述高分子材料包括聚偏氟乙烯和纤维素中的至少一种。进一步可选地，所述纤维素的分子量为50000-2500000。所述分子量可根据实际情况进行具体选择。Optionally, the polymer material comprises at least one of polyvinylidene fluoride and cellulose. Further optionally, the cellulose has a molecular weight of from 50,000 to 250,000. The molecular weight can be specifically selected according to actual conditions.
可选地，所述高分子材料与所述二维碲纳米片的质量比为1∶10-1∶100。进一步可选地，所述高分子材料与所述二维碲纳米片的质量比为1∶10-1∶50。进一步可选地，所述高分子材料与所述二维碲纳米片的质量比为1∶50-1∶100。进一步可选地，所述高分子材料与所述二维碲纳米片的质量比为1∶10、1∶20、1∶30、1∶40、1∶50、1∶60、1∶70、1∶80、1∶90或1∶100。Optionally, the mass ratio of the polymer material to the two-dimensional tantalum nanosheet is 1:10-1:100. Further optionally, the mass ratio of the polymer material to the two-dimensional tantalum nanosheet is 1:10 to 1:50. Further optionally, the mass ratio of the polymer material to the two-dimensional cerium nanosheet is 1:50-1:100. Further, the mass ratio of the polymer material to the two-dimensional cerium nanosheet is 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90 or 1:100.
本发明实施方式中，步骤S03中，通过封装材料将所述工作电极、所述对电极和所述电解液封装。可选地，所述封装材料包括玻璃纤维膜。In an embodiment of the invention, in step S03, the working electrode, the counter electrode, and the electrolyte solution are encapsulated by a packaging material. Optionally, the encapsulating material comprises a fiberglass membrane.
本发明第二方面提供的光探测器的制备方法，方法简单易操作，制得的光探测器具有良好光电探测性能。The method for preparing a photodetector provided by the second aspect of the invention is simple and easy to operate, and the obtained photodetector has good photoelectric detection performance.
实施例1：Example 1:
一种二维碲纳米片的制备方法，包括以下步骤：A method for preparing a two-dimensional tantalum nanosheet comprises the following steps:
(1)将500mg的碲粉加入100ml的异丙醇中。然后选择探头超声240W，超声10h。选择超声开/关时间为2/4s，并且是在冰浴环境下进行超声。探头超 声完后，接着采用水浴超声。水浴超声功率为360W。超声时间为8h。水浴温度保持10℃；(1) 500 mg of cerium powder was added to 100 ml of isopropyl alcohol. Then select the probe ultrasound 240W, ultrasound for 10h. The ultrasound on/off time was chosen to be 2/4 s and ultrasound was performed in an ice bath environment. After the probe is over-sounded, it is then ultrasonically probed in a water bath. The water bath ultrasonic power is 360W. The ultrasound time was 8 h. The bath temperature is maintained at 10 ° C;
(2)超声过后采用离心的办法得到需要的二维碲纳米片。首先采用2000g的离心力，离心30min。取上清，然后将上清采用12000g继续离心30min，得到沉淀，真空干燥后即得二维碲纳米片。(2) After ultrasonication, the required two-dimensional bismuth nanosheets are obtained by centrifugation. First, the centrifugal force of 2000g was used and centrifuged for 30 minutes. The supernatant was taken, and then the supernatant was centrifuged for 30 min at 12000 g to obtain a precipitate, which was vacuum dried to obtain a two-dimensional tantalum nanosheet.
如图2所示，为二维金属单质碲纳米片的电镜形貌图。其尺寸小于100nm。图3显示的是原子力显微图片。由图可以看出，二维碲纳米片的厚度在4nm左右。因此通过透射电镜和原子力显微镜的观察，通过液相剥离法确实可以剥离出二维单质碲纳米片。As shown in Fig. 2, it is an electron microscopic topography of a two-dimensional metal elemental tantalum nanosheet. Its size is less than 100 nm. Figure 3 shows an atomic force micrograph. As can be seen from the figure, the thickness of the two-dimensional tantalum nanosheet is about 4 nm. Therefore, by observation by transmission electron microscopy and atomic force microscopy, two-dimensional elemental germanium nanosheets can be peeled off by liquid phase stripping.
如图4所示，分别为异丙醇(IPA)中、水中、甲基吡咯烷酮和丙酮中剥离的相同浓度的二维碲纳米片的吸收光谱。很明显，异丙醇中剥离的二维碲纳米片的吸收光谱具有更高的吸收值和更大的斜率。这说明异丙醇中可以充分将比较大的碲颗粒剥离成尺寸较小的二维碲纳米片。As shown in Fig. 4, the absorption spectra of the same concentration of two-dimensional cerium nanosheets exfoliated in isopropyl alcohol (IPA), water, methylpyrrolidone and acetone, respectively. It is apparent that the absorption spectrum of the two-dimensional tantalum nanosheet exfoliated in isopropanol has a higher absorption value and a larger slope. This indicates that the relatively large ruthenium particles can be sufficiently stripped into two-dimensional ruthenium nanosheets of smaller size in isopropyl alcohol.
图5a为不同离心力(转速)下，不同尺寸二维碲纳米片的吸收光谱图。图5b为不同转速下的碲纳米片的不同的带隙图。对应第一次离心转速0.5-1kg，1-3kg和3-6kg的二维碲纳米片的尺寸分别为200nm左右，100nm左右和50nm左右。吸收光谱采用紫外-分光光度计测量。将不同尺寸的碲纳米片分散液装入石英比色皿中，放入紫外分光光度计卡槽中测量吸收度。根据不同尺寸下的碲纳米片的吸收度，进而计算得到其不同的带隙，如图5b所示。由图可知，对应转速0.5-1kg，1-3kg和3-6kg的碲纳米片的带隙分别为1.63eV，1.72eV和1.90eV。较大尺寸的二维碲纳米片的带隙较小，可以获得更长波长的响应。较小尺寸的二维碲纳米片，由于其具有更大的表面积，可以获得更高的光电探测 信号。Figure 5a is an absorption spectrum of two-dimensional tantalum nanosheets of different sizes under different centrifugal forces (rotational speeds). Figure 5b shows different bandgap plots for tantalum nanosheets at different speeds. The dimensions of the two-dimensional tantalum nanosheets corresponding to the first centrifugal speed of 0.5-1 kg, 1-3 kg and 3-6 kg are about 200 nm, about 100 nm and about 50 nm, respectively. The absorption spectrum was measured using an ultraviolet-spectrophotometer. Different sizes of cerium nanosheet dispersions were placed in a quartz cuvette and placed in an ultraviolet spectrophotometer card slot to measure absorbance. According to the absorption of the yttrium nanosheets of different sizes, different band gaps are calculated, as shown in Fig. 5b. As can be seen from the figure, the band gaps of the yttrium nanosheets corresponding to the rotational speeds of 0.5-1 kg, 1-3 kg and 3-6 kg were 1.63 eV, 1.72 eV and 1.90 eV, respectively. Larger size two-dimensional germanium nanosheets have smaller band gaps and can achieve longer wavelength response. Smaller size two-dimensional germanium nanosheets can achieve higher photodetection signals due to their larger surface area.
实施例2：Example 2:
一种二维碲纳米片的制备方法，包括以下步骤：A method for preparing a two-dimensional tantalum nanosheet comprises the following steps:
(1)将500mg的碲粉加入100ml的异丙醇中。然后选择探头超声200W，超声15h。选择超声开/关时间为2/4s，并且是在冰浴环境下进行超声。探头超声完后，接着采用水浴超声。水浴超声功率为300W。超声时间为10h。水浴温度保持15℃；(1) 500 mg of cerium powder was added to 100 ml of isopropyl alcohol. Then select the probe ultrasound 200W, ultrasound for 15h. The ultrasound on/off time was chosen to be 2/4 s and ultrasound was performed in an ice bath environment. After the probe is ultrasonicated, it is then ultrasonically probed in a water bath. The water bath ultrasonic power is 300W. The ultrasound time was 10 h. The bath temperature is maintained at 15 ° C;
(2)超声过后采用离心的办法得到需要的二维碲纳米片。首先采用1800g的离心力，离心35min。取上清，然后将上清采用15000g继续离心25min，得到沉淀，真空干燥后即得二维碲纳米片。(2) After ultrasonication, the required two-dimensional bismuth nanosheets are obtained by centrifugation. First, centrifugal force of 1800 g was used and centrifuged for 35 min. The supernatant was taken, and then the supernatant was centrifuged at 15000 g for 25 min to obtain a precipitate, which was vacuum dried to obtain a two-dimensional tantalum nanosheet.
实施例3：Example 3:
一种二维碲纳米片的制备方法，包括以下步骤：A method for preparing a two-dimensional tantalum nanosheet comprises the following steps:
(1)将500mg的碲块体加入100ml的异丙醇中。然后选择探头超声250W，超声8h。选择超声开/关时间为2/4s，并且是在冰浴环境下进行超声。探头超声完后，接着采用水浴超声。水浴超声功率为380W。超声时间为3h。水浴温度保持5℃；(1) 500 mg of a mash block was added to 100 ml of isopropyl alcohol. Then select the probe ultrasound 250W, ultrasound for 8h. The ultrasound on/off time was chosen to be 2/4 s and ultrasound was performed in an ice bath environment. After the probe is ultrasonicated, it is then ultrasonically probed in a water bath. The water bath ultrasonic power is 380W. The ultrasound time was 3 h. The bath temperature is maintained at 5 ° C;
(2)超声过后采用离心的办法得到需要的二维碲纳米片。首先采用2200g的离心力，离心20min。取上清，然后将上清采用10000g继续离心35min，得到沉淀，真空干燥后即得二维碲纳米片。(2) After ultrasonication, the required two-dimensional bismuth nanosheets are obtained by centrifugation. First, the centrifugal force of 2200 g was used and centrifuged for 20 min. The supernatant was taken, and then the supernatant was centrifuged for 35 min using 10000 g to obtain a precipitate, which was vacuum dried to obtain a two-dimensional tantalum nanosheet.
实施例4Example 4
一种光探测器的制备方法，包括以下步骤：A method of preparing a photodetector includes the following steps:
取一定转速下的二维碲纳米片，比如第一次离心时离心力为1-3kg得到的二维碲纳米片。具体地，采用实施例1制得的二维碲纳米片；Take two-dimensional 碲 nanosheets at a certain speed, such as two-dimensional 碲 nanosheets with a centrifugal force of 1-3kg at the first centrifugation. Specifically, the two-dimensional tantalum nanosheet prepared in Example 1 is used;
取聚偏氟乙烯，将聚偏氟乙烯溶解在甲基吡咯烷酮中，然后加入实施例1制得的二维碲纳米片形成二维碲纳米片分散液，二维碲纳米片分散液中二维碲纳米片的浓度为5mg/mL，聚偏氟乙烯与二维碲纳米片的质量比为1∶10；The polyvinylidene fluoride is taken, the polyvinylidene fluoride is dissolved in the methylpyrrolidone, and then the two-dimensional tantalum nanosheet prepared in the first embodiment is added to form a two-dimensional tantalum nanosheet dispersion, and the two-dimensional tantalum nanosheet dispersion is two-dimensionally The concentration of the nanosheet is 5 mg/mL, and the mass ratio of the polyvinylidene fluoride to the two-dimensional tantalum nanosheet is 1:10;
将二维碲纳米片分散液均匀地涂在ITO玻璃上，干燥后得到工作电极；The two-dimensional cerium nanosheet dispersion is uniformly coated on the ITO glass, and dried to obtain a working electrode;
提供铂电极，在工作电极和铂电极之间注入电解液，电解液为1mol/L的KOH溶液，经封装后得到光探测器。A platinum electrode is provided, and an electrolyte is injected between the working electrode and the platinum electrode, and the electrolyte is a 1 mol/L KOH solution, and a photodetector is obtained after being packaged.
将实施例4制得的光探测器在不同光强(黑暗，I，II，III，IV以及VI)以及不同施加电压下(0，0.1，0.2，0.3，0.4，0.5以及0.6V)的信号。白光源的I，II，III，IV以及VI光强分别对应26.2，53.0，83.1，118.0，和122.0mW/cm 2。测试结果如图6所示。如图6所示，随着施加电压的增加，光强的增加，光电信号也在增加。此外，可以看到在长达600s的光电探测中，光电信号并未衰减，说明该二维碲纳米片以及光探测器具有很好的稳定性。 The photodetector prepared in Example 4 was subjected to signals of different light intensities (dark, I, II, III, IV, and VI) and different applied voltages (0, 0.1, 0.2, 0.3, 0.4, 0.5, and 0.6 V). . The light intensities of I, II, III, IV and VI of the white light source correspond to 26.2, 53.0, 83.1, 118.0, and 122.0 mW/cm 2 , respectively . The test results are shown in Figure 6. As shown in FIG. 6, as the applied voltage increases, the light intensity increases, and the photoelectric signal also increases. In addition, it can be seen that in the photoelectric detection of up to 600 s, the photoelectric signal is not attenuated, indicating that the two-dimensional 碲 nanosheet and the photodetector have good stability.
实施例5Example 5
一种光探测器的制备方法，包括以下步骤：A method of preparing a photodetector includes the following steps:
采用实施例2制得的二维碲纳米片；Using the two-dimensional tantalum nanosheet prepared in Example 2;
取纤维素，将纤维素溶解在甲基吡咯烷酮中，然后加入实施例2制得的二维碲纳米片形成二维碲纳米片分散液，二维碲纳米片分散液中二维碲纳米片的 浓度为10mg/mL，纤维素与二维碲纳米片的质量比为1∶100；Taking cellulose, dissolving cellulose in methylpyrrolidone, and then adding the two-dimensional tantalum nanosheet prepared in Example 2 to form a two-dimensional tantalum nanosheet dispersion, two-dimensional tantalum nanosheet dispersion in two-dimensional tantalum nanosheet The concentration is 10 mg / mL, the mass ratio of cellulose to two-dimensional tantalum nanosheet is 1:100;
将二维碲纳米片分散液均匀地涂在ITO玻璃上，干燥后得到工作电极；The two-dimensional cerium nanosheet dispersion is uniformly coated on the ITO glass, and dried to obtain a working electrode;
提供铂电极，在工作电极和铂电极之间注入电解液，电解液为10mol/L的氯化钠溶液，经封装后得到光探测器。A platinum electrode is provided, and an electrolyte is injected between the working electrode and the platinum electrode, and the electrolyte is a 10 mol/L sodium chloride solution, and a photodetector is obtained after being packaged.
实施例6Example 6
一种光探测器的制备方法，包括以下步骤：A method of preparing a photodetector includes the following steps:
采用实施例3制得的二维碲纳米片；Using the two-dimensional tantalum nanosheet prepared in Example 3;
取聚偏氟乙烯，将聚偏氟乙烯溶解在甲基吡咯烷酮中，然后加入实施例3制得的二维碲纳米片形成二维碲纳米片分散液，二维碲纳米片分散液中二维碲纳米片的浓度为8mg/mL，聚偏氟乙烯与二维碲纳米片的质量比为1∶50；Polyvinylidene fluoride was taken, polyvinylidene fluoride was dissolved in methylpyrrolidone, and then two-dimensional cerium nanosheets prepared in Example 3 were added to form a two-dimensional cerium nanosheet dispersion, two-dimensional bismuth nanosheet dispersion in two-dimensional The concentration of the nanosheet is 8 mg/mL, and the mass ratio of the polyvinylidene fluoride to the two-dimensional tantalum nanosheet is 1:50;
将二维碲纳米片分散液均匀地涂在ITO玻璃上，干燥后得到工作电极；The two-dimensional cerium nanosheet dispersion is uniformly coated on the ITO glass, and dried to obtain a working electrode;
提供铂电极，在工作电极和铂电极之间注入电解液，电解液为5mol/L的硫酸钾溶液，经封装后得到光探测器。A platinum electrode is provided, and an electrolyte is injected between the working electrode and the platinum electrode, and the electrolyte is a 5 mol/L potassium sulfate solution, and a photodetector is obtained after being packaged.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims (20)

  1. 一种光探测器，其中，包括工作电极、对电极以及设于所述工作电极和所述对电极之间的电解液，所述工作电极包括导电基底和设置在所述导电基底上的半导体层，所述半导体层的材料包括二维碲纳米片。A photodetector comprising a working electrode, a counter electrode, and an electrolyte disposed between the working electrode and the counter electrode, the working electrode including a conductive substrate and a semiconductor layer disposed on the conductive substrate The material of the semiconductor layer comprises a two-dimensional germanium nanosheet.
  2. 如权利要求1所述的光探测器，其中，所述二维碲纳米片的厚度为1-50nm。The photodetector of claim 1 wherein said two-dimensional tantalum nanosheets have a thickness of from 1 to 50 nm.
  3. 如权利要求2所述的光探测器，其中，所述二维碲纳米片的厚度为1-5nm。The photodetector of claim 2 wherein said two-dimensional germanium nanosheets have a thickness of from 1 to 5 nm.
  4. 如权利要求2所述的光探测器，其中，所述二维碲纳米片的厚度为5-10nm。The photodetector of claim 2, wherein the two-dimensional germanium nanosheet has a thickness of 5-10 nm.
  5. 如权利要求1所述的光探测器，其中，所述二维碲纳米片的长宽尺寸为10-200nm。The photodetector of claim 1 wherein said two-dimensional germanium nanosheets have a length to width dimension of from 10 to 200 nm.
  6. 如权利要求5所述的光探测器，其中，所述二维碲纳米片的长宽尺寸为10-50nm。The photodetector according to claim 5, wherein said two-dimensional germanium nanosheet has a length to width dimension of from 10 to 50 nm.
  7. 如权利要求5所述的光探测器，其中，所述二维碲纳米片的长宽尺寸为50-100nm。The photodetector according to claim 5, wherein said two-dimensional tantalum nanosheet has a length to width dimension of 50 to 100 nm.
  8. 如权利要求5所述的光探测器，其中，所述二维碲纳米片的长宽尺寸为100-200nm。The photodetector according to claim 5, wherein said two-dimensional germanium nanosheet has a length to width dimension of from 100 to 200 nm.
  9. 如权利要求1所述的光探测器，其中，所述半导体层还包括高分子材料，所述高分子材料与所述二维碲纳米片均匀分布在所述半导体层中。The photodetector according to claim 1, wherein said semiconductor layer further comprises a polymer material, said polymer material and said two-dimensional germanium nanosheet being uniformly distributed in said semiconductor layer.
  10. 如权利要求9所述的光探测器，其中，所述高分子材料包括聚偏氟乙烯和纤维素中的至少一种。The photodetector according to claim 9, wherein said high molecular material comprises at least one of polyvinylidene fluoride and cellulose.
  11. 如权利要求9所述的光探测器，其中，所述高分子材料与所述二维碲纳米片的质量比为1∶10-1∶100。The photodetector according to claim 9, wherein a mass ratio of said high molecular material to said two-dimensional cerium nanosheet is from 1:10 to 1:100.
  12. 如权利要求11所述的光探测器，其中，所述高分子材料与所述二维碲纳米片的质量比为1∶10-1∶50。The photodetector according to claim 11, wherein a mass ratio of said polymer material to said two-dimensional cerium nanosheet is from 1:10 to 1:50.
  13. 如权利要求1所述的光探测器，其中，所述电解液包括碱性电解液或中性电解液，所述碱性电解液包括碱液，所述中性电解液包括中性盐溶液。The photodetector of claim 1 wherein said electrolyte comprises an alkaline electrolyte or a neutral electrolyte, said alkaline electrolyte comprising an alkali solution, said neutral electrolyte comprising a neutral salt solution.
  14. 如权利要求13所述的光探测器，其中，所述碱液包括氢氧化钾溶液和氢氧化钠溶液中的至少一种；所述盐溶液包括硫酸钠溶液、硫酸钾溶液、氯化钠溶液和氯化钾溶液中的至少一种。The photodetector according to claim 13, wherein said alkali solution comprises at least one of a potassium hydroxide solution and a sodium hydroxide solution; and said salt solution comprises a sodium sulfate solution, a potassium sulfate solution, a sodium chloride solution And at least one of potassium chloride solutions.
  15. 如权利要求1所述的光探测器，其中，所述电解液的浓度为0.1-10mol/L。The photodetector according to claim 1, wherein the electrolyte has a concentration of 0.1 to 10 mol/L.
  16. 如权利要求15所述的光探测器，其中，所述电解液的浓度为0.1mol/L-1mol/L。The photodetector according to claim 15, wherein the concentration of the electrolytic solution is from 0.1 mol/L to 1 mol/L.
  17. 如权利要求1所述的光探测器，其中，所述半导体层的厚度为100nm-500nm。The photodetector of claim 1, wherein the semiconductor layer has a thickness of from 100 nm to 500 nm.
  18. 一种光探测器的制备方法，其中，包括以下步骤：A method for preparing a photodetector, comprising the steps of:
    提供碲原料，采用液相剥离的方法对所述碲原料进行剥离，得到二维碲纳米片；Providing a bismuth raw material, and stripping the bismuth raw material by a liquid phase stripping method to obtain a two-dimensional bismuth nanosheet;
    将所述二维碲纳米片分散在有机溶剂中形成二维碲纳米片分散液，将所述二维碲纳米片分散液均匀涂布在导电基底上，干燥后得到工作电极；Dispersing the two-dimensional cerium nanosheet in an organic solvent to form a two-dimensional cerium nanosheet dispersion, uniformly coating the two-dimensional cerium nanosheet dispersion on a conductive substrate, and drying to obtain a working electrode;
    提供对电极，在所述工作电极和所述对电极之间注入电解液，经封装后得到光探测器。A counter electrode is provided, an electrolyte is injected between the working electrode and the counter electrode, and a photodetector is obtained after being packaged.
  19. 如权利要求18所述的光探测器的制备方法，其中，所述液相剥离的方法具体包括以下操作：The method of producing a photodetector according to claim 18, wherein the method of liquid phase stripping specifically comprises the following operations:
    将所述碲原料加入至剥离溶剂中，在冰浴环境下采用探头超声8-15h；所述探头超声结束后，继续采用水浴超声，所述水浴超声时间为3-10h，所述水浴的温度保持5-15℃；超声后，进行离心和干燥得到二维碲纳米片。The bismuth raw material is added to the stripping solvent, and the probe is ultrasonicated for 8-15 hours in an ice bath environment; after the probe is ultrasonicated, the water bath ultrasonication is continued, and the ultrasonic bath time is 3-10 h, the temperature of the water bath Maintain 5-15 ° C; after sonication, centrifuge and dry to obtain two-dimensional tantalum nanosheets.
  20. 如权利要求18所述的光探测器的制备方法，其中，所述工作电极的具体制备方法包括：The method of fabricating a photodetector according to claim 18, wherein the specific preparation method of the working electrode comprises:
    提供高分子材料，将所述高分子材料溶解在有机溶剂中，然后将所述二维碲纳米片分散在含有所述高分子材料的所述有机溶剂中，形成二维碲纳米片分散液，将所述二维碲纳米片分散液均匀涂布在所述导电基底上形成半导体层，干燥后得到所述工作电极。Providing a polymer material, dissolving the polymer material in an organic solvent, and then dispersing the two-dimensional tantalum nanosheet in the organic solvent containing the polymer material to form a two-dimensional tantalum nanosheet dispersion. The two-dimensional cerium nanosheet dispersion is uniformly coated on the conductive substrate to form a semiconductor layer, and the working electrode is obtained after drying.
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