A radiation-resistant reinforcement method for electronic devices based on perovskite / resin composite materials

Abstract

The present invention discloses a method for strengthening the radiation resistance of electronic devices based on perovskite / resin composite materials, which belongs to the field of radiation resistance strengthening. The radiation resistance strengthening method of the present invention includes three parts: preparation of Lewis base-modified perovskite powder, preparation of Lewis base-modified perovskite / resin slurry, and radiation resistance strengthening of electronic devices. A precursor solution containing a Lewis base is added to a reaction solvent containing a ligand and vigorously stirred to obtain a Lewis base-modified perovskite material, which is then compounded with a resin and coated on the surface of an electronic device to achieve radiation resistance strengthening of the electronic device. The interaction between the perovskite / resin composite material of the present invention and the incident high-energy electrons significantly attenuates the radiation energy, thereby reducing the energy deposition in the device and ensuring the electrical performance stability of the electronic device under high-energy electron radiation. It also has broad application prospects in aerospace engineering, radiation medicine, nuclear engineering and other fields.

Description

Technical Field

[0001] This invention belongs to the field of radiation hardening, specifically a method for hardening electronic devices against radiation using a perovskite / resin composite material. This invention is primarily used in aerospace engineering, but also has broad application prospects in fields such as radiation medicine and nuclear engineering. Background Art

[0002] With the rapid development of aerospace technology, the number of space exploration missions has increased significantly. A series of electronic devices, represented by MOSFET (Metal-Oxide-Semiconductor Field-Effect Transistor), play a vital role in space missions. Therefore, ensuring the normal operation of electronic devices is a prerequisite for the successful execution of space missions. The large amount of high-energy radiation in outer space interacts with electronic devices, causing various radiation damages such as total dose effect, single event effect, and displacement damage effect, which in turn cause a series of failures such as device flipping, latching, and burning. Therefore, it is necessary to carry out radiation hardening on electronic devices to ensure the normal operation of space exploration missions.

[0003] Currently, the main methods for radiation reinforcement of electronic devices include design reinforcement, packaging reinforcement, and process reinforcement. Among them, packaging reinforcement has the advantages of good protection effect, easy implementation, and strong versatility, and has received widespread attention from researchers in recent years. Studies have shown that the use of shielding materials to package and reinforce devices has a significant effect on shielding high-energy electrons in the space radiation environment, and is a direct and effective way to extend the service life of electronic devices. However, the radiation shielding materials currently used in electronic devices are mainly metal materials with higher atomic numbers such as lead and tantalum. Although they have excellent shielding effects, they have disadvantages such as high density and the tendency to generate bremsstrahlung when interacting with high-energy electrons, which limits their large-scale application. Therefore, there is an urgent need to develop lightweight and efficient radiation shielding materials.

[0004] Polymer-based composite materials are made by combining functional fillers and polymer matrices. They have the advantages of low density, good processability, and strong designability. By selecting appropriate functional fillers, they can effectively shield radiation. Lead halide perovskite has the advantages of high atomic number, abundant extranuclear electrons, and large inner electron binding energy, and is expected to become an excellent electron radiation shielding functional filler. The essence of electron radiation shielding is to use the interaction between radiation and the material's extranuclear electrons to attenuate energy. Therefore, electronic structure design and regulation is an effective strategy to improve the radiation shielding performance of materials. However, current research on radiation shielding functional fillers in composite materials remains at the macro level of filler size, filler dispersion, and filler component regulation. There are no reports on how to improve the radiation shielding performance of fillers from the perspective of electronic structure. Summary of the Invention

[0005] The present invention aims to enrich current design approaches for improving the radiation shielding properties of materials. By regulating the electronic structure of the material, a method for radiation-hardening electronic devices using a lightweight, low-toxic, and excellent radiation-shielding perovskite / resin composite material is provided. This radiation-hardening method comprises three steps: preparing a Lewis base-modified perovskite powder, preparing a Lewis base-modified perovskite / resin slurry, and then strengthening the electronic device against radiation. The present invention involves adding a Lewis base-containing precursor solution to a reaction solvent containing a ligand and vigorously stirring to produce a Lewis base-modified perovskite material. This material is then composited with a resin and coated on the surface of an electronic device to achieve radiation-hardening of the electronic device.

[0006] The method of the present invention has the advantages of fast reaction speed, controllable product size, mild reaction conditions, and the like.

[0007] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0008] The object of the present invention is to provide a method for strengthening the radiation resistance of electronic devices based on perovskite / resin composite materials, comprising the following steps:

[0009] Step 1: Preparation of Lewis base modified perovskite powder:

[0010] Using lead salt, cationic salt, oleic acid, oleylamine and Lewis base as raw materials, Lewis base modified perovskite powder can be prepared through ligand-assisted reprecipitation method;

[0011] Step 2: Prepare Lewis base modified perovskite / resin slurry:

[0012] Grinding the Lewis base modified perovskite powder obtained in step 1 with resin to obtain a Lewis base modified perovskite / resin slurry;

[0013] Step 3: Radiation hardening of electronic devices:

[0014] The slurry obtained in step 2 is coated on the surface of the electronic device and cured, thereby forming a Lewis base modified perovskite / resin composite material on the surface of the electron-emitting device.

[0015] Further defined, the specific operation of step 1 is as follows: dissolving the lead salt, the cationic salt and the Lewis base in N,N-dimethylformamide (DMF) to form a precursor solution A;

[0016] Add oleic acid and oleylamine to the organic solvent, stir and dissolve to form solution B;

[0017] The precursor solution A is quickly dropped into the solution B. After the reaction is completed, the Lewis base-modified perovskite powder is obtained by centrifugation, washing and drying.

[0018] It is further defined that the lead salt is one of lead bromide, lead iodide, lead chloride, etc.; the cationic salt is one of cesium bromide, methylamine hydrobromide, formamidine hydrobromide, etc.; and the Lewis base is a Lewis base such as thioacetamide (TAA), potassium thiocyanate (KSCN) or thiourea.

[0019] Further defined, the ratio of (0.01-0.1) mmol of lead salt, (0.04-0.4) mmol of cationic salt, and (0.001-0.01) mmol of Lewis base is added to 1 ml of DMF.

[0020] It is further defined that the organic solvent is n-hexane or ethyl acetate.

[0021] It is further defined that the volume ratio of the organic solvent to the total volume of oleic acid and oleylamine is 10 mL: (60-150) μL; the volume ratio of oleic acid to oleylamine is 1:2-2:1.

[0022] It is further defined that the volume ratio of solution A to solution B is 1:1 to 1:10.

[0023] It is further defined that in step 2, the mass ratio of the Lewis base modified perovskite powder to the resin is 1:9 to 7:3; and the resin is epoxy resin, polyethylene, polyurethane or cyanate ester.

[0024] It is further defined that in step 2, the grinding time is 5 minutes to 20 minutes, and a three-roll grinder can be used for grinding.

[0025] It is further defined that in step three, the coating method is scraping, brushing, spraying, or injection molding.

[0026] It is further defined that in step three, curing is carried out at 30° C. to 150° C. for 2 h to 24 h; and the thickness of the obtained composite material is 0.5 mm to 3 mm.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The present invention uses a simple ligand-assisted reprecipitation method to prepare Lewis base-modified perovskite powder with excellent radiation shielding performance;

[0029] The present invention modifies the perovskite material at the electronic level, increases the local electron density, and significantly improves the radiation shielding performance of the material. The prepared Lewis base-modified perovskite / resin composite material achieves excellent radiation-resistant reinforcement effect on electronic devices.

[0030] The Lewis base-modified perovskite prepared by the present invention has a smaller size than the unmodified perovskite, which increases the probability of collision between radiation and the material, and better achieves radiation resistance reinforcement for electronic devices;

[0031] Compared with existing anti-radiation reinforcement methods, the present invention uses a resin-based composite material system with characteristics such as light weight, low toxicity, and excellent radiation shielding performance, and has better technical effects in the anti-radiation reinforcement of electronic devices.

[0032] The present invention adopts a ligand-assisted reprecipitation method to prepare a Lewis base-modified perovskite powder. A precursor solution containing the reaction raw materials is quickly added to an antisolvent and vigorously stirred. After the perovskite is precipitated under the action of the antisolvent, the Lewis base is grafted onto the A and B position cations of the perovskite through Lewis acid-base pairing to obtain a Lewis base-modified perovskite powder.

[0033] The present invention uses Lewis acid-base pairing to graft Lewis bases onto the A and B cations in the perovskite material. The electron-donating group characteristics are used to increase the local electron density of the perovskite material, thereby increasing the probability of collision with electrons in the material when incident radiation is emitted. This makes it easier for incident electrons to collide multiple times in the material and attenuate their energy, thereby improving the radiation shielding performance of the material.

[0034] The Lewis base modifier added in the present invention can be grafted onto the perovskite material to generate inelastic scattering with the incident electrons, thereby changing the energy spectrum of the incident high-energy electrons and reducing the probability and energy of bremsstrahlung generated by the interaction between the high-energy electrons and the perovskite material, thereby forming a multi-level loss of incident electron energy.

[0035] The present invention uses a Lewis base as a passivating agent to reduce defects in the prepared perovskite material. The reduction of defects can increase the order of the atomic arrangement in the perovskite crystal material, thereby increasing the probability of interaction between the material and the incident electrons and also increasing the stability of the material under high-energy radiation.

[0036] The Lewis base modifier added in the present invention can act as a ligand to further limit the increase in the size of the perovskite grains. The reduction in the size of the functional filler increases the probability of its interaction with the incident electrons, further improving the radiation shielding performance of the material.

[0037] The interaction between the Lewis base modified perovskite / resin composite material of the present invention and the incident high-energy electrons significantly attenuates the radiation energy, thereby reducing the energy deposition in the device and ensuring the electrical performance stability of the electronic device under high-energy electron radiation.

[0038] In order to further understand the features and technical contents of the present invention, please refer to the following detailed description of the present invention and the accompanying drawings. However, the accompanying drawings are provided for reference and illustration only and are not intended to limit the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1(a) is the SEM image of Cs4PbBr6 powder;

[0040] Figure 1 (b) is the SEM image of KSCN-Cs4PbBr6 powder;

[0041] Figure 1 (c) is the SEM image of TAA-Cs4PbBr6 powder;

[0042] Figure 2 It is the XRD of Cs4PbBr6 powder, KSCN-Cs4PbBr6 powder and TAA-Cs4PbBr6 powder. DETAILED DESCRIPTION

[0043] The present invention will be described in detail below with reference to specific embodiments. The following embodiments will help those skilled in the art further understand the present invention and are not intended to limit the present invention in any way. It should be noted that those skilled in the art may make various modifications and improvements without departing from the scope of the present invention. These modifications and improvements are all within the scope of protection of the present invention.

[0044] Example 1: The radiation-resistant reinforcement method for electronic devices based on the perovskite / resin composite material in this embodiment includes the following steps:

[0045] (1) Preparation of potassium thiocyanate (KSCN) modified Cs4PbBr6 powder

[0046] First, accurately weigh 0.01mmol of lead bromide, 0.04mmol of cesium bromide, and 0.001mmol of KSCN into a clean beaker. Add 1mL of N,N-dimethylformamide (DMF) solvent to the beaker and stir until the powder is completely dissolved in DMF to form precursor solution A. Add 100μL of oleic acid and 50μL of oleylamine to 10ml of n-hexane and stir for 10 minutes to mix thoroughly to form solution B. Quickly drop 1mL of precursor solution A into solution B with vigorous stirring. Stop the reaction after 30 minutes. Then, centrifuge, wash, and dry to obtain KSCN-modified Cs4PbBr6 powder.

[0047] (2) Preparation of KSCN-modified Cs4PbBr6 / epoxy resin slurry

[0048] The KSCN-modified Cs4PbBr6 powder obtained above was mixed with epoxy resin in a mass ratio of 2:8. The mixture was thoroughly ground using a three-roll mill for 10 minutes to obtain a modified KSCN-Cs4PbBr6 / epoxy resin slurry.

[0049] (3) Radiation hardening of electronic devices

[0050] The obtained slurry was coated on the surface of the electronic device by blade coating with a thickness of 1 mm, and then placed in a forced air drying oven and cured at 60°C for 6 hours to form a KSCN-Cs4PbBr6 / epoxy resin composite material to obtain a radiation-resistant electronic device.

[0051] Example 2: The radiation-resistant reinforcement method for electronic devices based on the perovskite / resin composite material in this example includes the following steps:

[0052] (1) Preparation of thioacetamide (TAA) modified Cs4PbBr6 powder

[0053] First, accurately weigh 0.01mmol of lead bromide, 0.04mmol of cesium bromide, and 0.001mmol of TAA into a clean beaker. Add 1mL of N,N-dimethylformamide (DMF) solvent to the beaker and stir until the powder is completely dissolved in DMF to form precursor solution A. Add 100μL of oleic acid and 50μL of oleylamine to 10ml of n-hexane and stir for 10 minutes to mix thoroughly to form solution B. Quickly drop 1mL of precursor solution A into solution B with vigorous stirring. Stop the reaction after 30 minutes, then centrifuge, wash, and dry to obtain TAA-modified Cs4PbBr6 powder.

[0054] (2) Preparation of TAA-modified Cs4PbBr6 / epoxy resin slurry

[0055] The TAA-modified Cs4PbBr6 powder obtained above was mixed with epoxy resin in a mass ratio of 2:8. The two were thoroughly ground using a three-roll mill for 10 minutes to obtain a modified TAA-Cs4PbBr6 / epoxy resin slurry.

[0056] (3) Radiation hardening of electronic devices

[0057] The obtained slurry was coated on the surface of the electronic device by blade coating with a thickness of 1 mm, and then placed in a forced air drying oven and cured at 60°C for 6 hours to form a TAA-Cs4PbBr6 / epoxy resin composite material to obtain a radiation-resistant electronic device.

[0058] The radiation-resistant electronic devices in Examples 1 and 2 were tested for electron irradiation performance using the following method:

[0059] Electron irradiation test: Using an electron accelerator to generate 1MeV electrons to irradiate radiation-resistant electronic devices, the following performance data was obtained.

[0060] Table 1: Threshold voltage shift after irradiation of unreinforced electronic devices, electronic devices not reinforced with modified materials, and radiation-resistant electronic devices prepared in Examples 1 and 2

[0061]

[0062] The perovskite powders in Examples 1 and 2 were tested for morphology and phase composition, and the test results are as follows:

[0063] The morphology test results are as follows Figure 1 As shown by Figure 1 It can be seen that the particle size of the Lewis base-modified perovskite powder prepared in Examples 1 and 2 is significantly smaller than that of the unmodified perovskite powder, indicating that the Lewis base modification successfully reduces the particle size of the perovskite powder. The reduction in particle size helps to increase the probability of collision between radiation and materials, and better achieves anti-radiation reinforcement of electronic devices.

[0064] Phase composition test, the results are as follows Figure 2 As shown by Figure 2 It can be seen that the XRD spectra of the Lewis base-modified perovskite powders prepared in Examples 1 and 2 do not have diffraction peaks of other impurities, have high purity, and the Lewis base modification does not change the phase structure of the material.

[0065] The above describes the specific embodiments of the present invention. It should be noted that the present invention is not limited to the above specific embodiments, and those skilled in the art may make various variations or modifications within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A method for strengthening the radiation resistance of electronic devices based on perovskite / resin composite materials, characterized in that: The following steps are involved: Step 1: Using lead salt, cationic salt, oleic acid, oleylamine and Lewis base as raw materials, a ligand-assisted reprecipitation method can be used to controllably prepare Lewis base-modified perovskite powder; Step 2: Grinding the Lewis base modified perovskite powder obtained in step 1 with resin to obtain a perovskite / resin slurry; Step 3: applying the slurry obtained in step 2 to the surface of the electronic device and curing it to form a perovskite / resin composite material on the surface of the electronic device; The specific operation of step 1 is as follows: dissolving the lead salt, cationic salt and Lewis base in N,N-dimethylformamide (DMF) to form a precursor solution A; Add oleic acid and oleylamine to the organic solvent, stir and dissolve to form solution B; Precursor solution A is quickly added to solution B. After the reaction is completed, the Lewis base-modified perovskite powder is obtained by centrifugation, washing, and drying. The lead salt is lead bromide, lead iodide or lead chloride; the cationic salt is cesium bromide, methylamine hydrobromide or formamidine hydrobromide; the Lewis base is thioacetamide (TAA), potassium thiocyanate (KSCN) or thiourea; Add (0.01-0.1) mmol of lead salt, (0.04-0.4) mmol of cationic salt, and (0.001-0.01) mmol of Lewis base to 1 ml of DMF; The mass ratio of perovskite powder to resin is 1:9-7:3; the resin is epoxy resin, polyethylene, polyurethane or cyanate ester.

2. The method according to claim 1, characterized in that The organic solvent is n-hexane or ethyl acetate.

3. The method according to claim 1, characterized in that The volume ratio of the organic solvent to the total volume of oleic acid and oleylamine is 10 mL: (60-150) μL; the volume ratio of oleic acid to oleylamine is 1:2-2:

1.

4. The method according to claim 1, characterized in that The volume ratio of solution A to solution B is 1:1~1:

10.

5. The method according to claim 1, characterized in that: The grinding time is 5 min~20 min.

6. The method according to claim 1, characterized in that The coating methods include scraping, brushing, spraying, and injection molding; the curing time is 2 h to 24 h at 30 ℃ to 150 ℃; and the thickness of the obtained composite material is 0.5 mm to 3 mm.

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