CN114203325A

CN114203325A - Preparation method of wide-bandgap oxide Schottky junction beta nuclear battery unit

Info

Publication number: CN114203325A
Application number: CN202111194615.9A
Authority: CN
Inventors: 吴巍炜; 张永峰; 胡文文; 张劲松; 徐盼; 周春林; 杨毓枢; 王旭
Original assignee: Wuhu Research Institute of Xidian University
Current assignee: Wuhu Research Institute of Xidian University
Priority date: 2021-10-13
Filing date: 2021-10-13
Publication date: 2022-03-18

Abstract

The invention belongs to the technical field of semiconductor devices and nuclear science, and particularly relates to a preparation method of a wide bandgap oxide Schottky junction beta nuclear battery unit₂O₃A texture film is annealed at high temperature and then assembled with a graphene or carbon nano tube or a metal Ti/Au film top electrode to obtain Ga₂O₃A schottky diode cell; finally in Ga₂O₃An ultrathin 63Ni radiation source film is attached to the Schottky diode unit to obtain a wide-bandgap oxide Schottky junction beta radiation volt nuclear battery, and the prepared beta radiation volt nuclear battery provides a reliable power supply which can continuously supply power independent of external input energy for extremely severe environments such as deep space, deep sea, polar regions and the like; the control of the wide bandgap semiconductor energy band structure is realized by doping metal elements, and the growth form regulation and the energy band structure control of the wide bandgap semiconductor are realized by using a surfactant to regulate the growth form of the wide bandgap semiconductor.

Description

Preparation method of wide-bandgap oxide Schottky junction beta nuclear battery unit

Technical Field

The invention belongs to the technical field of semiconductor devices and nuclear science, and particularly relates to a preparation method of a wide bandgap oxide Schottky junction beta nuclear battery unit.

Background

Under extremely severe environments, the existing battery systems of various types of electronic device systems, such as chemical batteries, solar batteries, fuel batteries and the like, cannot adapt to harsh working conditions of ultrahigh/low temperature, strong radiation, high vacuum, difficult charging and the like. Therefore, the adaptive power supply which can be free of maintenance, long in service life and high in conversion efficiency in extreme environments has important scientific and application values for people to go to deep space, step to deep sea and step into the polar region. The beta radiation voltaic nuclear battery has the characteristics of long service life, high unit energy density, strong external interference resistance, stability, reliability, no need of maintenance and replacement, easiness in miniaturization and integration and the like, is an ideal, reliable and long-acting miniature energy source, and becomes an important development direction in the fields of MEMS and new energy sources.

The working principle of the beta radiation volt battery is similar to that of a solar battery, and the energy conversion device of the beta radiation volt battery is mainly a semiconductor device (a p-n junction, a p-i-n junction or a Schottky diode). As shown in fig. 4, the beta particles are first emitted by isotopes, and when the beta particles interact with a semiconductor substance, ionization of the beta particles generates radiative electron-hole pairs. And then, after beta rays generate radiation electron-hole pairs, the electron-hole pairs are separated and collected by two electrodes under the action of an electric field built in a p-n junction, a p-i-n junction or a Schottky junction and converted into electric energy based on a beta radiation volt effect nuclear battery with a p-n junction or a p-i-n junction, the principle is similar to that of a photovoltaic battery. Commonly used structures in beta-radiation voltaic nuclear cells are p-n and schottky structures. The built-in electric field of the p-n junction enables the electron-hole pairs to be separated, the preparation process is relatively simple, and the cost is low. With the development of semiconductor processing technology, the Schottky junction is more and more applied to the p-n junction contrast ratio in the isotope battery, the radiation resistance of the Schottky junction is strong, and the electrical output of the prepared isotope battery is more stable.

Several key problems of beta-ray volt batteries remain to be effectively solved: 1) the radiation protection problem is as follows: the performance of the semiconductor material can gradually decline under the irradiation of beta rays, but the wide-bandgap semiconductor Ga₂O₃Materials are expected to ameliorate this problem; 2) the doping of wide bandgap semiconductors is difficult: as a battery transduction material, a semiconductor is required to have good carrier mobility, the intrinsic carrier concentration of a wide-bandgap semiconductor is low, doping is required to improve the concentration, but in the growth process, the defects of doping and doping elements are difficult to activate, and long-term research and overcoming are required; 3) difficulty in integrally increasing output power: the two effective ways for improving the performance of the beta-ray volt battery are proved, wherein one way is to improve the output of a single device, and the other way is to carry out series-parallel connection integration.

beta-Ga compared with third generation semiconductor₂O₃The material has the advantages of larger forbidden band width, higher breakdown field strength, larger Baliga quality factor, shorter absorption cut-off edge, lower growth cost and simple energy band engineering regulation and control, and is expected to become a preferred material for high-voltage, high-power and low-loss power devices and deep ultraviolet electronic devices. Meanwhile, beta-Ga as a wide bandgap semiconductor₂O₃Has strong bonding property, and the energy of the atoms replaced from the lattice positions is high, so the radiation resistance is strong. beta-Ga₂O₃The doping research is more, the doping of various elements can be realized, and the regulation and control of the gallium oxide energy band structure, the number of carriers and the carrier mobility are easy to realize. Thus beta-Ga₂O₃Has excellent prospect in the field of beta-radiation voltaic nuclear batteries.

Based on Ga₂O₃The beta radiation volt effect nuclear battery made of the semiconductor material with the equal-width forbidden band shows higher open-circuit voltage, higher energy conversion efficiency and stronger radiation resistance, thereby being paid attention to by researchers. On the other hand, in order to obtain a high-power nuclear battery device, compared with the method of optimizing the structural design of the transduction material and the device, the performance of a single device is further improved, and the method of carrying out series-parallel connection integration on the device is a more efficient and feasible method at present. However, in the existing device preparation and integration method, the volume of a single device is not largeThe method is further reduced, and the energy conversion material cannot be stably prepared, so that the integration density is low, and the output power cannot be substantially improved.

Disclosure of Invention

The invention aims to solve the technical problem in the prior art and provides a preparation method of a wide bandgap oxide Schottky junction beta nuclear battery unit.

The technical scheme is as follows for solving the technical problem of the invention:

a preparation method of a wide bandgap oxide Schottky junction beta nuclear battery unit comprises the following specific processes: firstly, growing n-type beta-Ga on a substrate by a two-step hydrothermal method₂O₃A texture film is annealed at high temperature and then assembled with a graphene or carbon nano tube or a metal Ti/Au film top electrode to obtain Ga₂O₃A schottky diode cell; finally in Ga₂O₃And attaching an ultrathin 63Ni radiation source film on the Schottky diode unit to obtain the wide-bandgap oxide Schottky junction beta radiation volt nuclear battery.

The preparation method of the wide bandgap oxide Schottky junction beta radiation volt nuclear battery comprises the following steps:

step a, using gallium nitrate as a gallium source on an FTO substrate to hydrothermally grow n-type Ga by a two-step method₂O₃The texture film, wherein the first step of hydrothermal growth uses the mixed solution of ethanol and deionized water as a solvent to grow Ga₂O₃Seed layer, second step Ga growth using aqueous solution₂O₃A texture film, and performing high-temperature annealing after the two-step hydrothermal growth to obtain n-type beta-Ga₂O₃A textured film;

step b, in n-type beta-Ga₂O₃Covering the surface of the texture film with a graphene top electrode through floating transfer or plating a Ni/Au film top electrode through electron beam thermal evaporation or constructing a carbon nanotube film top electrode through an L-B film method to obtain Ga₂O₃A schottky diode cell;

step c, obtaining Ga₂O₃The Schottky diode unit and the self-supporting ultrathin 63Ni radiation source film prepared based on the electroplating method are attached through floating transfer, and a sample is naturally attached after the attachment is finishedAnd drying and baking, taking down the sample after baking, and naturally cooling to room temperature to obtain the wide bandgap oxide Schottky junction beta radiation volt nuclear battery.

The preparation method of the wide bandgap oxide Schottky junction beta radiation volt nuclear battery comprises the following specific steps:

step a, growing n-type beta-Ga on FTO substrate by hydrothermal method₂O₃And (3) texturing a film:

(1) cleaning the FTO substrate by using acetone, ethanol and deionized water in sequence, and drying the cleaned FTO substrate for later use;

(2) fully mixing ethanol and deionized water in a volume ratio of 1:1, and then adding Ga₂(NO₃)₆·nH₂The Ga with the concentration of 1mol/L is formed after the O is fully stirred and mixed₂(NO₃)₆·nH₂O ethanol water solution;

(3) putting the cleaned FTO substrate into a 10ml specification reaction kettle in an inclined way, and adding 8ml Ga into the reaction kettle₂(NO₃)₆·nH₂Aqueous O ethanol with FTO face down;

(4) reacting the mixture for 1 to 2 hours at the temperature of between 90 and 100 ℃ in a closed reaction kettle, naturally cooling the mixture to room temperature after the reaction is finished, and removing the solution in the inner container of the reaction kettle;

(5) adding Ga into deionized water₂(NO₃)₆·nH₂The O is fully stirred and dissolved to form Ga with the concentration of 1mol/L₂(NO₃)₆·nH₂Adding 8ml of O aqueous solution into the reaction kettle in the step (4), reacting for 24-36h at the temperature of 140-₂O₃An FTO substrate of textured film;

(6) will grow Ga₂O₃The FTO substrate of the texture film is put into a high temperature furnace to be annealed for 12 to 18 hours at the temperature of 550-850 ℃, and the n-type beta-Ga with compact structure is obtained on the FTO substrate₂O₃A textured film;

step b, beta-Ga₂O₃Assembling the texture film and the graphene top electrode to obtain Ga₂O₃Schottky diodeA tube unit;

(1) growing single crystal graphene on the surface of a Cu foil by adopting a CVD method, then covering a PMMA film on the graphene, and then putting 3mol/L ferric chloride FeCl₃Etching in the solution for 30-60min to completely remove Cu, so that the graphene film protected by PMMA floats on the surface of the solution for later use;

(2) with beta-Ga₂O₃The graphene film protected by PMMA is slightly dragged out to be transferred to deionized water by an FTO substrate of the texture film to keep the graphene film in a floating state, and after the graphene film is soaked for 30-60min to remove clean ferric trichloride and then dried for 2-4 hours at 40-100 ℃ in a vacuum state, the graphene film is tightly attached to Ga₂O₃Textured film to obtain Ga₂O₃A schottky diode cell;

step c, attaching a self-supporting ultrathin 63Ni radiation source film with the thickness of 20-23um and prepared based on an electroplating method, drying the sample in a vacuum oven at the temperature of 40-100 ℃ for 2-4 hours after the attachment is finished, taking down the sample, and naturally cooling to room temperature to obtain the wide-bandgap oxide Schottky junction beta radiation voltaic nuclear battery;

the step b is as follows:

(1) will carry n-type beta-Ga₂O₃Cleaning an FTO substrate of the textured film by using ethanol and deionized water in sequence, and then drying the FTO substrate by using a nitrogen gun for later use;

(2) dispersing 0.05g of carbon nanotube powder in 10ml of a mixed solution of chloroform and dimethylformamide DMF, wherein the volume ratio of the chloroform to the dimethylformamide DMF is 1: 1;

(3) injecting distilled water into the drawing machine to the horizontal plane position of the drawing machine, and sucking 500ul of the solution prepared in the step (2) by using a 1000ul injector to disperse the solution into the distilled water one drop by one drop;

(4) the beta-Ga with n type is prepared by a Langmuir-Blodgett method₂O₃The FTO substrate of the texture membrane extends into the solution in the step (3), and is slowly pulled at the speed of 0.5-2cm/min under the surface membrane pressure of 30-35Pa to obtain Ga₂O₃A schottky diode cell.

The step b is as follows:

(1) will carry n-type beta-Ga₂O₃Cleaning and drying an FTO substrate of the textured film, and attaching the FTO substrate to a carrying disc;

(2) opening a thermal evaporation cavity, putting a carrying disc into the cavity and attaching the carrying disc to an upper evaporation area, respectively putting Ni particles and Au particles into two heating crucibles of a thermal evaporation instrument, and closing an evaporation cavity;

(3) at a vacuum degree of 1X 10^-4-5×10^-4Evaporating under Pa, evaporating Ni as the first layer at a current of 70-80A, evaporating 50nmNi as the adhesion layer, evaporating 150nmAu as the electrode layer on the basis of the Ni layer at a current of 50-60A, and taking out Ga with Ni/Au electrode after cooling₂O₃A schottky diode cell.

The method for growing the single crystal graphene by the CVD method comprises the following steps:

(1) preparing a copper foil: cleaning two copper foils with the thickness of 20-25 mu m in acetone, alcohol and deionized water respectively, blow-drying the surfaces of the copper foils by using high-purity nitrogen, drying, putting the copper foils in a CVD (chemical vapor deposition) tube furnace respectively, heating to 1000-1050 ℃, and introducing H₂Cleaning for 1-1.2h, and introducing CH₄Cleaning for 1-1.2 h;

(2) and copper foil annealing: at H₂Annealing the copper foil at 1050 ℃ under the atmosphere for 30-90 min;

(3) and introducing a carbon source: under the temperature condition of 1050 ℃ of 1000-: 1H₂And CH₄Mixing the gases, and keeping for 10-20 min;

(4) and cooling: continuously introducing the mixture into a reactor with the volume ratio of 99: 1H₂And CH₄Directly opening the furnace body when the temperature of the mixed gas is reduced to 250-300 ℃, and taking out the copper foil attached with the graphene when the temperature of the furnace is rapidly reduced to below 40 ℃;

(5) and coating: and taking out the copper foil attached with the graphene, putting the copper foil on a spin coater, dropwise adding 200ul of polymethyl methacrylate PMMA solution with the mass concentration of 5.5%, operating at 500-800rmp for 10-30 seconds and at high speed at 3000-5000rmp for 20-40 seconds, and spin-coating to form the graphene covering the PMMA film.

In the step aSecond step Ga growth using aqueous solution₂O₃And when the film is textured, adding metal salts of metal elements Ni, Sn, Al and Mn to realize doping modification.

The second step in step a is to grow Ga by using an aqueous solution₂O₃When the film is textured, cetyl trimethyl ammonium bromide or lauryl sodium sulfate surfactant is used for regulating and controlling the surface growth state of gallium oxide, and Ga with more compact surface state is obtained₂O₃And (3) texturing the film.

The specific method of the self-supporting 63Ni radiation source film obtained by the electroplating method in the step c comprises the following steps:

(1) 210g of NiSO₄·6H₂O、55g NiCl₂·6H₂O、65g NaCl、30g H₃BO₃Dissolving in 1L deionized water, and adjusting pH to 4-5;

(2) pouring the solution in the step (1) into an electroplating bath, putting the electroplating bath into a water bath at 25-30 ℃, and placing for 30-60 Min;

(3) placing ITO glass with the size of 5cmx6cm into an electroplating bath and vertically fixing;

(4) putting a nickel sheet with the size of 5cmx6cm into an electroplating bath, and vertically fixing the ITO in the step (3) in a parallel arrangement way with the distance of 8-10 cm;

(5) connecting the cathode of the electrochemical workstation with the ITO glass, and connecting the reference electrode and the counter electrode of the electrochemical workstation with the nickel sheet;

(6) setting the initial voltage to be 1.5V, the output current to be 100mA and the electroplating time to be 40-45min by adopting a constant current electroplating method to obtain a nickel film growing on the surface of the ITO;

(7) taking out the ITO glass with the nickel film in the step (6), attaching the ITO glass with the nickel film by using a transparent adhesive tape with the width of 5cm, adhering the nickel film on the adhesive tape, and tearing off the adhesive tape to obtain the transparent adhesive tape with the nickel film;

(8) flattening the transparent adhesive tape with the nickel film, gently placing the transparent adhesive tape on the surface of the acetone liquid, and dissolving the adhesive in the transparent adhesive tape to obtain a self-supporting nickel film;

(9) and (4) transferring the nickel film in the step (8) into deionized water, and cleaning for 3-5 times.

The invention adopts a two-step hydrothermal growth technology to form compact n-type beta-Ga on a substrate₂O₃The texture film is assembled with the top electrodes of different types of graphene carbon nanotubes or metal Ti/Au films to obtain Ga₂O₃A schottky diode cell; finally in Ga₂O₃An ultrathin 63Ni radiation source is attached to the Schottky diode unit to obtain a wide-bandgap oxide Schottky junction beta radiation volt nuclear battery₂O₃The technologies of Schottky diode preparation, wafer-level micron 63Ni radiation source preparation, floating transfer stacking and the like are effectively integrated, and the prepared beta radiation voltaic nuclear battery provides a reliable power supply which can continuously supply power without depending on external input energy for extremely severe environments such as deep space, deep sea, polar region and the like; the control of the wide bandgap semiconductor energy band structure is realized by doping metal elements, and the growth form regulation and the energy band structure control of the wide bandgap semiconductor are realized by using a surfactant to regulate the growth form of the wide bandgap semiconductor; the self-supporting single device of the beta radiation volt battery is prepared, the device outputs higher open-circuit voltage, and long-time energy output is realized.

Drawings

FIG. 1 shows n-type β -Ga of example 1 of the present invention₂O₃SEM images of textured films on FTO substrates;

FIG. 2 shows Sn-doped n-type β -Ga of example 3 of the present invention₂O₃SEM images of textured films on FTO substrates;

FIG. 3 shows n-type β -Ga of example 2 of the present invention using cetyltrimethylammonium bromide as a surfactant₂O₃SEM images of textured films on FTO substrates;

FIG. 4 shows Ga in example 3 of the present invention₂O₃And the preparation of the Schottky diode unit is shown schematically.

Detailed Description

Example 1

A preparation method of a wide bandgap oxide Schottky junction beta nuclear battery unit comprises growing n-type Ga on an FTO substrate by a hydrothermal method₂O₃A texture film, after high-temperature annealing, directly using an FTO substrate as a bottom electrode, and adopting CVD-grown graphene covering a PMMA filmUsing FeCl₃Removing the Cu substrate with the solution to obtain a self-supporting graphene film, dragging the film out of the solution, transferring the film into deionized water to keep the film in a floating state, and using the prepared Ga₂O₃The graphene film in the deionized water is fished up and assembled by the film to obtain Ga₂O₃A Schottky diode device unit, and then an ultrathin 63Ni film prepared by electroplating is transferred to Ga in a floating way₂O₃Drying the Schottky diode device unit to finally obtain the wide bandgap oxide Schottky junction beta radiation volt nuclear battery, which comprises the following specific steps:

step a: growth of Ga on FTO substrates using high temperature hydrothermal method₂O₃Textured film

(1) Cutting the FTO substrate into 2 x 1cm²Sequentially cleaning the materials with acetone, ethanol and deionized water, and drying for later use after cleaning;

(2) 5ml of ethanol and 5ml of deionized water were thoroughly mixed, and 0.2564g of Ga were weighed out in a concentration of 1mol/L₂(NO₃)₆·nH₂Adding O into a beaker, and fully stirring and mixing to obtain gallium nitrate ethanol aqueous solution;

(3) putting the cleaned FTO substrate into a 10ml reaction kettle liner with the FTO surface facing downwards at an inclination angle of 60 degrees, pouring 8ml of gallium nitrate ethanol aqueous solution into the reaction kettle liner, and screwing down the reaction kettle;

(4) reacting for 1h at 100 ℃, and naturally cooling to room temperature after the reaction is finished;

(5) opening the reaction kettle which is cooled after the reaction in the step (4) is finished, sucking out the solution in the inner container of the reaction kettle, and removing the solution after the reaction;

(6) weighing 10ml of deionized water, and weighing 0.2564g of Ga according to the concentration of 1mol/L₂(NO₃)₆·nH₂The O is fully stirred and dissolved to obtain Ga with the concentration of 1mol/L₂(NO₃)₆·nH₂An aqueous solution of O;

(7) pouring 8ml of the gallium nitrate aqueous solution obtained in the step (6) into a liner of a reaction kettle, screwing the reaction kettle tightly, reacting the sealed reaction kettle at 150 ℃ for 24 hours, and naturally cooling to room temperature after the reaction is finished;

(8) taking out Ga grown₂O₃Cleaning an FTO substrate of the textured film for 3 times by using ethanol and ultrasonic waves to remove surface attachments;

(9) putting the FTO substrate taken out in the step (8) into a high-temperature tube furnace to anneal for 18h at 550 ℃ to obtain n-type beta-Ga with compact structure on the FTO substrate₂O₃And (3) texturing the film.

Step b: beta-Ga₂O₃Assembling the texture film and the graphene top electrode to obtain Ga₂O₃Schottky diode cell

(1) Growing 2 x 2cm on the surface of the Cu foil by adopting a CVD method²The single crystal graphene of (2), wherein the method for growing the single crystal graphene by the CVD method comprises:

1. preparing a copper foil: two copper foils (2 cmx 2 cm) with the thickness of 20um are respectively put into acetone, alcohol and deionized water for cleaning for 2 times, then the surfaces of the copper foils are dried by high-purity nitrogen, the dried copper foils are respectively put in the center of a furnace tube heating zone of a CVD tubular furnace, the CVD tubular furnace is arranged to be heated to 1050 ℃ at the heating rate of 5 ℃/min, then the tubular furnace is sealed, and H is firstly introduced into the tubular furnace₂Cleaning for 1h, and introducing CH₄Cleaning for 1 h;

2. copper foil annealing: close CH in 1₄In H₂Annealing the copper foil at 1050 ℃ for 30min in the atmosphere to remove oxides on the surface of the copper foil, thereby obtaining the copper foil with single surface crystal orientation and strong catalytic activity;

3. introducing a carbon source: open CH₄And H₂A passage is communicated with a reaction chamber with the volume ratio of 99: 1H₂And CH₄Keeping the mixed gas for 10 min;

4. cooling: continuously introducing the mixture into a reactor with the volume ratio of 99: 1H₂And CH₄Directly opening the furnace body when the temperature of the mixed gas is reduced to 300 ℃, closing a vacuum and gas supply system when the temperature of the furnace is rapidly reduced to be below 40 ℃, and taking out the copper foil attached with the graphene;

5. coating: putting the taken copper foil attached with the graphene on a spin coater, dripping 200ul of polymethyl methacrylate (PMMA) solution with the mass concentration of 5.5% after vacuum absorption, running at a low speed of 500rmp for 10 seconds and a high speed of 3000rmp for 20 seconds, and performing spin coating to form the graphene covering the PMMA film;

6. etching: the graphene covered PMMA film was then placed in a 3mol/LFeCl chamber₃Enabling the graphene to float on the surface of the solution in the solution, and etching for 30min to completely remove Cu, so that the graphene prepared into a self-supporting film floats for later use;

(2) with beta-Ga₂O₃Slightly pulling out the PMMA/graphene film by the FTO substrate of the textured film, transferring the PMMA/graphene film into deionized water to keep the PMMA/graphene film in a floating state, soaking for 30min to remove ferric trichloride, then slightly pulling out the deionized water, drying for 2 hours at 100 ℃ in a vacuum state, and enabling the graphene film to be tightly attached to Ga₂O₃Texturing the film to obtain Ga₂O₃A schottky diode cell.

Step c, attaching an ultrathin 63Ni radiation source to obtain a wide bandgap oxide Schottky junction beta radiation volt nuclear battery;

(1) the self-supporting 63Ni radiation source film obtained by using an electroplating method comprises the following specific steps:

1. 210g of NiSO₄·6H₂O、55g NiCl₂·6H₂O、65g NaCl、30g H₃BO₃Dissolving in 1L deionized water, and adjusting pH to 4;

2. pouring the solution in the step 1 into an electroplating bath, putting the electroplating bath into a water bath at 30 ℃, and standing for 30 min;

3. placing ITO glass with the size of 5cmx6cm into an electroplating bath and vertically fixing;

4. putting a nickel sheet with the size of 5cmx6cm into an electroplating bath, and vertically fixing the ITO in 3 in parallel at a distance of 10 cm;

5. connecting the cathode of the electrochemical workstation with the ITO glass, and connecting the reference electrode and the counter electrode of the electrochemical workstation with the nickel sheet;

6. setting the initial voltage to be 1.5V, the output current to be 100mA and the electroplating time to be 40min by adopting a constant current electroplating method to obtain a nickel film growing on the surface of the ITO;

7. taking out the ITO glass with the nickel film in the step 6, attaching the ITO glass with the nickel film by using a transparent adhesive tape with the width of 5cm, attaching the nickel film on the adhesive tape, and tearing off the adhesive tape to obtain the transparent adhesive tape with the nickel film, wherein the film component of the transparent adhesive tape is BOPP, and the adhesive component is acrylate glue;

8. flattening the transparent adhesive tape with the nickel film, gently placing the transparent adhesive tape on the surface of acetone liquid, and dissolving an adhesive in the transparent adhesive tape to obtain a self-supporting ultrathin 63Ni film with the thickness of 20 mu m;

9. transferring the 8 medium-thin 63Ni film into deionized water, and cleaning for 3 times;

(2) use of ultra-thin 63Ni films with Ga₂O₃Contacting one end of the Schottky diode unit and lightly pressing Ga₂O₃The base film is drawn out to ensure that the base film and the Ga are completely attached to avoid generating bubbles in the middle, and after the attachment is finished, the sample is naturally dried and dried for 4 hours at 40 ℃ in a vacuum state to ensure that the 63Ni film and the Ga₂O₃And (3) tightly attaching the base diode film, taking down the sample after baking, and naturally cooling to room temperature to obtain the wide bandgap oxide Schottky junction beta radiation volt nuclear battery.

Example 2

A preparation method of a wide bandgap oxide Schottky junction beta nuclear battery unit comprises growing n-type Ga on an FTO substrate by a hydrothermal method₂O₃A texture film is obtained by using hexadecyl trimethyl ammonium bromide as a surfactant, an FTO substrate is directly used as a bottom electrode in high-temperature annealing, and the CVD-grown graphene covering the PMMA film is FeCl₃Removing the Cu substrate with the solution to obtain a self-supporting graphene film, dragging the film out of the solution, transferring the film into deionized water to keep the film in a floating state, and using the prepared Ga₂O₃The graphene film in the deionized water is fished up and assembled by the film to obtain Ga₂O₃A Schottky diode device unit, and then an ultrathin 63Ni film prepared by electroplating is transferred to Ga in a floating way₂O₃Drying the Schottky diode device unit to finally obtain the wide bandgap oxide Schottky junction beta radiation volt nuclear battery, which comprises the following specific steps:

(2) 5ml of ethanol and 5ml of deionized water were mixed thoroughly, and 0.2564g of Ga were weighed out in a concentration of 1mol/l₂(NO₃)₆·nH₂Adding O into a beaker, and fully stirring and mixing to obtain gallium nitrate ethanol aqueous solution;

(3) putting the cleaned FTO substrate into a 10ml reaction kettle liner with the FTO surface facing downwards at an inclination angle of 70 degrees, pouring 8ml of gallium nitrate ethanol aqueous solution into the reaction kettle liner, and screwing down the reaction kettle;

(4) reacting at 90 ℃ for 2h, and naturally cooling to room temperature after the reaction is finished;

(6) weighing 10ml of deionized water, adding 0.2564g of Ga weighed according to the concentration of 1mol/L₂(NO₃)₆·nH₂O, 0.0366g of hexadecyl trimethyl ammonium bromide weighed according to the concentration of 0.1mol/L is fully stirred and dissolved to obtain Ga with the concentration of 1mol/L₂(NO₃)₆·nH₂O water solution and surfactant are used for regulating and controlling the dense state of the surface of the gallium oxide textured film;

(7) pouring 8ml of the gallium nitrate aqueous solution obtained in the step (6) into a liner of a reaction kettle, screwing the reaction kettle tightly, reacting the sealed reaction kettle at 140 ℃ for 24 hours, and naturally cooling to room temperature after the reaction is finished;

(8) taking out Ga grown₂O₃Cleaning an FTO substrate of the textured film for 4 times by using ethanol and ultrasonic waves to remove surface attachments;

(9) and (3) annealing the FTO substrate taken out in the step (8) in a high-temperature tube furnace at 850 ℃ for 12h to obtain n-type beta-Ga with a compact structure on the FTO substrate₂O₃A textured film;

step b: beta-Ga₂O₃The texture film is assembled with the graphene top electrodeTo Ga₂O₃Schottky diode cell

1. preparing a copper foil: two copper foils (2 cmx 2 cm) with the thickness of 20um are respectively put into acetone, alcohol and deionized water for cleaning for 5 times, then the surfaces of the copper foils are dried by high-purity nitrogen, the dried copper foils are respectively put in the center of a furnace tube heating zone of a CVD tubular furnace, the CVD tubular furnace is arranged to be heated to 1000 ℃ at the heating rate of 6 ℃/min, then the tubular furnace is closed, H is firstly introduced₂Cleaning for 1.2h, and introducing CH₄Cleaning for 1.2 h;

2. copper foil annealing: close CH in 1₄In H₂Annealing the copper foil at 1000 ℃ for 90min in the atmosphere to remove oxides on the surface of the copper foil, thereby obtaining the copper foil with single surface crystal orientation and strong catalytic activity;

3. introducing a carbon source: open CH₄And H₂A passage, wherein under the temperature condition of 1000 ℃, the volume ratio of the inlet is 99: 1H₂And CH₄Keeping the mixed gas for 20 min;

4. cooling: continuously introducing the mixture into a reactor with the volume ratio of 99: 1H₂And CH₄Directly opening the furnace body when the temperature of the mixed gas is reduced to 250 ℃, closing a vacuum and gas supply system when the temperature of the furnace is rapidly reduced to be below 40 ℃, and taking out the copper foil attached with the graphene;

5. coating: putting the taken copper foil attached with the graphene on a spin coater, dripping 200ul of polymethyl methacrylate (PMMA) solution with the mass concentration of 5.5% after vacuum absorption, operating at a low speed of 800rmp for 30 seconds and a high speed of 5000rmp for 40 seconds, and performing spin coating to form the graphene covering the PMMA film;

6. etching: putting the graphene covered with the PMMA film into ferric trichloride 3mol/L FeCl₃Enabling the graphene to float on the surface of the solution in the solution, and etching for 60min to completely remove Cu, so that the graphene prepared into a self-supporting film floats for later use;

(2) with beta-Ga₂O₃Slightly pulling out the PMMA/graphene film by an FTO substrate of the textured film, transferring the PMMA/graphene film into deionized water to keep the PMMA/graphene film in a floating state, soaking for 60min to remove ferric trichloride, then slightly pulling out the deionized water, and drying for 4 hours at 40 ℃ in a vacuum state to ensure that the graphene film is tightly attached to Ga₂O₃Texturing the film to obtain Ga₂O₃A schottky diode cell.

(1) a self-supporting 63Ni radiation source film obtained by an electroplating method;

1. 210g of NiSO₄·6H₂O、55g NiCl₂·6H₂O、65g NaCl、30g H₃BO₃Dissolving in 1L deionized water, and adjusting pH to 5;

2. pouring the solution in the step 1 into an electroplating bath, putting the electroplating bath into a water bath kettle at 25 ℃, and standing for 60 min;

4. putting a nickel sheet with the size of 5cmx6cm into an electroplating bath, and vertically fixing the ITO in 3 in parallel at a distance of 8 cm;

6. setting the initial voltage to be 1.5V, the output current to be 100mA and the electroplating time to be 45min by adopting a constant current electroplating method to obtain a nickel film growing on the surface of the ITO;

8. flattening the transparent adhesive tape with the nickel film, gently placing the transparent adhesive tape on the surface of acetone liquid, and dissolving an adhesive in the transparent adhesive tape to obtain a self-supporting ultrathin 63Ni film with the thickness of 23 um;

9. transferring the 8 medium-thin 63Ni film into deionized water, and cleaning for 5 times;

(2) use of ultra-thin 63Ni films with Ga₂O₃Contacting one end of the Schottky diode unit and lightly pressing Ga₂O₃The base film is drawn out to ensure that the base film and the Ga are completely attached to avoid generating bubbles in the middle, and after the attachment is finished, the sample is naturally dried and dried for 2 hours at the temperature of 100 ℃ in a vacuum state to ensure that the 63Ni film and the Ga₂O₃And (3) tightly attaching the base diode film, taking down the sample after baking, and naturally cooling to room temperature to obtain the wide bandgap oxide Schottky junction beta radiation volt nuclear battery.

Example 3

A preparation method of a wide bandgap oxide Schottky junction beta nuclear battery unit comprises the steps of carrying out hydrothermal doping on Sn-containing metal salt, and growing n-type Ga on an FTO substrate by adopting a hydrothermal method₂O₃A texture film, directly using an FTO substrate as a bottom electrode after high-temperature annealing, and adopting FeCl to the CVD-grown graphene covering the PMMA film₃Removing the Cu substrate with the solution to obtain a self-supporting graphene film, dragging the film out of the solution, transferring the film into deionized water to keep the film in a floating state, and using the prepared Ga₂O₃The graphene film in the deionized water is fished up and assembled by the film to obtain Ga₂O₃A Schottky diode device unit, and then an ultrathin 63Ni film prepared by electroplating is transferred to Ga in a floating way₂O₃Drying the Schottky diode device unit to finally obtain the wide bandgap oxide Schottky junction beta radiation volt nuclear battery, which comprises the following specific steps:

(1) Cutting the FTO substrate into 2 x 2cm²Sequentially cleaning the materials with acetone, ethanol and deionized water, and drying for later use after cleaning;

(2) 5ml of ethanol and 5ml of deionized water are fully mixed in a beaker, and 0.2564g of Ga are weighed according to the concentration of 1mol/L₂(NO₃)₆·nH₂O, weighing 0.0185g SnCl₂·4H₂Adding O into a beaker, and fully stirring and mixing to obtain gallium nitrate ethanol aqueous solution;

(3) putting the cleaned FTO substrate into a 10ml reaction kettle liner with the FTO surface facing downwards by inclining the cleaned FTO substrate by 50 degrees, pouring 8ml gallium nitrate ethanol water solution into the reaction kettle liner, and screwing down the reaction kettle;

(8) taking out Ga grown₂O₃Cleaning an FTO substrate of the textured film for 5 times by using ethanol and ultrasonic waves to remove surface attachments;

(9) putting the FTO substrate taken out of the 9 into a high-temperature tube furnace to anneal for 12 hours at 850 ℃ to obtain n-type beta-Ga with compact structure on the FTO substrate₂O₃And (3) texturing the film.

1. preparing a copper foil: two copper foils (2 cmx 2 cm) with the thickness of 20um are respectively put into acetone, alcohol and deionized water for cleaning for 2 times, then the surfaces of the copper foils are dried by high-purity nitrogen, the dried copper foils are respectively put in the center of a furnace tube heating zone of a CVD tubular furnace, the CVD tubular furnace is arranged to be heated to 1015 ℃ at the heating rate of 5 ℃/min, then the tubular furnace is closed, H is firstly introduced₂Cleaning for a predetermined period of timeFor 1.2h, then CH is introduced₄Cleaning for 1.2 h;

2. copper foil annealing: close CH in 1₄In H₂Annealing the copper foil at 1015 ℃ for 30min in an atmosphere to remove oxides on the surface of the copper foil, thereby obtaining the copper foil with single surface crystal orientation and strong catalytic activity;

3. introducing a carbon source: open CH₄And H₂And a passage, wherein under the condition of 1015 ℃, the mixture is introduced into a reactor with the volume ratio of 99: 1H₂And CH₄Keeping the mixed gas for 20 min;

6. etching: putting the graphene covered with the PMMA film into ferric trichloride 3mol/L FeCl₃Enabling the graphene to float on the surface of the solution in the solution, and etching for 30min to completely remove Cu, so that the graphene prepared into a self-supporting film floats for later use;

(2) with beta-Ga₂O₃Slightly pulling out the PMMA/graphene film by an FTO substrate of the textured film, transferring the PMMA/graphene film into deionized water to keep the PMMA/graphene film in a floating state, soaking for 60min to remove ferric trichloride, then slightly pulling out the deionized water, and drying for 3 hours at 80 ℃ in a vacuum state to ensure that the graphene film is tightly attached to Ga₂O₃Texturing the film to obtain Ga₂O₃A schottky diode cell.

2. pouring the solution in the step 1 into an electroplating bath, putting the electroplating bath into a water bath kettle at 25 ℃, and standing for 30 min;

Example 4

Wide bangThe preparation method of the oxide Schottky junction beta nuclear battery unit adopts a hydrothermal method to grow n-type Ga on an FTO substrate₂O₃The texture membrane directly uses an FTO substrate as a bottom electrode, the carbon nano tube is self-assembled on the surface of deionized water by an L-B membrane method to obtain a self-supporting carbon nano tube membrane, and the prepared Ga is used₂O₃The film drags the carbon nanotube film in the deionized water to assemble to obtain Ga₂O₃A Schottky diode device unit, and then an ultrathin 63Ni film prepared by electroplating is transferred to Ga in a floating way₂O₃Drying the Schottky diode device unit to finally obtain the wide bandgap oxide Schottky junction beta radiation volt nuclear battery, which comprises the following specific steps:

(2) 5ml of ethanol and 5ml of deionized water are fully mixed in a beaker, and 0.2564g of Ga are weighed according to the concentration of 1mol/L₂(NO₃)₆·nH₂Adding O into a beaker, and fully stirring and mixing to obtain gallium nitrate ethanol aqueous solution;

(3) putting the cleaned FTO substrate into a 10ml reaction kettle liner with the FTO surface facing downwards at an inclination angle of 70 degrees, pouring a gallium nitrate ethanol aqueous solution into the reaction kettle liner, and screwing down the reaction kettle;

(6) weighing 10ml of deionized water, and weighing 0.2564g of Ga according to the concentration of 1mol/L₂(NO₃)₆·nH₂O, weighing 0.0185g SnCl₂·4H₂Fully stirring and dissolving the O to obtain a gallium nitrate aqueous solution;

(9) and (3) annealing the FTO substrate taken out in the step (8) in a high-temperature tube furnace at 850 ℃ for 12h to obtain n-type beta-Ga with a compact structure on the FTO substrate₂O₃And (3) texturing the film.

Step b: beta-Ga₂O₃Assembling the texture film and the carbon nanotube film top electrode to obtain Ga₂O₃Schottky diode cell

(2) dispersing 0.05g of carbon nanotube powder in 20ml of a mixed solution of chloroform and dimethylformamide DMF, wherein the volume ratio of the chloroform to the dimethylformamide DMF is 1: 1;

(3) injecting distilled water into the drawing machine to the horizontal plane position of the drawing machine, sucking 500ul of the solution prepared in the step (2) by using a 1000ul of injector, and dispersing the solution drop by drop into the distilled water, wherein the carbon nano tubes are automatically coagulated together;

(4) the method of Langmuir-Blodgett is to carry n-type beta-Ga₂O₃The FTO substrate of the texture membrane extends into the solution in the step (3), and is slowly pulled at the speed of 2cm/min under the surface membrane pressure of 30Pa to obtain Ga₂O₃A schottky diode cell.

(1) self-supporting 63Ni radiation source film obtained by electroplating stripping;

4. putting a nickel sheet with the size of 5cmx6cm into an electroplating bath, and vertically fixing the ITO in 3 in parallel at a distance of 9 cm;

6. adopting constant current electroplating method, setting initial voltage at 1.5V, output current at 100mA, and electroplating time at 42min to obtain nickel film grown on ITO surface

(2) use of ultra-thin 63Ni films with Ga₂O₃Contacting one end of the Schottky diode unit and lightly pressing Ga₂O₃The base film is drawn out to be completely attached to the base film, bubbles are prevented from being generated in the middle, and after the attachment is finished, the sample is naturally dried and is dried for 2 hours at the temperature of 100 ℃ in a vacuum state, so that the 63Ni film and Ga are attached to the sample₂O₃And (3) tightly attaching the base diode film, taking down the sample after baking, and naturally cooling to room temperature to obtain the wide bandgap oxide Schottky junction beta radiation volt nuclear battery.

Example 5

A preparation method of a wide bandgap oxide Schottky junction beta radiation volt nuclear battery adopts a hydrothermal method to grow n-type Ga on an FTO substrate₂O₃Textured film using FTO substrate as bottom electrode directlySelf-assembling carbon nano-tube on the surface of deionized water by an L-B membrane method to obtain a self-supporting carbon nano-tube film, and using the prepared Ga₂O₃The film drags the carbon nanotube film in the deionized water to assemble to obtain Ga₂O₃A Schottky diode device unit, and then an ultrathin 63Ni film prepared by electroplating is transferred to Ga in a floating way₂O₃Drying the Schottky diode device unit to finally obtain the wide bandgap oxide Schottky junction beta radiation volt nuclear battery, which comprises the following specific steps:

(5) and (4) opening the reaction kettle which is cooled after the reaction in the step (4) is finished, sucking out the solution in the inner container of the reaction kettle, and removing the solution after the reaction.

(6) Weighing 10ml of deionized water, adding 0.0366g of hexadecyl trimethyl ammonium bromide, and weighing 0.2564g of Ga according to the concentration of 1mol/L₂(NO₃)₆·nH₂O, fully stirring and dissolving to obtain a gallium nitrate aqueous solution;

(8) taking out the raw materialGrown with Ga₂O₃Cleaning an FTO substrate of the textured film for 4 times by using ethanol and ultrasonic waves to remove surface attachments;

(4) the method of Langmuir-Blodgett is to carry n-type beta-Ga₂O₃The FTO substrate of the texture membrane extends into the solution in the step (3), and is slowly pulled at the speed of 0.5cm/min under the surface membrane pressure of 35Pa to obtain Ga₂O₃A schottky diode cell.

6. setting the initial voltage to be 1.5V, the output current to be 100mA and the electroplating time to be 42min by adopting a constant current electroplating method to obtain a nickel film growing on the surface of the ITO;

Example 6

A preparation method of a wide bandgap oxide Schottky junction beta nuclear battery unit comprises growing n-type Ga on an FTO substrate by a hydrothermal method₂O₃Textured film, using FTO substrate directly as bottom electrode, Ga will be grown₂O₃Protecting FTO substrate of the texture film, reserving electrode position, and using electron beam thermal evaporation technology to carry out Ga deposition₂O₃Ni vapor deposition on textured filmGa from Au electrodes₂O₃A Schottky diode device unit, and then an ultrathin 63Ni film prepared by electroplating is transferred to Ga in a floating way₂O₃Drying the Schottky diode device unit to finally obtain the wide bandgap oxide Schottky junction beta radiation volt nuclear battery, which comprises the following specific steps:

(9) will be provided with(8) The FTO substrate taken out is put into a high-temperature tube furnace to be annealed for 12 hours at the temperature of 550 ℃ to obtain n-type beta-Ga with compact structure on the FTO substrate₂O₃And (3) texturing the film.

Step b: beta-Ga₂O₃Assembling the texture film and a metal Ni/Au film top electrode to obtain Ga₂O₃A schottky diode cell;

(2) opening a thermal evaporation cavity, putting a carrying disc into the cavity, attaching the carrying disc to an upper evaporation area, respectively putting Ni particles and Au particles into two heating crucibles of a thermal evaporation instrument, and closing an evaporation cavity;

(3) at a vacuum degree of 5X 10^-4Evaporating under Pa, evaporating Ni layer as first layer electrode at current of 70A, evaporating 50nmNi layer as adhesion layer, evaporating 150nmAu layer as electrode layer on the basis of Ni layer at current of 60A, cooling to room temperature, and taking out Ga with Ni/Au electrode₂O₃A schottky diode cell.

5. connecting the negative electrode of the electrochemical workstation with ITO glass, and connecting the reference electrode and the counter electrode of the electrochemical workstation with a nickel sheet

Example 7

A preparation method of a wide bandgap oxide Schottky junction beta nuclear battery unit comprises growing n-type Ga on an FTO substrate by a hydrothermal method₂O₃Textured film, using FTO substrate directly as bottom electrode, Ga will be grown₂O₃Protecting FTO substrate of the texture film, reserving electrode position, and using electron beam thermal evaporation technology to carry out Ga deposition₂O₃Evaporating Ni/Au electrode on the texture film to obtain Ga₂O₃A Schottky diode device unit, and then an ultrathin 63Ni film prepared by electroplating is transferred to Ga in a floating way₂O₃Drying the Schottky diode device unit to finally obtain the wide bandgap oxide Schottky junction beta radiation volt nuclear battery, which comprises the following specific steps:

step a: using high temperaturesGrowth of Ga on FTO substrate by hydrothermal method₂O₃Textured film

(9) and (3) annealing the FTO substrate taken out in the step (8) in a high-temperature tube furnace at 550 ℃ for 12h to obtain n-type beta-Ga with a compact structure on the FTO substrate₂O₃And (3) texturing the film.

(3) at a vacuum degree of 1X 10^-4Evaporating under Pa, evaporating Ni as the first layer at 80A current, evaporating 50nm Ni as the adhesion layer, evaporating 150nm Au layer as the electrode layer at 50A current, cooling to room temperature, and taking out Ga with Ni/Au electrode₂O₃A schottky diode cell.

9. transferring the 8 medium-thin 63Ni film into deionized water, and cleaning for 4 times;

Claims

1. A preparation method of a wide bandgap oxide Schottky junction beta nuclear battery unit is characterized by comprising the following specific processes: firstly, growing n-type beta-Ga on a substrate by a two-step hydrothermal method₂O₃A texture film is annealed at high temperature and then assembled with a graphene or carbon nano tube or a metal Ni/Au film top electrode to obtain Ga₂O₃A schottky diode cell; finally in Ga₂O₃And attaching an ultrathin 63Ni radiation source film on the Schottky diode unit to obtain the wide-bandgap oxide Schottky junction beta radiation volt nuclear battery.

2. The method for preparing a wide bandgap oxide Schottky junction beta-nuclear battery cell according to claim 1, comprising the steps of:

step c, obtaining Ga₂O₃The Schottky diode unit and a self-supporting ultrathin 63Ni radiation source film prepared based on an electroplating method are attached through floating transfer, a sample is naturally dried and baked after the attachment is finished, and the sample is taken down and naturally cooled to room temperature after the baking is finished, so that the wide-bandgap oxide Schottky junction beta radiation volt nuclear battery is obtained.

3. The method for preparing the wide bandgap oxide Schottky junction beta nuclear battery unit according to claim 1 or 2, which is characterized by comprising the following specific steps:

step b, beta-Ga₂O₃Assembling the texture film and the graphene top electrode to obtain Ga₂O₃A schottky diode cell;

and c, attaching a self-supporting ultrathin 63Ni radiation source film with the thickness of 20-23um and prepared based on an electroplating method, drying the sample in a vacuum oven at the temperature of 40-100 ℃ for 2-4 hours after the attachment is finished, taking down the sample, and naturally cooling to room temperature to obtain the wide-bandgap oxide Schottky junction beta radiation voltaic nuclear battery.

4. The method for preparing a wide bandgap oxide schottky junction beta-nuclear battery cell according to claim 1 or 2, wherein the step b is:

5. The method for preparing a wide bandgap oxide schottky junction beta-nuclear battery cell according to claim 1 or 2, wherein the step b is:

6. The method for preparing the wide bandgap oxide Schottky junction beta nuclear battery unit according to claim 3, wherein the method for growing the single crystal graphene by the CVD method comprises the following steps:

7. The method for preparing the wide bandgap oxide Schottky junction beta nuclear battery unit as claimed in claim 3 or 6, wherein the second step in the step a is to grow Ga by using an aqueous solution₂O₃And when the film is textured, adding metal salts of metal elements Ni, Sn, Al and Mn to realize doping modification.

8. The method according to claim 7, wherein the second step in the step a is to grow Ga by using an aqueous solution₂O₃When the film is textured, cetyl trimethyl ammonium bromide or lauryl sodium sulfate surfactant is used for regulating and controlling the surface growth state of gallium oxide, and Ga with more compact surface state is obtained₂O₃And (3) texturing the film.

9. The method for preparing a wide bandgap oxide Schottky junction beta nuclear battery cell as claimed in claim 3 or 8, wherein the specific method of using the self-supporting 63Ni radiation source film obtained by electroplating in step c is as follows: