90Sr (NO3) 2 base-based three-dimensional array photovoltaic double-effect beta nuclear battery and preparation method thereof

Abstract

The invention discloses a 90Sr (NO3) 2 base-based three-dimensional array photovoltaic double-effect beta nuclear battery and a preparation method thereof, the three-dimensional structure is formed by taking a Si microchannel structure as an integral skeleton, depositing ZnO in a Si microchannel array pore channel and packaging an organic liquid scintillator loaded with CsPbI3 quantum dots, and the structure sequentially comprises, from inside to outside, an organic liquid scintillator loaded with CsPbI3 quantum dots, an organic liquid scintillator loaded with the CsPbI3 quantum dots, an organic liquid scintillator loaded with the CsPbI3 quantum dots, an organic liquid According to the three-dimensional array beta nuclear battery, a hydroxylated n-type doped Si-based micro-channel structure, p-type doped ZnO, an organic liquid scintillator loaded with CsPbI3 quantum dots, a radiation source 90Sr (NO3) 2, a positive electrode, a back electrode and a sealing shell are adopted, and compared with a traditional plane coupling structure, the prepared three-dimensional array beta nuclear battery has the advantages that the contact area of the scintillator and a semiconductor transducer is increased, the carrier diffusion length in a pn junction is increased, and the performance of the scintillator is improved; compounding of electron hole pairs is limited, separation and directional collection of the electron hole pairs are facilitated, and the performance of the battery is further improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of nuclear batteries and specifically relates to a 90 Sr(NO3)2-based three-dimensional array photovoltaic dual-effect beta-nuclear battery and preparation method thereof. Background Art

[0002] Nuclear batteries are devices that generate electrical energy through ionizing radiation, radiation heat effect, and radiation light effect from alpha particles, beta particles, X-rays, and gamma rays released by the natural decay of radioactive isotopes. Compared with traditional chemical batteries, nuclear batteries have stronger environmental adaptability and are not affected by temperature, humidity, air pressure and other conditions; the energy released by the decay of radioactive sources has a higher energy density, which is conducive to the energy application of miniaturized devices; the half-life of radioactive sources is longer, which ensures a longer maintenance-free cycle for the battery. Therefore, the advantages of high environmental adaptability, high energy density, long life, and low output power make nuclear batteries an excellent stable energy source in many fields such as deep sea and deep space exploration, biomedicine, and MEMS.

[0003] In order to obtain a longer working life and reduce the radiation damage caused by the radioactive source in the nuclear battery to the transducer device, in practical applications, a radioactive source with a longer half-life, lower source activity, lower average decay energy, and higher energy density is usually used. This directly affects the power density of the nuclear battery and limits the development of nuclear battery applications in certain fields requiring high power density.

[0004] 90 As a typical high-energy β source, Sr not only has extremely high power density, but also is relatively cheap and easy to obtain as radioactive waste from nuclear reactors, which is a breakthrough in improving the power density of β nuclear batteries. However, it is also limited by the radiation damage of high-energy particles to the transducer components. 90 The application of Sr in β-nuclear batteries is difficult to promote on a large scale.

[0005] Cesium lead halide perovskite quantum dots are a new type of fluorescent material with a general chemical formula of CsPbX3 (X = Br, Cl, I), which has a high quantum yield and an extremely narrow emission band. By controlling the composition and size of quantum dots, the entire visible spectrum can be emitted, so it has attracted widespread attention in the fields of light-emitting diodes, solar cells, biological detection, etc. 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 90 Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-core battery.

[0009] In order to solve the above technical problems, the present invention provides the following technical solutions: the structure of the three-dimensional array photovoltaic dual-effect β-nuclear battery from inside to outside includes:

[0010] Hydroxylated n-type doped Si-based microchannel structure 1;

[0011] p-type doped ZnO 2;

[0012] Organic liquid scintillator 3 loaded with CsPbI3 quantum dots;

[0013] Radiation source 90 Sr (NO3)24;

[0014] Positive electrode 5, back electrode 6, sealing shell 7.

[0015] As the present invention is based on 90 A preferred solution of a Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-core battery, wherein: the three-dimensional structure of the three-dimensional array photovoltaic dual-effect β-core battery uses a Si microchannel structure as the overall skeleton, ZnO is deposited in the Si microchannel array pores and an organic liquid scintillator loaded with CsPbI3 quantum dots is encapsulated.

[0016] The purpose of the present invention is to provide a 90 A method for preparing a Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery.

[0017] In order to solve the above technical problems, the present invention provides the following technical solutions: the structure of the three-dimensional array photovoltaic dual-effect β-nuclear battery from inside to outside includes:

[0018] The Si microporous structure 1 is formed by photolithography combined with electrochemical etching;

[0019] The surface of the Si microporous structure 1 is subjected to hydroxylation treatment using a piranha solution to obtain a hydroxylated Si microporous structure;

[0020] A ZnO layer was deposited on the surface of the hydroxylated Si microporous structure by ALD method to obtain p-type doped ZnO 2;

[0021] The organic liquid scintillator loaded with CsPbI3 quantum dots is encapsulated in a hydroxylated Si microporous structure deposited with p-type doped ZnO2 to obtain an organic liquid scintillator 3;

[0022] The corresponding load radiation source is on the organic liquid scintillator 390 Sr(NO3)24;

[0023] Then, under the cover of the mask, the corresponding positive electrode 5 and the back electrode 6 are sealed to form a sealed shell 7, that is, a 90 Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-core battery.

[0024] As the present invention is based on 90 A preferred method for preparing a Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery, wherein: the Si microporous structure 1 is a micro square hole.

[0025] As the present invention is based on 90 A preferred method for preparing a Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery, wherein: the electrochemical etching method for forming the Si microporous structure 1 includes:

[0026] The Si substrate is corroded using a KOH corrosion solution to obtain square induced pits. The silicon wafer containing the induced pits is placed in the corrosion solution. The positive pole of the power supply is connected to the silicon wafer containing the induced pits, and the negative pole of the power supply is connected to the platinum electrode. The silicon wafer containing the induced pits reacts chemically with the corrosion solution.

[0027] As the present invention is based on 90 A preferred method for preparing a Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery, wherein: the hydroxylation treatment includes:

[0028] The Si microporous structure 1 is completely immersed in the piranha solution and allowed to react. After the reaction is completed, the structure is placed in a megahertz ultrasonic cleaning machine for megasonic cleaning. Finally, the sample is taken out and rinsed and blown dry.

[0029] As the present invention is based on 90 A preferred method for preparing a Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery, wherein: the matrix material of the organic liquid scintillator is toluene.

[0030] As the present invention is based on 90 A preferred method for preparing a Sr(NO3)2-based three-dimensional array photovoltaic dual-effect beta-nuclear battery, wherein: the first scintillation material of the organic liquid scintillator is 2-(4-biphenyl)-5-phenyloxadiazole.

[0031] As the present invention is based on 90 A preferred method for preparing a Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery, wherein: the wave shifter of the organic liquid scintillator is 9,10-diphenylanthracene.

[0032] As the present invention is based on 90 A preferred method for preparing a Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery, wherein: the material of the positive electrode 5 and the back electrode 6 is Au.

[0033] Beneficial effects of the present invention:

[0034] (1) The present invention transforms the traditional energy conversion method in which high-energy decay particles directly interact with semiconductor energy conversion materials into one in which high-energy decay particles interact with scintillators and semiconductor energy conversion materials respectively, wherein most of the decay energy acts on the scintillator, and the photons generated by its radioluminescence in the scintillator further interact with the semiconductor energy conversion device, forming electron-hole pairs in the semiconductor energy conversion device, which are separated by the built-in electric field of the depletion region of ZnO / Si, and move in a directional manner respectively, and current can be formed after the external circuit is connected. The energy conversion process from decay energy to light energy to electrical energy is completed, thereby effectively avoiding radiation damage caused by the direct interaction of high-energy decay particles with semiconductor energy conversion devices, and expanding the 90 Application of Sr-based β-nuclear batteries.

[0035] (2) Compared with the traditional planar coupling structure, the three-dimensional array β-nuclear battery prepared by the present invention increases the contact area between the scintillator and the semiconductor transducer device, increases the carrier diffusion length in the pn junction, limits the recombination of electron-hole pairs, and helps to separate and directional collect electron-hole pairs, thereby improving battery performance.

[0036] (3) The method of hydroxylating the pores of the Si-based microchannel structure using piranha solution adopted in the present invention can effectively improve the deposition quality of the radiation source in the ALD process and optimize the quality of the pn junction.

[0037] (4) The silver-plated closed shell used in the present invention can effectively reduce the energy loss caused by backscattering of the radiation source, which helps to increase energy utilization. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] 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 labor. Among them:

[0039] Figure 1 The present invention is based on 90 Schematic diagram of the structure of Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery. DETAILED DESCRIPTION

[0040] 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.

[0041] 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.

[0042] 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.

[0043] Unless otherwise specified, the raw materials used in the present invention are all commercially available in the art.

[0044] Example 1

[0045] Reference Figure 1 The present invention provides a method based on 90 Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery and its preparation method, Figure 1 1 represents the hydroxylated n-type doped Si-based microchannel structure, 2 represents the p-type doped ZnO, 3 represents the organic liquid scintillator loaded with CsPbI3 quantum dots, and 4 represents the radiation source 90 Sr (NO3)2, 5 represents the positive electrode, 6 represents the back electrode, and 7 represents the sealed shell. Specifically:

[0046] S1. Photolithography combined with electrochemical etching to obtain Si-based microchannel structure:

[0047] Photolithography part: First, a layer of SiO2 film is grown on a silicon substrate by thermal oxidation method (thermal oxidation temperature is 1000℃), and a Si3N4 mask is prepared by low-pressure chemical vapor deposition (LPCVD, growth temperature is set to 700℃, argon oxygen ratio is 200:10, growth pressure is 180Pa, substrate bias angle is 4°). P is doped by diffusion to prepare an ohmic contact layer, and micro square holes of the required size are etched by photolithography. The silicon substrate is corroded with KOH etching solution to prepare square hole induction pits.

[0048] Electrochemical etching part: put the silicon wafer containing the induced pit into the corrosion solution, connect the positive electrode of the power supply to the silicon wafer containing the induced pit, connect the negative electrode of the power supply to the platinum electrode, put it into the KOH corrosion solution, and the silicon wafer with the induced pit reacts chemically with the corrosion solution. The power supply current density is 35mA / cm 2 , the applied voltage was 0.3 V, the etching time was 12 hours, and finally a silicon microchannel array structure was prepared.

[0049] S2. Hydroxylation treatment is performed on the pores of the silicon microchannel array using piranha solution:

[0050] The Si microchannel array was placed in a beaker filled with piranha solution (98% concentrated sulfuric acid and 30% hydrogen peroxide mixed in a ratio of 7:3), and the beakers were placed in a water bath at 80°C for 20 minutes, and then placed in a megahertz ultrasonic cleaner for cleaning for 8 minutes. After the sample was taken out, it was washed three times with deionized water for 2 minutes each time, and then dried with N2 for use.

[0051] S3. Depositing ZnO in the hydroxylated Si microchannel array channels by ALD:

[0052] Diethyl zinc (DEZn) and H2O were used as precursors. The chamber temperature was set at 200°C. DEZn vapor was first blown into the chamber in a pulsed form at 150°C and adsorbed on the surface of the Si microchannel array. Excess precursor was blown away with N2 as the purge gas. Then H2O was introduced to reduce the DEZn precursor adsorbed on the surface of the Si microchannel array. 30 ALD cycles were performed.

[0053] After the cycle, the sample was cooled to room temperature in a 100 sccm N2 atmosphere, and then the chamber was opened to take out the prepared sample, followed by annealing at 400°C for 30 min in a 5% H2 and 95% Ar atmosphere.

[0054] S4. Encapsulate the organic liquid scintillator loaded with CsPbI3 quantum dots in the microporous structure processed by S3.

[0055] S5. The corresponding loaded metal electrode under the cover of the mask:

[0056] A mask with pore distribution consistent with the Si-based microchannel array is covered thereon, Au is loaded as a positive electrode, and Au is loaded on the back side of the Si-based microchannel array as a back electrode.

[0057] S6. Fill the corresponding load radiation source layer on the scintillator layer in step S3:

[0058] Under the action of mechanical pressure 90 Sr(NO3)2 is loaded in the depressions on the scintillator.

[0059] Finally, the battery is encapsulated in a closed shell with silver plating inside, and the battery is obtained. 90 Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-core battery.

[0060] The present invention transforms the traditional energy conversion mode in which high-energy decay particles directly interact with semiconductor energy conversion materials into one in which high-energy decay particles interact with scintillators and semiconductor energy conversion materials respectively, wherein most of the decay energy acts on the scintillator, and the photons generated by its radioluminescence in the scintillator further interact with the semiconductor energy conversion device, and the electron-hole pairs formed in the semiconductor energy conversion device are separated by the built-in electric field of the depletion region of ZnO / Si, and move in a directional manner respectively, and current can be formed after the external circuit is connected. The energy conversion process from decay energy to light energy to electrical energy is completed, thereby effectively avoiding radiation damage caused by the direct interaction of high-energy decay particles with semiconductor energy conversion devices, and expanding the 90 Application of Sr-based β-nuclear batteries.

[0061] Compared with the traditional planar coupling structure, the three-dimensional array β-nuclear battery prepared by the present invention increases the contact area between the scintillator and the semiconductor transducer device, increases the carrier diffusion length in the pn junction, limits the recombination of electron-hole pairs, and helps to separate and directional collect electron-hole pairs, thereby improving battery performance.

[0062] The method of hydroxylating the pores of the Si-based microchannel structure by using a piranha solution adopted by the present invention can effectively improve the deposition quality of the radiation source in the ALD process and optimize the quality of the pn junction.

[0063] The closed shell with silver plating inside adopted by the present invention can effectively reduce the energy loss caused by the backscattering of the radiation source, which is helpful to increase the energy utilization rate.

[0064] 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 method based on 90 Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery, characterized by: The structure of the three-dimensional array photovoltaic dual-effect β-nuclear battery from inside to outside includes: Hydroxylated n-type doped Si-based microchannel structure (1); p-type doped ZnO(2); Organic liquid scintillator loaded with CsPbI3 quantum dots (3); Radiation Source 90 Sr(NO3)2(4); Positive electrode (5), back electrode (6), sealing shell (7).

2. The method according to claim 1 90 Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery, characterized by: The three-dimensional structure of the three-dimensional array photovoltaic dual-effect beta-core battery uses a Si microchannel structure as an overall skeleton, and ZnO is deposited in the Si microchannel array pores and an organic liquid scintillator loaded with CsPbI3 quantum dots is encapsulated.

3. The method according to any one of claims 1 or 2. 90 The preparation method of Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery is characterized by: include, Forming Si microporous structure (1) by photolithography combined with electrochemical etching; The surface of the Si microporous structure (1) is subjected to hydroxylation treatment using a piranha solution to obtain a hydroxylated Si microporous structure; A ZnO layer was deposited on the surface of the hydroxylated Si microporous structure by ALD method to obtain p-type doped ZnO (2); Encapsulating an organic liquid scintillator loaded with CsPbI3 quantum dots in a hydroxylated Si microporous structure deposited with a p-type doped ZnO layer (2) to obtain an organic liquid scintillator (3); A corresponding load radiation source 90 is placed on the organic liquid scintillator (3). Sr (NO3)2(4); Then, under the cover of the mask, the corresponding positive electrode (5) and the back electrode (6) are sealed to form a sealed shell (7), thus obtaining a base 90 Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-core battery.

4. The method according to claim 2 90 The preparation method of Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery is characterized by: The Si microporous structure (1) is micro square pores.

5. The method according to claim 2 90 The preparation method of Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery is characterized by: The electrochemical etching method for forming the Si microporous structure (1) comprises: The Si substrate is corroded using a KOH corrosion solution to obtain square induced pits. The silicon wafer containing the induced pits is placed in the corrosion solution. The positive pole of the power supply is connected to the silicon wafer containing the induced pits, and the negative pole of the power supply is connected to the platinum electrode. The silicon wafer containing the induced pits reacts chemically with the corrosion solution.

6. The method according to claim 2 90 The preparation method of Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery is characterized by: The hydroxylation treatment comprises: The Si microporous structure (1) is completely immersed in the piranha solution and allowed to react. After the reaction is completed, it is placed in a megahertz ultrasonic cleaning machine for megasonic cleaning. Finally, the sample is taken out and rinsed and blown dry.

7. The method according to claim 2 90 The preparation method of Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery is characterized by: The base material of the organic liquid scintillator is toluene.

8. The method according to claim 7 90 The preparation method of Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery is characterized by: The first scintillating material of the organic liquid scintillator is 2-(4-biphenyl)-5-phenyloxadiazole.

9. The method according to claim 8 90 The preparation method of Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery is characterized by: The wave shifter of the organic liquid scintillator is 9,10-diphenylanthracene.

10. The method according to claim 2 90 The preparation method of Sr(NO3)2-based three-dimensional array photovoltaic dual-effect β-nuclear battery is characterized by: The material of the positive electrode (5) and the back electrode (6) is Au.

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