CN114188433A - h-BN photoelectric conversion device capable of being excited by near infrared light and preparation method thereof - Google Patents
h-BN photoelectric conversion device capable of being excited by near infrared light and preparation method thereof Download PDFInfo
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- 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 at least one potential-jump barrier or surface barrier, 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 or surface barrier
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- 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
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- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
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- 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
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Abstract
The invention discloses an h-BN photoelectric conversion device capable of being excited by near infrared light and a preparation method thereof, belonging to the technical field of near infrared light excitation of wide bandgap semiconductors, and the h-BN photoelectric conversion device is formed by up-conversion of microcrystalline NaYF4Yb, Tm, Gd is obtained by attaching and combining the h-BN @ electrode; when the photoelectric conversion device is irradiated by a near infrared light source, the micro-crystal NaYF is up-converted on the surface4Yb, Tm and Gd can generate ultraviolet fluorescence with the wavelengths of 205nm and 195.3nm through internal 7-photon up-conversion luminescence, and provide energy for optical excitation of h-BN, thereby realizing near infrared light excitation of the h-BN. Because the h-BN material is a wide bandgap semiconductor, the light source required for realizing the optical excitation is deep ultraviolet light with the wavelength less than 210nm, and the photoelectric conversion device made of the h-BN material is mainly used for detecting the deep ultraviolet light. The near infrared light can be usedThe excited h-BN photoelectric conversion device enriches the wavelength range of a detectable light source of the photoelectric conversion device taking h-BN as a raw material, and simultaneously solves the key technical difficulty of using the h-BN as a photocatalyst to be applied to the field of photocatalysis.
Description
Technical Field
The invention belongs to the technical field of near infrared light excitation of wide bandgap semiconductors, and particularly relates to an h-BN photoelectric conversion device capable of being excited by near infrared light and a preparation method thereof.
Background
The photoelectric conversion device refers to a device manufactured according to a photoelectric effect of a semiconductor, and is also called a photovoltaic device or a photosensitive device. The device has the advantages of high precision, quick response, non-contact, simple structure, flexible and various forms and the like, and is widely applied to photoelectric detection and automatic control. Among them, h-BN is one of the excellent raw materials for manufacturing photoelectric conversion devices due to its advantages of wide forbidden band width, low density, high melting point, low hardness, good thermal shock resistance and good mechanical processing performance.
At present, a photoelectric conversion device manufactured by taking h-BN as a raw material is mostly used for detecting deep ultraviolet light, and an h-BN photoelectric conversion device capable of responding to near infrared light is not developed.
Disclosure of Invention
The invention provides an h-BN photoelectric conversion device capable of being excited by near infrared light and a preparation method thereof4Yb, Tm and Gd, and h-BN near infrared light excitation is realized by an optical frequency up-conversion technology. The h-BN photoelectric conversion device prepared by the preparation method can realize the near infrared light excitation of h-BN and generateA large number of high-energy electrons have strong application potential in the aspects of photocatalysis, biological medical treatment, cosmic exploration and the like.
The invention is realized by the following technical scheme:
an h-BN photoelectric converter excited by near-infrared light is prepared by up-conversion of micron crystal NaYF4Yb, Tm, Gd is obtained by attaching and combining the h-BN @ electrode; specifically, the sapphire substrate 7, the h-BN film layer 6, the interdigital electrode layer 5 and the converted micron crystal NaYF are sequentially arranged from bottom to top4Yb, Tm and Gd4, and when the photoelectric conversion device is irradiated by a near infrared light source, the surface of the photoelectric conversion device is up-converted into micron crystal NaYF4Yb, Tm and Gd can generate deep ultraviolet fluorescence with the wavelength of 205nm and 195.3nm through an internal 7-photon up-conversion luminescence process to provide energy for optical excitation of h-BN, thereby realizing near infrared light excitation of the h-BN.
Preferably, the interdigital electrode layer 5 has a size of 10 μm × 10 μm, the h-BN thin film layer 6 has a thickness of 1 μm, and the sapphire substrate 7 has a size of 1.5cm × 1.5 cm.
In a second aspect, the invention provides a method for preparing an h-BN photoelectric conversion device capable of being excited by near infrared light, which comprises the following specific steps:
the method comprises the following steps: firstly, preparing up-conversion micron crystal NaYF by using a hydrothermal method4Yb, Tm and Gd, and then annealing the prepared up-conversion micro-crystal to obtain the up-conversion micro-crystal with high crystallization quality;
step two: preparing an h-BN @ electrode with an interdigital structure on a sapphire substrate;
step three: the up-conversion micron crystal NaYF obtained in the step (1)4Yb, Tm and Gd are attached and combined with the h-BN @ electrode obtained in the step (2) to obtain the h-BN photoelectric conversion device capable of being excited by near infrared light.
Preferably, the upconversion microcrystalline NaYF in step one4The specific preparation method of Yb, Tm and Gd comprises the following steps:
(1) mixing yttrium nitrate (Y (NO)3)3) Ytterbium nitrate (Yb (NO)3)3) Thulium nitrate (Tm (NO)3)3) Gadolinium nitrate (Gd (NO)3)3) Respectively dissolved in deionized water to prepare the concentrationIs a rare earth nitrate solution of 1M to 2M; dissolving the rare earth nitrate solution according to Y3+:Yb3+:Gd3+:Tm3+Adding the mixture into a beaker according to a molar weight ratio of 69.5:20:10:0.5, adding 2g to 5g of Ethylene Diamine Tetraacetic Acid (EDTA) as a surfactant, and stirring the mixed solution at 80r/min by using a stirrer for 20 to 40 minutes to form white flocculent turbid liquid as a precursor liquid; adding into white flocculent turbid liquid according to RE3+:F_Adding sodium fluoride (NaF) into the mixture according to a molar ratio of 1:3 to provide a fluorine source and a sodium source for reaction, and stirring the mixed solution at 80r/min by using a stirrer for 20 to 40 minutes; putting the liquid in the beaker into a stainless steel autoclave with a polytetrafluoroethylene lining, and putting the autoclave into an oven to heat so as to enable the reaction to occur, wherein the temperature of the oven is set to be 180 ℃, and the reaction time is 4 to 8 hours; taking out the reaction kettle after the reaction is finished, and naturally cooling to room temperature to obtain NaYF4Yb, Tm, Gd turbid liquid;
(2) the NaYF obtained by the reaction4Putting Yb, Tm and Gd turbid liquid into a centrifuge tube, and putting the centrifuge tube into a centrifuge for centrifugation, wherein the rotation speed of the centrifuge is set to be 800r/min to 1200r/min, and the centrifugation time is set to be 5 minutes; pouring the centrifuged supernatant into a waste liquid barrel to obtain the up-conversion micron crystal NaYF4:Yb,Tm,Gd；
(3) The up-conversion micron crystal NaYF obtained by the step (2)4Yb, Tm and Gd also have a small amount of Ethylene Diamine Tetraacetic Acid (EDTA) on the surface, and further cleaning is needed; the cleaning method comprises the following steps: carrying out up-conversion micron crystal NaYF obtained in the step (2) by an ultrasonic machine4Yb, Tm and Gd are dispersed in absolute ethyl alcohol and centrifuged by a centrifuge, wherein the rotating speed of the centrifuge is set to be 800r/min to 1200r/min, the centrifugation time is set to be 5 minutes, the centrifuged supernatant is poured into a waste liquid barrel, and the obtained up-conversion micron-crystal NaYF is obtained4Yb, Tm and Gd are dispersed in deionized water through an ultrasonic machine and are centrifuged by a centrifuge, wherein the rotating speed of the centrifuge is set to be 800r/min to 1200r/min, the centrifugation time is set to be 5 minutes, and the centrifuged supernatant is poured into a waste liquid barrel; repeating the above operation 3-5 times to obtain the up-conversion micron crystal NaYF4Cleaning Ethylene Diamine Tetraacetic Acid (EDTA) on the surfaces of Yb, Tm and Gd;
(4) the up-conversion micron crystal NaYF obtained in the step (3)4Yb, Tm and Gd are dried in a vacuum drying oven with the vacuum degree set to 8.104X 105Pa to-1.013X 107Pa, setting the temperature of the vacuum drying box to be 60-80 ℃, and drying for 10-12 hours, namely removing the moisture on the surface of the upconversion microcrystalline NaYF4: Yb, Tm and Gd;
(5) in order to improve the up-conversion micron crystal NaYF finally obtained4Yb, Tm, Gd crystallization rate, the upconversion microcrystalline NaYF obtained in step (4) is required4Annealing Yb, Tm, Gd; the method comprises the following specific steps: converting up-conversion micron crystal NaYF4Putting Yb, Tm and Gd into a pollution-free quartz mortar for grinding, subpackaging into a plurality of quartz crucibles, putting the quartz crucibles into a tube furnace for annealing in an argon atmosphere, wherein the temperature in the tube furnace is set to be 100-120 ℃, the annealing time is 4-6 hours, naturally cooling the tube furnace to room temperature after the annealing is finished, and taking out the quartz crucibles to obtain the up-conversion micron crystal NaYF4:Yb,Tm,Gd。
Preferably, the h-BN @ electrode in the second step is prepared by the following specific method:
selecting a sapphire substrate with good appearance, and using Low Pressure Chemical Vapor Deposition (LPCVD) to remove ammonia gas (NH)3) And boron trichloride (BCl)3) Preparing a layer of uniform and compact h-BN film on the surface of a sapphire substrate by taking raw materials as raw materials, wherein the growth temperature is 1300-1400 ℃, growing a layer of gold (Au) metal layer on the h-BN film by using a magnetron sputtering or evaporation method, and then forming an interdigital electrode on the surface of the metal layer by inductive coupling plasma etching (ICP) or wet etching to obtain the h-BN @ electrode.
Preferably, the upconversion microcrystalline NaYF in step three4The method for the adhesive bonding of Yb, Tm and h-BN @ electrodes is as follows:
the up-conversion micron crystal NaYF obtained in the step one is processed by an ultrasonic machine4Yb, Tm and Gd are dispersed in absolute ethyl alcohol, the dispersed liquid is dripped on the surface of the h-BN @ electrode in the step two, the absolute ethyl alcohol on the surface of the h-BN is evaporated by a vacuum drying oven, and the absolute ethyl alcohol is obtainedIn the process, the temperature of the vacuum drying oven is set to be 40-60 ℃, and the operation is repeatedly carried out for 3-5 times to obtain the up-conversion micron crystal NaYF4Yb, Tm and Gd are dispersed on the whole surface of the h-BN @ electrode to realize the up-conversion microcrystalline NaYF4Yb, Tm, Gd, and h-BN.
The h-BN photoelectric conversion device capable of being excited by near infrared light has the following working principle:
when the h-BN photoelectric conversion device prepared by the invention is excited by 980nm light, NaYF4Yb ions in Yb, Tm, Gd are first excited and then Tm ions are sensitized to make them transit to1G4、1D2、1I6、3P0,1,2And high energy excitation state. By both radiation re-absorption and energy transfer in1I6、3P0,1,2The Tm ions with high-energy excited state transfer energy to Gd ions to make the Gd ions jump to the excited state energy level6IJ、6PJ. At the position of6IJ、6PJThe Gd ions in the energy level are sensitized again by Yb ions to make the Gd ions transit to the excited state6DJAnd finally arrive at6GJEnergy level. Arrive at6GJThe process of energy levels is a 7-photon optical frequency up-conversion process, increasing the single-photon energy by a factor of about 4.76 (from 1.26eV to 6.0 eV). At the position of6GJA part of the high energy Gd ions of the energy level are passed through
Resonance Energy Transfer (FRET) or radiative reabsorption transfers energy to valence band electrons of h-BN to make them transition to conduction band, and another part makes radiative transition to8S7/2Energy level and emits fluorescence with wavelengths of 205nm and 195.3 nm. The part of fluorescence is reabsorbed by the h-BN to generate photon-generated carriers, thereby realizing the near infrared light excitation of the h-BN.
Compared with the prior art, the invention has the following advantages:
the h-BN photoelectric conversion device and the preparation method thereof have the advantages of easy manufacture, good thermal shock resistance and good machining performance, and the photoelectric conversion device which is manufactured by using ultra-wide forbidden band semiconductor materials and can be excited by near infrared light for the first time; the most important advantage is that the LED lamp can respond to near infrared light and deep ultraviolet (the wavelength is less than 210nm) light;
the h-BN photoelectric conversion device and the preparation method thereof enrich the wavelength range of a detectable light source of the photoelectric conversion device taking h-BN as a raw material, solve the key technical problem of using h-BN as a photocatalyst to be applied to the photocatalysis field in a large scale, and have strong application potential in the aspects of photocatalysis, biological medical treatment, cosmic detection and the like.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the description of the embodiment or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic diagram of an h-BN photoelectric conversion device capable of being excited by near infrared light according to the invention;
wherein: the copper wire 1 is connected with an external electrode and an interdigital electrode inside the h-BN photoelectric conversion device, the external electrode 2 and the h-BN photoelectric conversion device 3 are connected;
FIG. 2 is a schematic diagram of an h-BN photoelectric conversion device capable of being excited by near infrared light according to the present invention;
wherein: upconversion microcrystalline NaYF4Yb, Tm, Gd4, interdigital electrode layer 5, h-BN thin film 6 grown using Low Pressure Chemical Vapor Deposition (LPCVD), sapphire substrate 7;
FIG. 3 is a schematic diagram of an h-BN photoelectric conversion device capable of being excited by near infrared light according to the present invention;
FIG. 4 is a 100 times magnified topography of the surface of an h-BN photoelectric conversion device capable of being excited by near infrared light according to the invention through a transmission electron microscope;
can be seen from the figureOut-conversion micron crystal NaYF4Yb, Tm and Gd are dispersedly attached to the surface of the h-BN @ electrode;
FIG. 5 is a graph showing a comparison between a photocurrent inside the h-BN photoelectric conversion device when irradiated at 980nm and a dark current inside the h-BN photoelectric conversion device when irradiated without at 980nm as a function of an applied voltage;
as can be seen from the figure, the h-BN photoelectric conversion device provided by the invention can be excited by near infrared light through comparison of photocurrent and dark current;
FIG. 6 is a graph showing the change of the internal current of the h-BN photoelectric conversion device with time in the whole excitation process, wherein the external voltage is +300V at the stage of fixing the h-BN photoelectric conversion device, a 980nm semiconductor laser is used as a light source, and laser light with the time length of about 1s is applied to the h-BN photoelectric conversion device for irradiation;
FIG. 7 is a graph showing the comparison between the photocurrent inside the h-BN photoelectric conversion device when irradiated by a deep ultraviolet light source (wavelength less than 210nm) and the dark current inside the h-BN photoelectric conversion device when not irradiated by a deep ultraviolet light source, which vary with the applied voltage;
as can be seen from the figure, the comparison between the photocurrent and the dark current proves that the h-BN photoelectric conversion device can respond to near infrared light and deep ultraviolet light (the wavelength is less than 210 nm).
Detailed Description
The following embodiments are only used for illustrating the technical solutions of the present invention more clearly, and therefore, the following embodiments are only used as examples, and the protection scope of the present invention is not limited thereby. The specific implementation steps are as follows:
it is to be noted that, unless otherwise specified, technical or scientific terms used in this patent specification should have the ordinary meaning as understood by those skilled in the art to which the present invention pertains.
Example 1
The voltage source meter (Jishili 2410) used in the embodiment of the invention is connected to two ends of the electrode of the h-BN photoelectric conversion device, and provides external voltage for the h-BN photoelectric conversion device so as to improve the collection rate of photo-generated carriers in the h-BN, and simultaneously converts the h-BN near infrared light excitation phenomenon into photocurrent to be read out from the voltage source meter, thereby realizing the digitization and visualization of the experimental phenomenon.
As shown in fig. 1 and fig. 2, this embodiment provides an h-BN photoelectric conversion device capable of being excited by near infrared light, and the h-BN photoelectric conversion device is formed by up-conversion of microcrystalline NaYF4Yb, Tm, Gd is obtained by attaching and combining the h-BN @ electrode; specifically, the sapphire substrate 7, the h-BN film layer 6, the interdigital electrode layer 5 and the converted micron crystal NaYF are sequentially arranged from bottom to top4Yb, Tm and Gd4, and when the photoelectric conversion device is irradiated by a near infrared light source, the surface of the photoelectric conversion device is up-converted into micron crystal NaYF4Yb, Tm and Gd can generate deep ultraviolet fluorescence with the wavelength of 205nm and 195.3nm through an internal 7-photon up-conversion luminescence process to provide energy for optical excitation of h-BN, thereby realizing near infrared light excitation of the h-BN.
The size of the interdigital electrode layer 5 is 10 micrometers multiplied by 10 micrometers, the thickness of the h-BN thin film layer 6 is 1 micrometer, and the size of the sapphire substrate 7 is 1.5cm multiplied by 1.5 cm.
As shown in FIG. 3, which is a schematic diagram of the operation of an h-BN photoelectric conversion device capable of being excited by near infrared light according to the present invention, when the h-BN photoelectric conversion device is excited by 980nm light, NaYF is formed4Yb ions in Yb, Tm, Gd are first excited and then Tm ions are sensitized to make them transit to1G4、1D2、1I6、3P0,1,2And high energy excitation state. By both radiation re-absorption and energy transfer in1I6、3P0,1,2The Tm ions with high-energy excited state transfer energy to Gd ions to make the Gd ions jump to the excited state energy level6IJ、6PJ. At the position of6IJ、6PJThe Gd ions in the energy level are sensitized again by Yb ions to make the Gd ions transit to the excited state6DJAnd finally arrive at6GJEnergy level. The whole process involves a light frequency conversion process of 7 photons, increasing the energy of a single photon by a factor of about 4.76 (from 1.26eV to 6.0 eV). At the position of6GJA part of the high energy Gd ions of the energy level are passed through
Resonance Energy Transfer (FRET) or radiative reabsorption transfers energy to valence band electrons of h-BN to make them transition to conduction band, and another part makes radiative transition to8S7/2Energy level and emits fluorescence with wavelengths of 205nm and 195.3 nm. The part of fluorescence is reabsorbed by the h-BN to generate photon-generated carriers, thereby realizing the near infrared light excitation of the h-BN.
Example 2
The embodiment provides a preparation method of an h-BN photoelectric conversion device capable of being excited by near infrared light, which comprises the following specific steps:
the method comprises the following steps: firstly, preparing up-conversion micron crystal NaYF by using a hydrothermal method4Yb, Tm and Gd, and then annealing the prepared up-conversion micro-crystal to obtain the up-conversion micro-crystal with high crystallization quality;
(1) firstly, synthesizing 5mmol upconversion micron crystal NaYF4Yb, Tm, Gd: mixing yttrium nitrate (Y (NO)3)3) Ytterbium nitrate (Yb (NO)3)3) Thulium nitrate (Tm (NO)3)3) Gadolinium nitrate (Gd (NO)3)3) Dissolving the raw materials in deionized water according to a certain proportion to prepare solutions; dissolving the rare earth nitrate solution according to Y3+:Yb3+:Gd3+:Tm3+The mixture was added to a beaker at a molar ratio of 69.5:20:10:0.5, 2.975g of ethylenediaminetetraacetic acid (EDTA) was added thereto as a surfactant, and the mixed solution was stirred at 80r/min for 30 minutes using a stirrer to form a white cloudy solution as a precursor solution. To the white cloudy solution was added 3.625g of sodium fluoride (NaF) to supply a fluorine source and a sodium source for the reaction, and the mixed solution was stirred at 80r/min for 30 minutes using a stirrer. And (3) putting the liquid in the beaker into a reaction kettle, and putting the reaction kettle into an oven for heating to enable reaction to occur, wherein the temperature of the oven is set to be 180 ℃, and the reaction time is 8 hours. Taking out the reaction kettle after the reaction is finished, and naturally cooling to room temperature to obtain NaYF4Yb, Tm, Gd turbid liquid;
(2) the NaYF obtained by the reaction4Putting Yb, Tm and Gd turbid liquid into a centrifugal tube, and putting the centrifugal tube into a centrifuge for centrifugation, wherein the rotation speed of the centrifuge is set to be 1000r/min, the centrifugation time was set at 5 minutes. Pouring the centrifuged supernatant into a waste liquid barrel to obtain the up-conversion micron crystal NaYF4:Yb,Tm,Gd；
(3) The up-conversion micron crystal NaYF obtained by the step (2)4Yb, Tm, Gd also carry small amounts of ethylenediaminetetraacetic acid (EDTA) on the surface, which requires further cleaning. Converting up-conversion micron crystal NaYF through ultrasonic machine4Yb, Tm and Gd are dispersed in absolute ethyl alcohol and are centrifuged by a centrifuge, wherein the rotating speed of the centrifuge is set as 1000r/min, the centrifugation time is set as 5 minutes, the centrifuged supernatant is poured into a waste liquid barrel, and the obtained up-conversion micron crystal NaYF is obtained4Yb, Tm and Gd are dispersed in deionized water through an ultrasonic machine, and are centrifuged by a centrifuge, wherein the rotating speed of the centrifuge is set to 1000r/min, the centrifugation time is set to 5 minutes, and the centrifuged supernatant is poured into a waste liquid barrel. Repeating the above operation for 5 times to convert the micron crystal NaYF4Cleaning Ethylene Diamine Tetraacetic Acid (EDTA) on the surfaces of Yb, Tm and Gd;
(4) the up-conversion micron crystal NaYF obtained in the step (3)4Yb, Tm and Gd are dried in a vacuum drying oven with the vacuum degree set at 2.026X 103Pa, setting the temperature of a vacuum drying oven to be 60-80 ℃, setting the drying time to be 12 hours, and removing the up-conversion micron crystal NaYF4Yb, Tm, moisture of Gd surface;
(5) in order to improve the up-conversion micron crystal NaYF finally obtained4Yb, Tm, Gd crystallization rate, the upconversion microcrystalline NaYF obtained in step (4) is required4Yb, Tm, Gd. Converting up-conversion micron crystal NaYF4Putting Yb, Tm and Gd into a pollution-free quartz mortar for grinding, subpackaging into a plurality of quartz crucibles, putting the quartz crucibles into a tube furnace for annealing in argon atmosphere, wherein the temperature in the tube furnace is set to be 100 ℃, the annealing time is 6 hours, naturally cooling the tube furnace to room temperature after the annealing is finished, and taking out the quartz crucibles to obtain the up-conversion micron crystal NaYF meeting the requirements of the method of the invention4:Yb,Tm,Gd。
Step two: preparing an h-BN @ electrode with an interdigital structure on a sapphire substrate;
selecting a sapphire substrate with excellent appearance of 1.5cm multiplied by 1.5cm, and using Low Pressure Chemical Vapor Deposition (LPCVD) to use ammonia gas (NH)3) And boron trichloride (BCl)3) Preparing a layer of uniform and compact h-BN film with the thickness of 1 mu m on the surface of the sapphire substrate at 1350 ℃ as a raw material. Growing a layer of gold (Au) metal layer on the h-BN film by using magnetron sputtering or a method, and finally forming 10 mu m multiplied by 10 mu m interdigital electrodes on the surface of the metal layer by using inductively coupled plasma etching (ICP);
step three: the up-conversion micron crystal NaYF obtained in the step (1)4Yb, Tm and Gd are attached and combined with the h-BN @ electrode obtained in the step (2) to obtain an h-BN photoelectric conversion device capable of being excited by near infrared light;
the up-conversion micron crystal NaYF obtained in the step one is processed by an ultrasonic machine4Yb, Tm and Gd are dispersed in absolute ethyl alcohol, the dispersed liquid is dripped on the surface of the h-BN @ electrode in the step two, the absolute ethyl alcohol on the surface of the h-BN is evaporated by a vacuum drying oven, wherein the temperature of the vacuum drying oven is set to be 50 ℃, and the operation is repeatedly carried out for 5 times to obtain the up-conversion micron crystal NaYF4Yb, Tm and Gd are dispersed on the whole surface of the h-BN @ electrode to realize the up-conversion microcrystalline NaYF4Yb, Tm and Gd are combined with h-BN, and the h-BN photoelectric conversion device which can be excited by near infrared light is prepared.
Example 3: near infrared excitation of h-BN;
two ends of the electrode of the prepared h-BN photoelectric conversion device are respectively connected with the positive pole and the negative pole of a voltage source meter (Jishili 2410), and an external voltage is provided for the h-BN photoelectric conversion device through the voltage source meter. A980 nm semiconductor laser is used as a light source, a light path is adjusted to enable a laser focus to be converged at the center of the h-BN photoelectric conversion device, and a voltage source meter is controlled to measure the change of the photocurrent inside the h-BN photoelectric conversion device in the process that the applied voltage is changed from-300V to 300V. The 980nm semiconductor laser is turned off, the voltage source meter is controlled to measure the change of dark current in the h-BN photoelectric conversion device in the process that the applied voltage is changed from-300V to 300V, and the change of the dark current is compared with the magnitude of light dark current, so that the h-BN photoelectric conversion device provided by the invention can be excited by near infrared light.
As shown in fig. 6, the voltage applied to the h-BN electrode is fixed to be +300V, a 980nm semiconductor laser is used as a light source, a light path is adjusted to converge a laser focus at the center of the h-BN photoelectric conversion device, the h-BN photoelectric conversion device is irradiated by applying laser for a time period of about 1s, and a voltage source meter is used to read the change of the internal current of the h-BN photoelectric conversion device along with time in the whole excitation process, so that the h-BN photoelectric conversion device provided by the invention can be excited by near infrared light.
As can be seen from the figure, the internal current of the h-BN photoelectric conversion device rapidly increases in a very short time after the 980nm laser is irradiated to the surface of the h-BN photoelectric conversion device (stage 1), which is a near-infrared light excitation process for realizing the h-BN photoelectric conversion device by using the method of the present invention; over a longer period of time thereafter, the photocurrent begins to increase slowly (phase 2). This stage produces a large amount of heat accumulation for long laser irradiation to increase h-BN internal carriers. And the internal current of the h-BN photoelectric conversion device returns to the magnitude of dark current in a short time after the laser irradiation is stopped. This phenomenon occurs for two reasons: 1) the method does not meet the condition for realizing near infrared light excitation of the h-BN photoelectric conversion device without a near infrared light source, and the photocurrent disappears rapidly; 2) the laser irradiation is stopped, the surface temperature of the h-BN photoelectric conversion device cannot be continuously maintained, and the dark current is restored to the level before the irradiation.
Example 4: response of the h-BN photoelectric conversion device to a deep ultraviolet light source (the wavelength is less than 210 nm);
two ends of the electrode of the prepared h-BN photoelectric conversion device are respectively connected with the positive pole and the negative pole of a voltage source meter (Jishili 2410), and an external voltage is provided for the h-BN photoelectric conversion device through the voltage source meter. An ultraviolet pen lamp is used as a deep ultraviolet light source, a light path is adjusted to enable the light source to irradiate the center of the h-BN photoelectric conversion device, and a voltage source meter is controlled to measure the change of the photocurrent inside the h-BN photoelectric conversion device in the process that the applied voltage is changed from-300V to 300V. The light source is turned off, the voltage source meter is controlled to measure the change of dark current in the h-BN photoelectric conversion device in the process that the applied voltage is changed from-300V to 300V, and the contrast of the light dark current proves that the h-BN photoelectric conversion device provided by the invention can be excited by deep ultraviolet light (the wavelength is less than 210 nm).
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (6)
1. An h-BN photoelectric conversion device capable of being excited by near infrared light is characterized in that up-conversion micron crystal NaYF is adopted4Yb, Tm, Gd is obtained by attaching and combining the h-BN @ electrode; specifically, the sapphire substrate 7, the h-BN film layer 6, the interdigital electrode layer 5 and the converted micron crystal NaYF are sequentially arranged from bottom to top4Yb, Tm and Gd4, and when the photoelectric conversion device is irradiated by a near infrared light source, the surface of the photoelectric conversion device is up-converted into micron crystal NaYF4Yb, Tm and Gd can generate deep ultraviolet fluorescence with the wavelength of 205nm and 195.3nm through an internal 7-photon up-conversion luminescence process to provide energy for optical excitation of h-BN, thereby realizing near infrared light excitation of the h-BN.
2. The near-infrared light-excitable h-BN photoelectric conversion device according to claim 1, wherein the interdigital electrode layer 5 has a size of 10 μm x 10 μm, the h-BN thin film layer 6 has a thickness of 1 μm, and the sapphire substrate 7 has a size of 1.5cm x 1.5 cm.
3. The method for manufacturing an h-BN photoelectric conversion device capable of being excited by near infrared light according to claim 1, comprising the following steps:
the method comprises the following steps: firstly, preparing up-conversion micron crystal NaYF by using a hydrothermal method4Yb, Tm and Gd, and then annealing the prepared up-conversion micro-crystal to obtain the up-conversion micro-crystal with high crystallization quality;
step two: preparing an h-BN @ electrode with an interdigital structure on a sapphire substrate;
step three: the up-conversion micron crystal NaYF obtained in the step (1)4Yb, Tm and Gd are attached and combined with the h-BN @ electrode obtained in the step (2) to obtain the h-BN photoelectric conversion device capable of being excited by near infrared light.
4. The method of claim 3, wherein the first step of the upconversion of the NaYF is performed by using a microcrystalline film4The specific preparation method of Yb, Tm and Gd comprises the following steps:
(1) mixing yttrium nitrate (Y (NO)3)3) Ytterbium nitrate (Yb (NO)3)3) Thulium nitrate (Tm (NO)3)3) Gadolinium nitrate (Gd (NO)3)3) Respectively dissolving the rare earth nitrate into deionized water to prepare a rare earth nitrate solution with the concentration of 1M to 2M; dissolving the rare earth nitrate solution according to Y3+:Yb3+:Gd3+:Tm3+Adding the mixture into a beaker according to a molar weight ratio of 69.5:20:10:0.5, adding 2g to 5g of Ethylene Diamine Tetraacetic Acid (EDTA) as a surfactant, and stirring the mixed solution at 80r/min by using a stirrer for 20 to 40 minutes to form white flocculent turbid liquid as a precursor liquid; adding into white flocculent turbid liquid according to RE3+:F_Adding sodium fluoride (NaF) into the mixture according to a molar ratio of 1:3 to provide a fluorine source and a sodium source for reaction, and stirring the mixed solution at 80r/min by using a stirrer for 20 to 40 minutes; putting the liquid in the beaker into a stainless steel autoclave with a polytetrafluoroethylene lining, and putting the autoclave into an oven to heat so as to enable the reaction to occur, wherein the temperature of the oven is set to be 180 ℃, and the reaction time is 4 to 8 hours; taking out the reaction kettle after the reaction is finished, and naturally cooling to room temperature to obtain NaYF4Yb, Tm, Gd turbid liquid;
(2) the NaYF obtained by the reaction4Putting Yb, Tm and Gd turbid liquid into a centrifuge tube, and putting the centrifuge tube into a centrifuge for centrifugation, wherein the rotation speed of the centrifuge is set to be 800r/min to 1200r/min, and the centrifugation time is set to be 5 minutes; pouring the centrifuged supernatant into a waste liquid barrel to obtain the up-conversion micron crystal NaYF4:Yb,Tm,Gd；
(3) The up-conversion micron crystal NaYF obtained by the step (2)4Yb, Tm and Gd also have a small amount of Ethylene Diamine Tetraacetic Acid (EDTA) on the surface, and further cleaning is needed; the cleaning method comprises the following steps: carrying out up-conversion micron crystal NaYF obtained in the step (2) by an ultrasonic machine4Yb, Tm and Gd are dispersed in absolute ethyl alcohol and centrifuged by a centrifuge, wherein the rotating speed of the centrifuge is set to be 800r/min to 1200r/min, the centrifugation time is set to be 5 minutes, the centrifuged supernatant is poured into a waste liquid barrel, and the obtained up-conversion micron-crystal NaYF is obtained4Yb, Tm and Gd are dispersed in deionized water through an ultrasonic machine and are centrifuged by a centrifuge, wherein the rotating speed of the centrifuge is set to be 800r/min to 1200r/min, the centrifugation time is set to be 5 minutes, and the centrifuged supernatant is poured into a waste liquid barrel; repeating the above operation 3-5 times to obtain the up-conversion micron crystal NaYF4Cleaning Ethylene Diamine Tetraacetic Acid (EDTA) on the surfaces of Yb, Tm and Gd;
(4) the up-conversion micron crystal NaYF obtained in the step (3)4Yb, Tm and Gd are dried in a vacuum drying oven with the vacuum degree set to 8.104X 105Pa to-1.013X 107Pa, setting the temperature of the vacuum drying oven to be 60-80 ℃, and setting the drying time to be 10-12 hours, namely removing the up-conversion micron crystal NaYF4Yb, Tm, moisture of Gd surface;
in order to improve the up-conversion micron crystal NaYF finally obtained4Yb, Tm, Gd crystallization rate, the upconversion microcrystalline NaYF obtained in step (4) is required4Annealing Yb, Tm, Gd; the method comprises the following specific steps: converting up-conversion micron crystal NaYF4Putting Yb, Tm and Gd into a pollution-free quartz mortar for grinding, subpackaging into a plurality of quartz crucibles, putting the quartz crucibles into a tube furnace for annealing under argon atmosphere, wherein the temperature in the tube furnace is set to be 100-120 ℃, and the annealing time is setThe time is 4 to 6 hours, the tube furnace is naturally cooled to the room temperature after the annealing is finished, and the quartz crucible is taken out to obtain the up-conversion micron crystal NaYF4:Yb,Tm,Gd。
5. The method for preparing an h-BN photoelectric conversion device capable of being excited by near infrared light as claimed in claim 3, wherein the h-BN @ electrode in the second step is prepared by the following specific method:
selecting a sapphire substrate with good appearance, and using Low Pressure Chemical Vapor Deposition (LPCVD) to remove ammonia gas (NH)3) And boron trichloride (BCl)3) Preparing a layer of uniform and compact h-BN film on the surface of a sapphire substrate by taking raw materials as raw materials, wherein the growth temperature is 1300-1400 ℃, growing a layer of gold (Au) metal layer on the h-BN film by using a magnetron sputtering or evaporation method, and then forming an interdigital electrode on the surface of the metal layer by inductive coupling plasma etching (ICP) or wet etching to obtain the h-BN @ electrode.
6. The method for preparing a near-infrared-light-excitable h-BN photoelectric conversion device according to claim 3, wherein the upconversion microcrystalline NaYF is obtained in step three4The method for the adhesive bonding of Yb, Tm and h-BN @ electrodes is as follows:
the up-conversion micron crystal NaYF obtained in the step one is processed by an ultrasonic machine4Yb, Tm and Gd are dispersed in absolute ethyl alcohol, the dispersed liquid is dripped on the surface of the h-BN @ electrode in the step two, the absolute ethyl alcohol on the surface of the h-BN is evaporated by a vacuum drying oven, wherein the temperature of the vacuum drying oven is set to be 40-60 ℃, and the operation is repeatedly carried out for 3-5 times to obtain the up-conversion micron crystal NaYF4Yb, Tm and Gd are dispersed on the whole surface of the h-BN @ electrode to realize the up-conversion microcrystalline NaYF4Yb, Tm, Gd, and h-BN.
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