Preparation method and application of three-dimensional structure based on Si microchannel array
By adopting a three-dimensional structure based on Si microchannel array in β-radiation volt-effect nuclear batteries, combining photolithography with electrochemical etching and ALD method to deposit radiation sources, the problems of radiation from absorption effects and limited deposition depth in existing nuclear batteries are solved, and more efficient energy conversion and cell performance improvement are achieved.
Patent Information
- Application Number
- CN202411602666.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-11
- Publication Date
- 2025-04-08
AI Technical Summary
The existing β-radiation volt-effect nuclear batteries have limited deposition depth due to the planar structure of the radiation source decayed particles, resulting in difficulty in improving output performance and low energy conversion efficiency.
The Si microchannel array is prepared by combining photolithography and electrochemical etching, and then hydroxylation is performed using a piranha solution, and a radio source is deposited in the Si microchannel array channel by the ALD method to form a structure of the radio source and the semiconductor transduction unit.
Through the design of the three-dimensional structure, the decayed particles of the radiosource directly interact with the semiconductor material, avoiding the self-absorbing effect, improving the energy conversion efficiency, and increasing the carrier diffusion length, limiting the recombination of electron-hole pairs, thereby improving battery performance.
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Figure CN119786113A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of semiconductor device preparation, and in particular relates to a preparation method of a three-dimensional structure based on a Si microchannel array and an application thereof. Background Art
[0002] As human beings continue to explore deep space and deep sea, long-life, stable output power, and energy have become a research hotspot. Different from traditional micro power sources, β-radiation voltaic effect nuclear batteries have the characteristics of high power density, maintenance-free and long life, and are ideal stable power sources in extreme environments.
[0003] Existing β-radiation voltaic effect nuclear batteries mainly make the radiation source into a planar structure and place it on the surface of a semiconductor transducer unit device. This structure will cause the battery to be limited by the absorption effect of the radiation source, making it difficult to significantly improve the output performance. In addition, the planar stacked structure inevitably leads to a limited deposition depth of the radiation source decay particles in the semiconductor transducer device, which is also the reason for the low energy conversion efficiency of nuclear batteries.
[0004] At present, there is still a large gap between the actual value of the energy conversion efficiency of wide bandgap semiconductors and the theoretical prediction value. Researchers have conducted extensive research to further improve the energy conversion efficiency. Among them, the three-dimensional array structure can further expand the contact area between the radiation source and the semiconductor transducer device, effectively increase the energy deposition of the radiation source decay particles in the semiconductor transducer unit, and thus significantly improve the output performance of the battery. Summary of the invention
[0005] 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.
[0006] In view of the above problems and / or the problems existing in the prior art, the present invention is proposed.
[0007] Therefore, the object of the present invention is to overcome the deficiencies in the prior art and provide a method for preparing a three-dimensional structure based on a Si microchannel array.
[0008] In order to solve the above technical problems, the present invention provides the following technical solutions: a method for preparing a three-dimensional structure based on a Si microchannel array is provided, characterized in that: it comprises:
[0009] The Si microchannel array was prepared by combining photolithography with electrochemical etching: etching-induced pits were prepared by photolithography, and electrochemical etching was performed on the basis of the pits to wet-shape and polish the microchannels;
[0010] The piranha solution was used to hydroxylate the pores of the Si microchannel array;
[0011] ALD was used to deposit radioactive sources in the pores of hydroxylated Si microchannel arrays.
[0012] As a preferred solution of the preparation method of the present invention, wherein: the micro square holes of the required size are etched by photolithography.
[0013] As a preferred embodiment of the preparation method of the present invention, the Si substrate is corroded using a KOH corrosive solution to obtain square induced pits.
[0014] As a preferred embodiment of the preparation method described in the present invention, a silicon wafer containing induced pits is placed in a corrosion solution, the positive electrode of the power supply is connected to the silicon wafer containing the induced pits, the negative electrode of the power supply is connected to a platinum electrode, and placed in the corrosion solution, and the silicon wafer containing the induced pits reacts chemically with the corrosion solution.
[0015] As a preferred embodiment of the preparation method of the present invention, the piranha solution comprises H2O2 and concentrated H2SO4, and the volume ratio of concentrated 98% H2SO4:30% H2O2 is 7:3.
[0016] As a preferred embodiment of the preparation method of the present invention, the hydroxylation process of the Si microchannel array is to completely immerse the prepared Si microchannel array in a piranha solution and allow it to react, and after the reaction is completed, place it in a megahertz ultrasonic cleaning machine for megasonic cleaning, and finally take out the sample and rinse and blow dry.
[0017] As a preferred embodiment of the preparation method of the present invention, the deposition process of the radioactive source is to blow the radioactive source precursor into the reaction chamber in a pulsed form, and adsorb it on the growth sites on the surface of the hydroxylated Si microchannel array and undergo a self-limiting reaction. After all sites reach saturated adsorption, the excess precursor is blown out of the reaction chamber by an inert gas to complete a cycle.
[0018] As a preferred embodiment of the preparation method of the present invention, the radiation source used is 63 NiO.
[0019] Another object of the present invention is to overcome the deficiencies in the prior art and provide a three-dimensional structure of a Si microchannel array, wherein: the three-dimensional structure uses the Si microchannel structure as the overall skeleton and deposits radiation sources in the pores of the Si microchannel array.
[0020] Another object of the present invention is to overcome the shortcomings of the prior art and provide an application of a three-dimensional structure of a Si microchannel array in the preparation of a three-dimensional array integrated energy loading / conversion β-nuclear battery, wherein the three-dimensional skeleton structure and two electrodes derived from the Si microchannel structure and the radiation source layer.
[0021] Beneficial effects of the present invention:
[0022] 1. The present invention combines the radiation source and the semiconductor transducer unit into one. The decay particles of the radiation source directly interact with the semiconductor material, and the radiation-induced electron-hole pairs are 63 The built-in electric field in the depletion region of NiO / Si is separated and moves in a direction respectively, and current can be generated when the external circuit is connected.
[0023] 2. The present invention combines the radiation source and the semiconductor energy conversion unit into one, and the decay particles of the radiation source directly interact with the semiconductor material, thereby avoiding the negative impact of the self-absorption effect of the radiation source material on energy conversion and further improving the energy conversion efficiency of the device.
[0024] 3. Compared with the traditional planar coupling structure, the three-dimensional array carrier / converter integrated β-nuclear battery prepared by the present invention increases the carrier diffusion length in the pn junction, limits the recombination of electron-hole pairs, helps to separate and directional collect electron-hole pairs, and thus improves battery performance.
[0025] 4. The method of hydroxylating the pores of the Si-based microchannel structure by 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. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] 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:
[0027] Figure 1 Schematic diagram of a three-dimensional array energy-carrying / energy-converting integrated β-nuclear battery based on a Si-based microchannel structure in Example 1 of the present invention. DETAILED DESCRIPTION
[0028] 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.
[0029] 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.
[0030] 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.
[0031] Unless otherwise specified, the reagents and raw materials used in the present invention are commercially available.
[0032] Example 1
[0033] 1. Photolithography combined with electrochemical etching to obtain Si-based microchannel structure:
[0034] Photolithography part: First, a layer of SiO2 film is grown on the silicon substrate by thermal oxidation method, a Si3N4 mask is prepared by LPCVD, P is doped by diffusion to prepare an ohmic contact layer, micro square holes of the required size are etched by photolithography, and the silicon substrate is corroded by KOH etching solution to prepare square hole induction pits.
[0035] Electrochemical etching part: Place the silicon wafer containing the induced pits in the corrosion solution, connect the positive pole of the power supply to the silicon wafer containing the induced pits, and connect the negative pole of the power supply to the platinum electrode. Place it in the corrosion solution, and the silicon wafer with the induced pits will react chemically with the corrosion solution. The power current density is 30-40 mA / cm2, the applied voltage is 0.2-0.4 V, and the etching time is 12 hours. Finally, a silicon microchannel array structure is prepared.
[0036] 2. Use piranha solution to perform hydroxylation treatment on the pores of the Si microchannel array prepared in step S1:
[0037] The Si microchannel array was placed in a beaker filled with piranha solution, 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 cleaned three times with deionized water for 2 minutes each time, and then dried with N2 for use.
[0038] 3. Deposition of 63NiO radiation source in the hydroxylated Si microchannel array channels by ALD method:
[0039] 63Ni(iPr-DAD)2 and NH3 were used as precursors, and the chamber temperature was set to 200°C. First, 63Ni(iPr-DAD)2 vapor was blown into the chamber in a pulsed form at 150°C and adsorbed on the surface of the Si microchannel array pores. N2 was used as a purge gas to blow away the excess precursor, and then NH3 was introduced to reduce the 63Ni precursor adsorbed on the surface of the Si microchannel array pores. 30 ALD cycles were performed.
[0040] After preparation, it 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. Electrodes were drawn out from the Si and 63NiO ends respectively to obtain a three-dimensional array load / conversion integrated β-nuclear battery based on a Si-based microchannel structure.
[0041] The battery is encapsulated in a sealed shell, and a three-dimensional array of energy-carrying / converting integrated β-nuclear batteries based on Si-based microchannel structures are used. Figure 1 shown.
[0042] 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 for preparing a three-dimensional structure based on a Si microchannel array, characterized in that: include, The Si microchannel array was prepared by combining photolithography with electrochemical etching: etching-induced pits were prepared by photolithography, and electrochemical etching was performed on the basis of the pits to wet-shape and polish the microchannels; The piranha solution was used to hydroxylate the pores of the Si microchannel array; ALD was used to deposit radioactive sources in the pores of hydroxylated Si microchannel arrays.
2. The preparation method according to claim 1, characterized in that: The photolithography method is used to etch micro square holes of a required size.
3. The preparation method according to claim 1, characterized in that: The Si substrate was etched using a KOH etching solution to obtain square induced pits.
4. The preparation method according to claim 1, characterized in that: Place the silicon wafer containing the induced pits in the corrosion solution, connect the positive pole of the power supply to the silicon wafer containing the induced pits, and connect the negative pole of the power supply to the platinum electrode. Place it in the corrosion solution, and the silicon wafer with the induced pits will react chemically with the corrosion solution.
5. The preparation method according to claim 1, characterized in that: The piranha solution includes H2O2 and concentrated H2SO4, and the volume ratio of concentrated 98% H2SO4:30% H2O2 is 7:
3.
6. The preparation method according to claim 1, characterized in that: The hydroxylation process of the Si microchannel array is as follows: the prepared Si microchannel array is completely immersed in the piranha solution and allowed to react, and after the reaction is completed, the array is placed in a megahertz ultrasonic cleaning machine for megasonic cleaning, and finally the sample is taken out and rinsed and blown dry.
7. The preparation method according to claim 1, characterized in that: The deposition process of the radioactive source is to blow the radioactive source precursor into the reaction chamber in a pulsed form, and adsorb it on the growth sites on the surface of the hydroxylated Si microchannel array to undergo a self-limiting reaction. After all sites reach saturated adsorption, the excess precursor is blown out of the reaction chamber by an inert gas to complete a cycle.
8. The preparation method according to claim 1, characterized in that: The radioactive source used is 63 NiO.
9. The three-dimensional structure of the Si microchannel array prepared by the preparation method according to any one of claims 1 to 7, characterized in that: The three-dimensional structure uses the Si microchannel structure as the overall framework, and the radiation source is deposited in the Si microchannel array pores.
10. Application of a three-dimensional structure of a Si microchannel array in the preparation of a three-dimensional array integrated energy loading / conversion β-nuclear battery, characterized in that: It includes the three-dimensional skeleton structure and two electrodes derived from the Si microchannel structure and the radiation source layer.