Electronic device radiation hardening method based on perovskite / resin composite material

Abstract

The invention discloses an electronic device radiation hardening method based on a perovskite / resin composite material, and belongs to the field of radiation hardening. The anti-radiation hardening method comprises three parts of preparation of Lewis base modified perovskite powder, preparation of Lewis base modified perovskite / resin slurry and anti-radiation hardening of the electronic device, namely, a Lewis base-containing precursor solution is added into a ligand-containing reaction solvent and violently stirred to prepare a Lewis base modified perovskite material; and then the composite material is compounded with resin and is coated on the surface of an electronic device, so that the anti-radiation reinforcement of the electronic device can be achieved. The interaction between the perovskite / resin composite material and incident high-energy electrons significantly attenuates the radiation energy, thereby reducing the energy deposition in the device, and ensuring the electrical property stability of the electronic device under the radiation of the high-energy electrons. Wide application prospects are also realized in the fields of aerospace engineering, ray medical treatment, nuclear engineering and the like.

Description

Technical Field

[0001] The present invention belongs to the field of radiation-resistant reinforcement, and specifically relates to a method for radiation-resistant reinforcement of electronic devices based on perovskite / resin composite materials. The present invention is mainly used in the field of aerospace engineering, and secondly has broad application prospects in the fields of radiation medicine, nuclear engineering, etc. Background Art

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

[0003] At present, the main radiation reinforcement methods for 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 an obvious effect on high-energy electron shielding in space radiation environments, 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 easy generation of 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 prepared by combining functional fillers and polymer matrices. They have the advantages of low density, good processability, and strong designability. By selecting suitable functional fillers, radiation shielding can be well achieved. Lead halide perovskite has the advantages of high atomic number, rich extranuclear electrons, and large inner electron binding energy. It is expected to become an excellent electron radiation shielding functional filler. The essence of electron radiation shielding is to use the interaction process between radiation and the extranuclear electrons of the material to attenuate energy. Therefore, electronic structure design and regulation is an effective strategy to improve the radiation shielding performance of materials. However, the current research on radiation shielding functional fillers in composite materials is still at the macroscopic level of filler size, filler dispersibility, and filler component regulation. There is no report 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 the current design ideas for improving the radiation shielding performance of materials. By regulating the electronic structure of the material, a method for radiation-resistant reinforcement of electronic devices using a perovskite / resin composite material that is lightweight, low-toxic, and has excellent radiation shielding performance is provided. The radiation-resistant reinforcement method includes three parts: preparation of Lewis base-modified perovskite powder, preparation of Lewis base-modified perovskite / resin slurry, and radiation-resistant reinforcement of electronic devices. The present invention adds a precursor solution containing a Lewis base to a reaction solvent containing a ligand and stirs vigorously to obtain a Lewis base-modified perovskite material. After that, it is compounded with a resin and coated on the surface of an electronic device to achieve radiation-resistant reinforcement of the electronic device.

[0006] The method of the 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 by ligand-assisted reprecipitation method;

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

[0012] Grinding the Lewis base modified perovskite powder obtained in step 1 with the 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, so as to form 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 a lead salt, a cationic salt and a 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] Further limiting, 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.; the Lewis base is a Lewis base such as thioacetamide (TAA), potassium thiocyanate (KSCN) or thiourea.

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

[0020] In a further embodiment, 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 10mL:(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 min to 20 min, 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 performed 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 from 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 an excellent radiation resistance 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 materials, and better realizes the radiation resistance reinforcement of electronic devices;

[0031] Compared with the 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 Lewis base-modified perovskite powder, wherein a precursor solution containing reaction raw materials is quickly added to an anti-solvent and vigorously stirred, and after the perovskite is precipitated under the action of the anti-solvent, the Lewis base is grafted onto the A and B position cations of the perovskite through the Lewis acid-base pairing effect, thereby obtaining the Lewis base-modified perovskite powder;

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

[0034] After the Lewis base modifier added in the present invention is grafted onto the perovskite material, it can cause inelastic scattering with the incident electrons, change the energy spectrum of the incident high-energy electrons, and thus reduce the probability and energy of bremsstrahlung generated by the interaction between the high-energy electrons and the perovskite material, forming a multi-level loss of incident electron energy;

[0035] The present invention uses Lewis base as a passivating agent to reduce defects in the prepared perovskite material. The reduction of defects can increase the order of atomic arrangement in the perovskite crystal material, increase the probability of interaction between the material and the incident electrons, and also increase 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 and drawings of the present invention. However, the attached drawings are only provided for reference and illustration 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 in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, and do not limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention. These all fall within the scope of protection of the present invention.

[0044] Embodiment 1: The radiation-resistant reinforcement method for electronic devices based on the perovskite / resin composite material in this embodiment comprises 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 in 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, stir for 10min to mix evenly to form solution B. Quickly drop 1mL of precursor solution A into solution B and stir vigorously. Stop the reaction after 30min, 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, wherein the mass ratio of KSCN-modified Cs4PbBr6 powder to epoxy resin was 2:8. The two were fully ground using a three-roll mill for 10 minutes, and after the grinding was completed, a modified KSCN-Cs4PbBr6 / epoxy resin slurry was obtained;

[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] Embodiment 2: The radiation-resistant reinforcement method for electronic devices based on the perovskite / resin composite material in this embodiment comprises 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 in 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, stir for 10min to mix evenly to form solution B. Quickly drop 1mL of precursor solution A into solution B and stir vigorously. Stop the reaction after 30min, 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, wherein the mass ratio of TAA-modified Cs4PbBr6 powder to epoxy resin was 2:8. The two were fully ground using a three-roll mill for 10 minutes, and after the grinding was completed, a modified TAA-Cs4PbBr6 / epoxy resin slurry was obtained;

[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 in the following manner:

[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 reinforced by unmodified 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 radiation-resistant 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 physical structure of the material is not changed after Lewis base modification.

[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 can make various modifications or variations within the scope of the claims, which does not affect the essential content of the present invention.

Claims

1. A method for strengthening 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 Lewis base-modified perovskite powder can be prepared by a ligand-assisted reprecipitation method; Step 2: Grinding the Lewis base modified perovskite powder obtained in step 1 with resin to obtain a perovskite / resin slurry; Step 3: coating the slurry obtained in step 2 on the surface of the electronic device and curing it to form a perovskite / resin composite material on the surface of the electronic device.

2. The method according to claim 1, characterized in that: The specific operation of step 1 is as follows: dissolving 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; 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.

3. The method according to claim 1 or 2, characterized in that: The lead salt is lead bromide, lead iodide or lead chloride; the cationic salt is cesium bromide, methylamine hydrobromide or formamidine hydrobromide; and the Lewis base is thioacetamide (TAA), potassium thiocyanate (KSCN) or thiourea.

4. The method according to claim 2, characterized in that: 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 in a ratio of 1 ml of DMF.

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

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

1.

7. The method according to claim 2, characterized in that: The volume ratio of solution A to solution B is 1:1 to 1:

10.

8. The method according to claim 1, characterized in that: The mass ratio of perovskite powder to resin is 1:9 to 7:3; the resin is epoxy resin, polyethylene, polyurethane or cyanate ester.

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

10. The method according to claim 1, characterized in that: The coating method is scraping, brushing, spraying, and injection molding; curing is performed at 30° C. to 150° C. for 2 hours to 24 hours; and the thickness of the obtained composite material is 0.5 mm to 3 mm.

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