Nuclear battery based on zinc oxide nanowire-diamond heterojunction type beta-radiation volt effect and preparation method thereof

Abstract

The invention provides a zinc oxide nanowire-diamond heterojunction type beta radiation volt effect-based nuclear battery and a preparation method thereof, and belongs to the field of nuclear battery energy storage technology utilization. An n-type zinc oxide nanowire is combined with a p-type diamond film, and a radioactive source is integrated between a nano ZnO array and the diamond film, so that the problem of doping asymmetry of a wide bandgap semiconductor is avoided, the utilization efficiency of beta particles by a nuclear battery is improved, the influence of a surface state is reduced, the recombination rate of current carriers is reduced, and the conversion efficiency of the battery is improved; and higher open-circuit voltage and short-circuit current are obtained.

Description

Technical Field

[0001] The present invention belongs to the field of utilization of nuclear battery energy storage technology, and specifically relates to a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery and a preparation method thereof. Background Art

[0002] At present, conventional micro power sources are difficult to meet the needs of microelectromechanical systems (MEMS) for miniaturization, integration and long-life energy. Their working conditions will be affected by the external environment (such as light, temperature, etc.), and human intervention is required for long-term operation. This limits the application of MEMS in harsh environments and difficult to recharge situations.

[0003] Nuclear batteries have strong resistance to external interference, and do not require human intervention, care and maintenance during operation. In theory, they can work for decades or even longer if the radiation source and transducer are suitable. Among them, the beta radiation voltaic effect nuclear battery is the most suitable type of nuclear battery for MEMS power supply because its transducer is a semiconductor component, which is easy to integrate with semiconductor integrated circuits, has a small size, runs quietly and stably, and does not contain moving parts.

[0004] Current research shows that semiconductors with a bandgap width greater than 2.3eV (i.e., wide bandgap semiconductors) can significantly improve the radiation resistance and conversion efficiency of beta-radiovoltaic nuclear batteries, and nuclear batteries using non-planar structure transducers have better electrical performance than planar structure nuclear batteries. This is because the non-planar structure increases the contact area between the radiation source and the transducer, thereby improving the utilization rate of the radiation source. However, the doping asymmetry of wide bandgap semiconductors makes it difficult to obtain homogeneous pn junctions, and the barrier height of metal-semiconductor structures (i.e., Schottky junctions) is usually low, resulting in a very low open circuit voltage of nuclear batteries using Schottky structures, and it is difficult to improve electrical performance.

[0005] The pn heterojunction structure composed of two different wide bandgap semiconductors can circumvent the problem of doping asymmetry while more conveniently regulating the doping concentration. Among them, ZnO has extremely strong radiation resistance, is easy to grow nanostructures of various morphologies, and is easy to dope with n-type; diamond has a bandgap width of 5.5eV, has extremely strong thermal conductivity, high electron and hole mobility, and is easy to prepare p-type doped films. The heterojunction structure composed of n-type ZnO and p-type diamond has been applied to surface acoustic waves, ultraviolet detectors, sensors, etc., and has great application potential in high temperature environments. The device is expected to become a microbattery that can work stably in high temperature and strong radiation environments. Summary of the invention

[0006] The purpose of this section is to summarize some aspects of embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the specification abstract and the invention title of this application to avoid blurring the purpose of this section, the specification abstract and the invention title, and such simplifications or omissions cannot be used to limit the scope of the present invention.

[0007] In view of the above problems and / or the problems existing in the prior art, the present invention is proposed.

[0008] Therefore, the purpose of the present invention is to overcome the deficiencies in the prior art and provide a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery.

[0009] In order to solve the above technical problems, the present invention provides the following technical solutions, including:

[0010] ZnO nanowires;

[0011] p-type diamond film;

[0012] Si substrate;

[0013] Radioactive sources;

[0014] shell;

[0015] Wherein, the radiation source is loaded above the ZnO nanowire and between the ZnO nanowire and the p-type diamond film.

[0016] As a preferred solution of the zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery described in the present invention, the p-type diamond film and the ZnO nanowire form a heterojunction structure.

[0017] As a preferred solution of the zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery according to the present invention, the diameter of the ZnO nanowire is 100 to 500 nm.

[0018] As a preferred solution of the zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery of the present invention, the doping concentration of the p-type diamond film is 10 17 ~10 19 cm -3 .

[0019] Another object of the present invention is to overcome the deficiencies in the prior art and provide a method for preparing a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery.

[0020] In order to solve the above technical problems, the present invention provides the following technical solutions, including:

[0021] Pre-treating the Si substrate;

[0022] Growing p-type diamond films using MPCVD;

[0023] A ZnO seed crystal layer is plated on the surface of the p-type diamond film by using a radio frequency magnetron sputtering method: after the p-type diamond film is cleaned and dried, it is placed in a vacuum chamber of a magnetron sputtering device and evacuated, oxygen and argon are introduced, and the radio frequency distribution network is adjusted for ignition and pre-sputtering;

[0024] Preparation of ZnO nanowires using hydrothermal method: weigh Zn(NO3)2·6H2O and C6H 12 N4 powder is dissolved in deionized water to prepare a solution, and then H3BO3 solution is added and stirred. The mixed solution is poured into a reactor, and the mixture is sealed with a p-type diamond film coated with a ZnO seed layer and placed in the reactor together. The reactor is placed in a drying oven and heated at a constant temperature, and then naturally cooled to room temperature, the sample is taken out, the sample surface is rinsed and naturally dried;

[0025] The radioactive source is loaded on the surface of the ZnO nanowire;

[0026] Assemble the electrodes and housing.

[0027] As a preferred solution of the method for preparing a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery according to the present invention, the pretreatment includes mechanical grinding and ultrasonic cleaning.

[0028] As a preferred solution of the method for preparing a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery according to the present invention, the reaction gas of the MPCVD method includes CH4, H2, and B2H6.

[0029] As a preferred solution of the method for preparing a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery according to the present invention, the p-type diamond film is ultrasonically cleaned using acetone and ethanol solutions.

[0030] As a preferred solution of the method for preparing a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery according to the present invention, the diameter of the ZnO nanowire is 100 to 500 nm.

[0031] As a preferred solution of the method for preparing a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery according to the present invention, wherein: the doping concentration of the p-type diamond film is 10 17 ~10 19 cm -3 .

[0032] Beneficial effects of the present invention:

[0033] (1) The present invention provides a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery, in which the radiation source is integrated between the nano ZnO array and the diamond film, thereby improving the utilization efficiency of the nuclear battery for β particles, reducing the influence of the surface state, and reducing the recombination rate of carriers, thereby improving the conversion efficiency of the battery.

[0034] (2) The present invention provides a zinc oxide nanowire prepared by a hydrothermal method, and synthesizes a zinc oxide nanowire-diamond heterojunction type β-radiovoltaic effect nuclear battery. The nuclear battery avoids the asymmetric problem of wide bandgap semiconductor doping. The existence of the nanostructure makes the nuclear battery more efficient in utilizing β particles than the planar structure, the influence of the surface state is relatively small, and the recombination rate of carriers is significantly reduced, thereby improving the conversion efficiency of the battery and obtaining a higher open circuit voltage and short circuit current. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work. Among them:

[0036] Figure 1 It is a schematic structural diagram of the zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery of the present invention. DETAILED DESCRIPTION

[0037] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.

[0038] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0039] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The term "in one embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive with other embodiments.

[0040] Example 1

[0041] A schematic diagram of a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery is shown in Figure 1 ,in,

[0042] 100 is a ZnO nanowire, 200 is a p-type diamond film, 300 is a Si substrate, 400 is a radiation source, and 500 is a battery housing.

[0043] The present invention integrates the radiation source between the nano ZnO array and the diamond film. The p-type diamond film 200 and the ZnO nanowire 100 form a heterojunction structure, thereby improving the utilization efficiency of the nuclear battery for β particles, reducing the impact of the surface state, and reducing the recombination rate of carriers, thereby improving the conversion efficiency of the battery.

[0044] Example 2

[0045] The present invention uses MCNP and COMSOL software to perform theoretical simulation on the output performance of the nuclear battery and obtain the optimized parameters of each layer of the battery. The optimization results obtained by the present invention are as follows:

[0046] The diameter of zinc oxide nanowires is 100 to 500 nm;

[0047] The doping concentration of diamond film is 10 17 ~10 19 cm -3 .

[0048] Example 3

[0049] This embodiment is a preparation method of a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery, which is specifically as follows:

[0050] 1) The Si substrate 300 is pre-treated by grinding with diamond powder having a particle size of 0.5 mm until dense and uniform scratches appear on the silicon wafer, and then ultrasonically cleaning the silicon wafer with acetone and ethanol solution at a frequency of 40 kHz for 10 minutes.

[0051] 2) Using MPCVD method to grow p-type diamond film 200: the reaction gases are CH4, H2 and B2H6, wherein the flow rate of CH4 is 60sccm, the flow rate of H2 is 1000sccm, and the flow rate of B2H6 is 30sccm. The doping amount can be controlled by controlling the flow rate of the mixed gas. In this embodiment, the doping amount is controlled by adjusting the flow rate of B2H6, and the doping concentration is 5×10 18 cm -3 The p-type diamond film 200 was deposited on the Si substrate 300, with a microwave output power of 1 kW, a working gas pressure of 3 kPa, a substrate temperature of 750°C, and a deposition time of 2 h.

[0052] 3) A ZnO seed layer is plated on the surface of the p-type diamond film 200 by using a radio frequency magnetron sputtering method: the p-type diamond film 200 is ultrasonically cleaned with acetone and ethanol solution for 10 minutes, then rinsed with distilled water, and finally dried with nitrogen, placed in a vacuum chamber of a magnetron sputtering device and evacuated, oxygen and argon are introduced, and the flow ratio of oxygen and argon is 1:3, and the radio frequency distribution network is adjusted for ignition and sputtering. The growth conditions of magnetron sputtering are: radio frequency power 130W, sputtering temperature 400℃, and growth time 3 minutes.

[0053] 4) Using a hydrothermal method to prepare ZnO nanowires 100, weigh Zn(NO3)2·6H2O and C6H 12 N4 (hexamethylenetetramine) powder was dissolved in deionized water to prepare a mixed solution with a concentration of 0.1 mol / L, and then H3BO3 (boric acid) solution was added and stirred. The mixed solution was poured into a reactor, and sealed with a p-type diamond film 200 coated with a ZnO seed layer and placed together in the reactor. The reactor was placed in a drying oven and heated at a constant temperature of 120°C for 6 hours. After the reaction was completed, the sample was naturally cooled to room temperature, the sample surface was taken out, and the sample surface was rinsed and naturally dried.

[0054] 5) Loading the radiation source 400 onto the surface of the ZnO nanowire 100: Selecting a β radiation source 90 Sr- 90 Y is directly applied on the surface of ZnO nanowires, with a surface activity of 1 μCi / cm 2 .

[0055] 6) Assembling electrodes and housing 500: Using silver paste as the electrode material, coating both ends of the ZnO nanowires and the p-type diamond film.

[0056] In summary, the present invention provides a nuclear battery based on zinc oxide nanowire-diamond heterojunction type β-radiovoltaic effect, which integrates the radiation source between the nano ZnO array and the diamond film, thereby improving the utilization efficiency of the nuclear battery for β particles, reducing the influence of the surface state, and reducing the recombination rate of carriers, thereby improving the conversion efficiency of the battery. The nuclear battery avoids the asymmetric problem of wide bandgap semiconductor doping. The existence of the nanostructure makes the utilization efficiency of the nuclear battery for β particles higher than that of the planar structure, the influence of the surface state is relatively small, and the recombination rate of carriers is significantly reduced, thereby improving the conversion efficiency of the battery and obtaining a higher open circuit voltage and short circuit current.

[0057] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. A zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery, characterized in that: include, ZnO nanowires (100); p-type diamond film (200); Si substrate (300); Radioactive source (400); Housing (500); The radiation source (400) is loaded above the ZnO nanowire (100) and between the ZnO nanowire (100) and the p-type diamond film (200).

2. The zinc oxide nanowire-diamond heterojunction β-radiation voltaic effect nuclear battery according to claim 1, characterized in that: The p-type diamond film (200) and the ZnO nanowire (100) form a heterojunction structure.

3. The zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery according to claim 1, characterized in that: The diameter of the ZnO nanowire (100) is 100-500 nm.

4. The zinc oxide nanowire-diamond heterojunction β-radiation voltaic effect nuclear battery according to claim 1, characterized in that: The doping concentration of the p-type diamond film (200) is 10 17 ~10 19 cm -3 .

5. The method for preparing a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery according to any one of claims 1 to 4, characterized in that: include, Pre-treating the Si substrate (300); Growing a p-type diamond film (200) using an MPCVD method; A ZnO seed crystal layer is plated on the surface of a p-type diamond film (200) by using a radio frequency magnetron sputtering method: after the p-type diamond film (200) is cleaned and blown dry, it is placed in a vacuum chamber of a magnetron sputtering device and evacuated, oxygen and argon are introduced, and the radio frequency distribution network is adjusted for ignition and pre-sputtering; Preparation of ZnO nanowires (100) by hydrothermal method: Zn(NO3)2·6H2O and C6H 12 N4 powder is dissolved in deionized water to prepare a solution, and then H3BO3 solution is added and stirred. The mixed solution is poured into a reactor, and the mixture is sealed with a p-type diamond film (200) coated with a ZnO seed layer and placed in the reactor together. The reactor is placed in a drying oven and heated at a constant temperature, and then cooled naturally to room temperature. The sample is taken out, the sample surface is rinsed and dried naturally; Loading a radiation source (400) on the surface of the ZnO nanowire (100); The electrodes and housing (500) are assembled.

6. The method for preparing a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery according to claim 5, characterized in that: The pretreatment includes mechanical grinding and ultrasonic cleaning.

7. The method for preparing a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery according to claim 5, characterized in that: The reaction gases of the MPCVD method include CH4, H2, and B2H6.

8. The method for preparing a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery according to claim 5, characterized in that: The p-type diamond film (200) is ultrasonically cleaned using acetone and ethanol solutions.

9. The method for preparing a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery according to claim 5, characterized in that: The diameter of the ZnO nanowire (100) is 100-500 nm.

10. The method for preparing a zinc oxide nanowire-diamond heterojunction type β-radiation voltaic effect nuclear battery according to claim 5, characterized in that: The doping concentration of the p-type diamond film (200) is 10 17 ~10 19 cm -3 .

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