Semiconductor hydrogel electromagnetic wave regulation and control device with P-I-N structure and preparation method of semiconductor hydrogel electromagnetic wave regulation and control device

Abstract

The invention relates to a semiconductor hydrogel electromagnetic wave regulation and control device with a P-I-N structure, and belongs to the field of material science and engineering technologies and electromagnetic wave absorbing devices. The regulation and control device is mainly formed by assembling a top layer electrode, a multi-layer semiconductor hydrogel wave-absorbing body and a bottom layer reflection electrode. According to the invention, a P-I-N structure is introduced into the hydrogel wave-absorbing layer, and the interface polarization characteristic and the conductivity loss are changed by changing the thickness of the hydrogel layer and the P-type and N-type doping concentration, so that the wave-absorbing performance is enhanced. The top electrode allows efficient incidence of electromagnetic waves, the P-type semiconductor hydrogel and the N-type semiconductor hydrogel absorb energy through carrier relaxation and polarization loss, the porous hydrogel of the I-type layer enhances energy dissipation through multiple scattering and interface polarization, and the bottom electrode reflects the electromagnetic waves which are not absorbed to form a secondary absorption path. The flexible wave-absorbing material has the advantages of flexibility adjustability, high wave-absorbing efficiency, wide wave-absorbing frequency band and the like.

Description

Technical Field

[0001] This invention belongs to the field of functional materials and electromagnetic wave management technology, specifically relating to a device for electromagnetic wave absorption and modulation, particularly a PIN-structured semiconductor hydrogel multilayer device and its fabrication method. Electromagnetic waves are modulated by changing the N-type and P-type doping concentrations and by using ultrasonic spraying to alter the hydrogel film thickness, falling within the fields of materials science and engineering technology and electromagnetic shielding. Background Technology

[0002] Electromagnetic wave technology is an important research field in modern science and technology, widely used in wireless communication, radar detection, optoelectronics, and stealth technology. In many applications, the scattering and reflection of electromagnetic waves can lead to signal interference, information loss, and detection risks. Furthermore, electromagnetic radiation pollution is becoming increasingly serious. Therefore, the absorption and shielding of electromagnetic waves have received more attention, and the development of efficient electromagnetic wave absorbing devices has become an important research direction. Traditional electromagnetic wave absorbing materials are mainly based on metals, ceramics, and inorganic composite materials. These materials have many limitations, such as high weight, high brittleness, difficult processing, and difficulty in achieving biocompatibility. To cope with increasingly complex electromagnetic environments, absorbing materials need to have the ability to dynamically adjust the absorption and transmission of electromagnetic waves. Some traditional strategies, such as filler or matrix modulation, suffer from small variations and discontinuous electromagnetic wave modulation.

[0003] In recent years, hydrogels, as a novel functional material, have shown great potential in the field of electromagnetic wave absorption due to their unique physicochemical properties. Hydrogels are three-dimensional network structures formed by the physical or chemical cross-linking of hydrophilic polymers, possessing high water content, good mechanical flexibility, and biocompatibility. Furthermore, hydrogels exhibit flexible dynamic response, allowing for performance modulation through dielectric structure design. Traditional hydrogels lack semiconductor properties, limiting their application in electronics. This invention is based on recent major breakthroughs in the field of semiconductor hydrogels. The Wang Sihong research group at the University of Chicago proposed a processing method that decomposes the formation of the 3D network and water expansion of hydrogels into independent steps, achieving semiconductor hydrogels. The Lei Ting research group at Peking University achieved N-type semiconductor hydrogels with excellent mechanical properties, semiconductor properties, interfacial properties, and biocompatibility by cross-linking water-soluble cationic conjugated polymers with anti-ions or blending them with other hydrogels to form multi-network structures. Despite the progress made in semiconductor hydrogels, their application in electromagnetic wave modulation still faces challenges. For example, existing semiconductor hydrogels are mostly single homogeneous structures, making it difficult to achieve gradient attenuation and broadband absorption of electromagnetic waves within the material. More importantly, there is a lack of an effective structural design to dynamically and significantly adjust its electromagnetic parameters (such as dielectric constant and conductivity). Therefore, it is of great significance to develop a semiconductor hydrogel device with a stable PIN structure that can achieve efficient electromagnetic wave control through structural parameters.

[0004] This patent, through careful design of the molecular structure and composition of hydrogels, can endow them with semiconductor properties, introduce PIN structures into multilayer hydrogels and integrate them into microwave absorbing devices, enhance carrier relaxation and polarization loss by changing the doping concentration of P-type and N-type, adjust the porosity and thickness of the I-type layer to achieve gradient changes in dielectric constant, reduce surface reflection, and thus achieve dynamic control of electromagnetic waves. Summary of the Invention

[0005] 1. Objective of this invention

[0006] This invention provides a PIN-structured semiconductor hydrogel electromagnetic wave modulation device and its fabrication method. This device is formed by assembling P-type, I-type, and N-type doped semiconductor hydrogels layer by layer to create a PIN-structured multilayer absorber. Electromagnetic wave reflection and absorption are modulated by controlling the doping concentration and the thickness of the hydrogel layers using ultrasonic spraying. This device features flexibility, adjustability, and high electromagnetic wave absorption performance.

[0007] 2. Key Invention Points of this Technology

[0008] The key points of this invention are as follows:

[0009] I. A PIN-structured semiconductor hydrogel electromagnetic wave modulation device and its fabrication method, characterized in that P-type and N-type semiconductor polymers are respectively incorporated into a hydrogel network to form P-type semiconductor hydrogels and N-type semiconductor hydrogels, which are then assembled into a PIN-structured multilayer absorber, ultimately constructing an electromagnetic wave modulation device. Its features include the following:

[0010] 1. The PIN-type semiconductor hydrogel electromagnetic wave modulation device as described in claim 1, characterized in that: the top electrode is made of a loose and porous carbon material, such as carbon felt, allowing for efficient electromagnetic wave incidence; the bottom electrode is made of a polished thin metal plate, such as a nickel plate, reflecting unabsorbed electromagnetic waves and forming multiple reflection paths; the middle layer is made of prepared P-type, I-type, and N-type semiconductor hydrogels, assembled in sequence into a PIN-structured multilayer absorber. The device is assembled in a sandwich-like configuration to dynamically control the strength and frequency band of electromagnetic wave absorption by adjusting the voltage.

[0011] 2. The method for fabricating a PIN-type semiconductor hydrogel electromagnetic wave modulation device as described in claim 1, characterized by comprising the following steps:

[0012] Step 1, Synthesis of N-type semiconductor hydrogel:

[0013] (1) Dissolve N-type semiconductor polymer polynaphthalene dicarboxylate (PNDI-T) in dimethyl sulfoxide (DMSO) to prepare solutions with different concentration gradients. Stir the solutions at 60°C for 3 h using a magnetic stirrer until they are completely dissolved.

[0014] (2) Take a certain amount of acrylamide (AAm) and dissolve it in ultrapure water as a hydrogel monomer solution. Add crosslinking agent N,N'-methylenebisacrylamide (MBAA) and thermal initiator ammonium persulfate (APS) and stir until completely dissolved.

[0015] (3) The PNDI-T / DMSO mixed solution and the acrylamide monomer solution were divided into three groups according to different volume ratios. The solution obtained in step (1) was slowly added dropwise to the monomer solution while stirring with a magnetic stirrer. After stirring, the mixed solution was placed in an ultrasonic cleaner for ultrasonication for 10-20 min to further disperse the polymer.

[0016] (4) The dispersed solution was loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution propulsion speed and spray volume were controlled to change the film thickness. The airflow speed was 15 m / s, the distance from the nozzle to the receiving plate was 15 cm, and the temperature of the receiving plate was adjusted to 60℃. The solution was sprayed onto the bottom electrode using an ultrasonic sprayer, and in-situ polymerization was achieved at 60℃ to obtain an N-type semiconductor hydrogel film layer.

[0017] (5) Immerse the formed gel in ultrapure water for 24 h, changing the water every 4 h; then immerse the gel sequentially in DMSO / ultrapure water mixtures with different volume ratios, soaking for 2 h each time, to obtain N-type semiconductor hydrogel A;

[0018] Step 2, Synthesis of P-type semiconductor hydrogel:

[0019] (1) Water-soluble poly(3-hexylthiophene) (P3HT) nanoparticles with different mass fractions were added to ultrapure water and magnetically stirred for 1 h. 10 wt.% DMSO solution was slowly added to the P3HT dispersion and magnetically stirred for 30 min.

[0020] (2) Take a certain amount of acrylamide (AAm) and dissolve it in ultrapure water as a hydrogel monomer solution. Add crosslinking agent N,N'-methylenebisacrylamide (MBAA) and thermal initiator ammonium persulfate (APS) and stir until completely dissolved.

[0021] (3) The P3HT / DMSO mixed solution and the acrylamide monomer solution were divided into three groups according to different volume ratios. The P3HT / DMSO dispersion obtained in (1) was slowly added to the solution in (2) and magnetically stirred for 30 min. After stirring, the solution was ultrasonically treated for 40 min.

[0022] (4) The solution in (3) is loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution propulsion speed and spraying amount are controlled to change the film thickness. The airflow speed is 15 m / s, the distance from the nozzle to the receiving plate is 15 cm, the temperature of the receiving plate is adjusted to 60℃, and the solution is sprayed onto the customized template using an ultrasonic spraying machine. In-situ polymerization is achieved at 60℃ to obtain a P-type semiconductor hydrogel film layer.

[0023] (5) The formed gel was immersed in ultrapure water for 24 h, with the water changed every 4 h; then the gel was immersed in aqueous solutions of different concentrations of DMSO for 6 h to obtain P-type semiconductor hydrogel B;

[0024] Step 3, Synthesis of Layer I Porous Hydrogel:

[0025] (1) Take a certain amount of AAM, MBAA and NaCl and dissolve them in ultrapure water. Add APS and stir until completely dissolved. Place the solution in a mold and polymerize at 60°C. After polymerization, immerse the gel in ultrapure water for 48 h to obtain the intrinsic porous hydrogel C.

[0026] Step 4: Assembly of the PIN-type semiconductor hydrogel electromagnetic wave modulation device:

[0027] (1) Using a polished copper plate as the bottom electrode, place the N-type semiconductor hydrogel (A) solidified on the bottom electrode at the bottom layer, add 2 ml of AAm and HMPP solution to (A) to wet only the surface, then attach the intrinsic layer hydrogel (C) to (A), apply slight pressure to remove air bubbles; then add a small amount of 15 wt.% AAm and 0.3 wt.% HMPP solution to (C), attach the P-type semiconductor hydrogel (B) to (C), repeat the above operation, that is, the middle absorbing layer is BCA from top to bottom, then place it under UV light source for 2 min to make the hydrogel layer tightly bonded; finally attach the carbon paper to the P-type layer, apply slight pressure to ensure interface contact.

[0028] The accompanying drawings of this invention

[0029] Figure 1 Schematic diagram of a PIN-type semiconductor hydrogel electromagnetic control device.

[0030] Embodiments of the present invention

[0031] The following describes embodiments of the method of the present invention:

[0032] Example 1

[0033] PIN-structured multilayer semiconductor hydrogel electromagnetic wave modulation device and its fabrication method

[0034] First, an N-type semiconductor hydrogel was prepared by mixing a 2.5 mg / mL PNDI-T / DMSO solution and magnetically stirring it at 60 °C for 3 h. Then, 15 wt.% AAm, 0.4 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred until completely dissolved. The PNDI-T / DMSO solution was then slowly added dropwise to the monomer solution at a volume ratio of 1:5, while simultaneously magnetically stirring. After stirring, the solution was sonicated for 10–20 min. The dispersed solution was then loaded into a 10 mL syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 50 μL / h, the airflow velocity was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto the bottom electrode using an ultrasonic sprayer to obtain a liquid film layer, which was then subjected to polymerization at 60 °C until gel formation. The formed gel was immersed in ultrapure water for 24 hours, with the water changed every 4 hours. Then, the gel was immersed in a DMSO / ultrapure water mixture in sequence, with volume ratios of 3:1, 1:1, and 1:3, for 2 hours each time. After swelling, an N-type semiconductor hydrogel A with a thickness of 0.2 mm was obtained.

[0035] Then, a P-type semiconductor hydrogel was prepared by mixing a 5 wt.% P3HT solution with magnetic stirring for 1 h. A 10 wt.% DMSO solution was slowly added to the P3HT dispersion and magnetically stirred for 30 min. 15 wt.% AAm, 0.8 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred for 10 min. The P3HT / DMSO mixed solution was slowly added dropwise to the monomer solution at a volume ratio of 1:5 and magnetically stirred for 30 min. After stirring, the solution was sonicated for 40 min. The dispersed solution was loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 50 μL / h, the airflow velocity was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto a custom template using an ultrasonic sprayer to obtain a liquid film layer, which was then placed at 60℃ until gelation occurred. The formed gel was immersed in ultrapure water for 24 hours, with the water changed every 4 hours; then the gel was immersed in an aqueous solution containing 10% DMSO for 6 hours, and after swelling, a P-type semiconductor hydrogel B with a thickness of 0.2 mm was obtained;

[0036] The intrinsic porous hydrogel was prepared by dissolving 15 wt.% AAm, 1 wt.% MBAA, and 20 wt.% NaCl in ultrapure water, adding 0.3 wt.% HMPP, and stirring until completely dissolved. The solution was loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 50 μL / h, the airflow was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto a custom template using an ultrasonic sprayer to obtain a liquid film layer. The layer was placed at 60℃. After polymerization, the gel was immersed in ultrapure water for 48 h. After swelling, a porous hydrogel C with a thickness of 0.2 mm was obtained.

[0037] Finally, the device was assembled. A polished copper plate was used as the bottom electrode. The N-type semiconductor hydrogel (A) solidified on the bottom electrode was placed at the bottom layer. 2 ml of 15 wt.% AAm and 0.3 wt.% HMPP solution was dropped onto (A) to wet only the surface. Then, the intrinsic layer hydrogel (C) was attached to (A) and slight pressure was applied to remove air bubbles. A small amount of 15 wt.% AAm and 0.3 wt.% HMPP solution was then dropped onto (C). The P-type semiconductor hydrogel (B) was attached to (C). The above operation was repeated, i.e., the middle absorbing layer was arranged in the order BCABCA from top to bottom. Then, it was irradiated under a UV light source for 2 min to make the hydrogel layers bond tightly. The total thickness of the hydrogel layer was 1.2 mm. Finally, carbon paper was attached to the P-type layer and slight pressure was applied to ensure interface contact.

[0038] Example 2

[0039] PIN-structured multilayer semiconductor hydrogel electromagnetic wave modulation device and its fabrication method

[0040] First, an N-type semiconductor hydrogel was prepared by mixing a 2.5 mg / mL PNDI-T / DMSO solution and magnetically stirring it at 60 °C for 3 h. Then, 15 wt.% AAm, 0.4 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred until completely dissolved. The PNDI-T / DMSO solution was then slowly added dropwise to the monomer solution at a volume ratio of 1:5, while simultaneously magnetically stirring. After stirring, the solution was sonicated for 10–20 min. The dispersed solution was then loaded into a 10 mL syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 100 μL / h, the airflow velocity was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto the bottom electrode using an ultrasonic sprayer to obtain a liquid film layer, which was then placed at 60 °C until gelation occurred. The formed gel was immersed in ultrapure water for 24 hours, with the water changed every 4 hours. Then, the gel was immersed in a DMSO / ultrapure water mixture in sequence, with volume ratios of 3:1, 1:1, and 1:3, for 2 hours each time. After swelling, an N-type semiconductor hydrogel A with a thickness of 0.5 mm was obtained.

[0041] Then, a P-type semiconductor hydrogel was prepared by mixing a 5 wt.% P3HT solution with magnetic stirring for 1 h. 10 wt.% DMSO solution was slowly added to the P3HT dispersion and magnetically stirred for 30 min. 15 wt.% AAm, 0.8 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred for 10 min. The P3HT / DMSO mixed solution was slowly added dropwise to the monomer solution at a volume ratio of 1:5 and magnetically stirred for 30 min. After stirring, the solution was sonicated for 40 min. The dispersed solution was loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 100 μL / h, the airflow velocity was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto a custom template using an ultrasonic sprayer to obtain a liquid film layer, which was then placed at 60℃ until gelation occurred. The formed gel was immersed in ultrapure water for 24 hours, with the water changed every 4 hours; then the gel was immersed in an aqueous solution containing 10% DMSO for 6 hours, and after swelling, a P-type semiconductor hydrogel B with a thickness of 0.5 mm was obtained.

[0042] The intrinsic porous hydrogel was prepared by dissolving 15 wt.% AAm, 1 wt.% MBAA, and 20 wt.% NaCl in ultrapure water, adding 0.3 wt.% HMPP, and stirring until completely dissolved. The solution was loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 100 μL / h, the airflow velocity was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto a custom template using an ultrasonic sprayer to obtain a liquid film layer. The layer was placed at 60℃. After polymerization, the gel was immersed in ultrapure water for 48 h. After swelling, a porous hydrogel C with a thickness of 0.5 mm was obtained.

[0043] Finally, the device was assembled. A polished copper plate was used as the bottom electrode. The N-type semiconductor hydrogel (A) solidified on the bottom electrode was placed at the bottom layer. 2 ml of 15 wt.% AAm and 0.3 wt.% HMPP solution was dropped onto (A) to wet only the surface. Then, the intrinsic layer hydrogel (C) was attached to (A) and slight pressure was applied to remove air bubbles. Another 2 ml of 15 wt.% AAm and 0.3 wt.% HMPP solution was dropped onto (C), and the P-type semiconductor hydrogel (B) was attached to (C). The above operation was repeated, i.e., the middle absorbing layer was BCA from top to bottom. Then, it was irradiated under a UV light source for 2 min to make the hydrogel layers bond tightly. The total thickness of the hydrogel layer was 1.5 mm. Finally, carbon paper was attached to the P-type layer and slight pressure was applied to ensure interface contact.

[0044] Example 3

[0045] PIN-structured multilayer semiconductor hydrogel electromagnetic wave modulation device and its fabrication method

[0046] First, an N-type semiconductor hydrogel was prepared by mixing a 2.5 mg / mL PNDI-T / DMSO solution and magnetically stirring it at 60 °C for 3 h. Then, 15 wt.% AAm, 0.4 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred until completely dissolved. The PNDI-T / DMSO solution was slowly added dropwise to the monomer solution at a volume ratio of 1:5 while magnetically stirring. After stirring, the solution was sonicated for 10-20 min. The solution was poured into a mold and polymerized at 60 °C until gel formation. The formed gel was immersed in ultrapure water for 24 h, with the water changed every 4 h. Then, the gel was sequentially immersed in a DMSO / ultrapure water mixture at volume ratios of 3:1, 1:1, and 1:3, for 2 h each time. After swelling, an N-type semiconductor hydrogel A with a thickness of 1 mm was obtained.

[0047] Then, a P-type semiconductor hydrogel was prepared by mixing a 5 wt.% P3HT solution with magnetic stirring for 1 h. A 10 wt.% DMSO solution was slowly added to the P3HT dispersion, and the mixture was magnetically stirred for 30 min. 15 wt.% AAm, 0.8 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred for 10 min. The P3HT / DMSO mixture was slowly added dropwise to the monomer solution at a volume ratio of 1:5, and the mixture was magnetically stirred for 30 min. After stirring, the mixture was sonicated for 40 min. The solution was poured into a mold and polymerized at 60℃ until gel formation. The formed gel was immersed in ultrapure water for 24 h, with the water changed every 4 h. Then, the gel was immersed in an aqueous solution containing 10% DMSO for 6 h, and after swelling, a 1 mm thick P-type semiconductor hydrogel B was obtained.

[0048] The intrinsic layer porous hydrogel was prepared by dissolving 15 wt.% AAm, 1 wt.% MBAA and 20 wt.% NaCl in ultrapure water, adding 0.3 wt.% APS, stirring until completely dissolved, pouring the solution into a mold and polymerizing at 60℃. After polymerization, the gel was immersed in ultrapure water for 48 h and swollen to obtain a porous hydrogel C with a thickness of 1 mm.

[0049] Finally, the device was assembled. A polished copper plate was used as the bottom electrode. An N-type semiconductor hydrogel (A) was placed on the bottom electrode, and a small amount of 15 wt.% AAm and 0.3 wt.% HMPP solution was dropped onto (A) to wet only the surface. Then, the intrinsic layer hydrogel (C) was attached to (A) and slight pressure was applied to remove air bubbles. Then, 2 ml of 15 wt.% AAm and 0.3 wt.% HMPP solution was dropped onto (C), and a P-type semiconductor hydrogel (B) was attached to (C). The above operation was repeated, that is, the middle absorbing layer was BCA from top to bottom. Then, it was placed under a UV light source for 2 min to make the hydrogel layers bond tightly. The total thickness of the hydrogel layer was 3 mm. Finally, carbon paper was attached to the P-type layer and slight pressure was applied to ensure interface contact.

[0050] Example 4

[0051] PIN-structured multilayer semiconductor hydrogel electromagnetic wave modulation device and its fabrication method

[0052] First, an N-type semiconductor hydrogel was prepared by mixing a 1 mg / mL PNDI-T / DMSO solution and magnetically stirring it at 60°C for 3 h. Then, 15 wt.% AAm, 0.4 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred until completely dissolved. The PNDI-T / DMSO solution was slowly added dropwise to the monomer solution at a volume ratio of 1:10 while magnetically stirring. After stirring, the solution was sonicated for 10-20 min. The dispersed solution was then loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 50 μL / h, the airflow velocity was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto the bottom electrode using an ultrasonic sprayer to obtain a liquid film layer, which was then polymerized at 60°C until gel formation. The formed gel was immersed in ultrapure water for 24 hours, with the water changed every 4 hours. Then, the gel was immersed in a DMSO / ultrapure water mixture in sequence, with volume ratios of 3:1, 1:1, and 1:3, for 2 hours each time. After swelling, an N-type semiconductor hydrogel A with a thickness of 0.2 mm was obtained.

[0053] Then, a P-type semiconductor hydrogel was prepared by mixing a 2 wt.% P3HT solution and magnetically stirring for 1 h. A 10 wt.% DMSO solution was slowly added to the P3HT dispersion and magnetically stirred for 30 min. 15 wt.% AAm, 0.8 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred for 10 min. The P3HT / DMSO mixed solution was slowly added dropwise to the monomer solution at a volume ratio of 1:10 and magnetically stirred for 30 min. After stirring, the solution was ultrasonically treated for 40 min. The dispersed solution was loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 50 μL / h, the airflow velocity was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto a custom template using an ultrasonic sprayer to obtain a liquid film layer, which was then polymerized at 60 °C until gel formation. The formed gel was immersed in ultrapure water for 24 hours, with the water changed every 4 hours; then the gel was immersed in an aqueous solution containing 3% DMSO for 6 hours, and after swelling, a P-type semiconductor hydrogel B with a thickness of 0.2 mm was obtained;

[0054] The intrinsic porous hydrogel was prepared by dissolving 15 wt.% AAm, 1 wt.% MBAA, and 20 wt.% NaCl in ultrapure water, adding 0.3 wt.% APS, and stirring until completely dissolved. The solution was loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 50 μL / h, the airflow was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto a custom template using an ultrasonic sprayer to obtain a liquid film layer. This layer was then polymerized at 60 °C. After polymerization, the gel was immersed in ultrapure water for 48 h. After swelling, a porous hydrogel C with a thickness of 0.2 mm was obtained.

[0055] Finally, the device was assembled. A polished copper plate was used as the bottom electrode. The N-type semiconductor hydrogel (A) solidified on the bottom electrode was placed at the bottom layer. 2 ml of 15 wt.% AAm and 0.3 wt.% HMPP solution was dropped onto (A) to wet only the surface. Then, the intrinsic layer hydrogel (C) was attached to (A) and slight pressure was applied to remove air bubbles. A small amount of 15 wt.% AAm and 0.3 wt.% HMPP solution was then dropped onto (C). The P-type semiconductor hydrogel (B) was attached to (C). The above operation was repeated, i.e., the middle absorbing layer was arranged in the order BCABCA from top to bottom. Then, it was irradiated under a UV light source for 2 min to make the hydrogel layers bond tightly. The total thickness of the hydrogel layer was 1.2 mm. Finally, carbon paper was attached to the P-type layer and slight pressure was applied to ensure interface contact.

[0056] Example 5

[0057] PIN-structured multilayer semiconductor hydrogel electromagnetic wave modulation device and its fabrication method

[0058] First, an N-type semiconductor hydrogel was prepared by mixing a 1 mg / mL PNDI-T / DMSO solution and magnetically stirring it at 60°C for 3 h. Then, 15 wt.% AAm, 0.4 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred until completely dissolved. The PNDI-T / DMSO solution was slowly added dropwise to the monomer solution at a volume ratio of 1:10 while magnetically stirring. After stirring, the solution was sonicated for 10-20 min. The dispersed solution was then loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 50 μL / h, the airflow velocity was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto the bottom electrode using an ultrasonic sprayer to obtain a liquid film layer, which was then polymerized at 60°C until gel formation. The formed gel was immersed in ultrapure water for 24 hours, with the water changed every 4 hours. Then, the gel was immersed in a DMSO / ultrapure water mixture in sequence, with volume ratios of 3:1, 1:1, and 1:3, for 2 hours each time. After swelling, an N-type semiconductor hydrogel A with a thickness of 0.5 mm was obtained.

[0059] Then, a P-type semiconductor hydrogel was prepared by mixing a 2 wt.% P3HT solution and magnetically stirring for 1 h. 10 wt.% DMSO solution was slowly added to the P3HT dispersion and magnetically stirred for 30 min. 15 wt.% AAm, 0.8 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred for 10 min. The P3HT / DMSO mixed solution was slowly added dropwise to the monomer solution at a volume ratio of 1:10 and magnetically stirred for 30 min. After stirring, the solution was ultrasonically treated for 40 min. The dispersed solution was loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 100 μL / h, the airflow velocity was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto a custom template using an ultrasonic sprayer to obtain a liquid film layer, which was then polymerized at 60 °C until gel formation. The formed gel was immersed in ultrapure water for 24 hours, with the water changed every 4 hours; then the gel was immersed in an aqueous solution containing 3% DMSO for 6 hours, and after swelling, a P-type semiconductor hydrogel B with a thickness of 0.5 mm was obtained;

[0060] The intrinsic porous hydrogel was prepared by dissolving 15 wt.% AAm, 1 wt.% MBAA, and 20 wt.% NaCl in ultrapure water, adding 0.3 wt.% APS, and stirring until completely dissolved. The solution was loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 100 μL / h, the airflow velocity was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto a custom template using an ultrasonic sprayer to obtain a liquid film layer. This layer was then polymerized at 60 °C. After polymerization, the gel was immersed in ultrapure water for 48 h. After swelling, a porous hydrogel C with a thickness of 0.5 mm was obtained.

[0061] Finally, the device was assembled. A polished copper plate was used as the bottom electrode. The N-type semiconductor hydrogel (A) solidified on the bottom electrode was placed at the bottom layer. 2 ml of 15 wt.% AAm and 0.3 wt.% HMPP solution was dropped onto (A) to wet only the surface. Then, the intrinsic layer hydrogel (C) was attached to (A) and slight pressure was applied to remove air bubbles. A small amount of 15 wt.% AAm and 0.3 wt.% HMPP solution was then dropped onto (C). The P-type semiconductor hydrogel (B) was attached to (C). The above operation was repeated, i.e., the middle absorbing layer was BCA from top to bottom. Then, it was irradiated under a UV light source for 2 min to make the hydrogel layers bond tightly. The total thickness of the hydrogel layer was 1.5 mm. Finally, carbon paper was attached to the P-type layer and slight pressure was applied to ensure interface contact.

[0062] Example 6

[0063] PIN-structured multilayer semiconductor hydrogel electromagnetic wave modulation device and its fabrication method

[0064] First, an N-type semiconductor hydrogel was prepared by mixing a 1 mg / mL PNDI-T / DMSO solution and magnetically stirring it at 60°C for 3 h. Then, 15 wt.% AAm, 0.4 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred until completely dissolved. The PNDI-T / DMSO solution was slowly added dropwise to the monomer solution at a volume ratio of 1:10 while magnetically stirring. After stirring, the solution was sonicated for 10-20 min. The solution was poured into a mold and polymerized at 60°C until gel formation. The formed gel was immersed in ultrapure water for 24 h, with the water changed every 4 h. Then, the gel was sequentially immersed in a DMSO / ultrapure water mixture at volume ratios of 3:1, 1:1, and 1:3, for 2 h each time. After swelling, an N-type semiconductor hydrogel A with a thickness of 1 mm was obtained.

[0065] Then, a P-type semiconductor hydrogel was prepared by mixing a 2 wt.% P3HT solution with magnetic stirring for 1 h. A 10 wt.% DMSO solution was slowly added to the P3HT dispersion with magnetic stirring for 30 min. 15 wt.% AAm, 0.8 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred for 10 min. The P3HT / DMSO mixed solution was slowly added dropwise to the monomer solution at a volume ratio of 1:10 with magnetic stirring for 30 min. After stirring, the solution was sonicated for 40 min. The solution was poured into a mold and polymerized at 60℃ until gel formation. The formed gel was immersed in ultrapure water for 24 h, with the water changed every 4 h. Then, the gel was immersed in an aqueous solution containing 3% DMSO for 6 h, and after swelling, a 1 mm thick P-type semiconductor hydrogel B was obtained.

[0066] The intrinsic layer porous hydrogel was prepared by dissolving 15 wt.% AAm, 1 wt.% MBAA and 20 wt.% NaCl in ultrapure water, adding 0.3 wt.% APS, stirring until completely dissolved, pouring the solution into a mold and polymerizing at 60℃. After polymerization, the gel was immersed in ultrapure water for 48 h and swollen to obtain a porous hydrogel C with a thickness of 1 mm.

[0067] Finally, the device was assembled. A polished copper plate was used as the bottom electrode. An N-type semiconductor hydrogel (A) was placed on the bottom electrode, and 2 ml of 15 wt.% AAm and 0.3 wt.% HMPP solution was added to (A) to wet only the surface. Then, the intrinsic layer hydrogel (C) was attached to (A) and slight pressure was applied to remove air bubbles. A small amount of 15 wt.% AAm and 0.3 wt.% HMPP solution was added to (C), and a P-type semiconductor hydrogel (B) was attached to (C). The above operation was repeated, i.e., the middle absorbing layer was BCA from top to bottom. Then, it was irradiated under a UV light source for 2 min to make the hydrogel layers bond tightly. The total thickness of the hydrogel layer was 3 mm. Finally, carbon paper was attached to the P-type layer and slight pressure was applied to ensure interface contact.

[0068] Example 7

[0069] PIN-structured multilayer semiconductor hydrogel electromagnetic wave modulation device and its fabrication method

[0070] First, an N-type semiconductor hydrogel was prepared by mixing a 5 mg / mL PNDI-T / DMSO solution and magnetically stirring it at 60°C for 3 h. Then, 15 wt.% AAm, 0.4 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred until completely dissolved. The PNDI-T / DMSO solution was slowly added dropwise to the monomer solution at a volume ratio of 1:8 while simultaneously magnetically stirring. After stirring, the solution was sonicated for 10-20 min. The dispersed solution was then loaded into a 10 ml syringe with a 0.3 mm needle diameter. The solution was propelled at a rate of 50 μL / h, the airflow velocity was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto the bottom electrode using an ultrasonic sprayer to obtain a liquid film layer, which was then polymerized at 60°C until gel formation. The formed gel was immersed in ultrapure water for 24 hours, with the water changed every 4 hours. Then, the gel was immersed in a DMSO / ultrapure water mixture in sequence, with volume ratios of 3:1, 1:1, and 1:3, for 2 hours each time. After swelling, an N-type semiconductor hydrogel A with a thickness of 0.2 mm was obtained.

[0071] Then, a P-type semiconductor hydrogel was prepared by mixing a 10 wt.% P3HT solution with magnetic stirring for 1 h. A 10 wt.% DMSO solution was slowly added to the P3HT dispersion and magnetically stirred for 30 min. 15 wt.% AAm, 0.8 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred for 10 min. The P3HT / DMSO mixed solution was slowly added dropwise to the monomer solution at a volume ratio of 1:8 and magnetically stirred for 30 min. After stirring, the solution was sonicated for 40 min. The dispersed solution was loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 50 μL / h, the airflow velocity was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto a custom template using an ultrasonic sprayer to obtain a liquid film layer, which was then polymerized at 60 °C until gel formation. The formed gel was immersed in ultrapure water for 24 hours, with the water changed every 4 hours; then the gel was immersed in an aqueous solution containing 5% DMSO for 6 hours, and after swelling, a P-type semiconductor hydrogel B with a thickness of 0.2 mm was obtained.

[0072] The intrinsic porous hydrogel was prepared by dissolving 15 wt.% AAm, 1 wt.% MBAA, and 20 wt.% NaCl in ultrapure water, adding 0.3 wt.% APS, and stirring until completely dissolved. The solution was loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 50 μL / h, the airflow was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto a custom template using an ultrasonic sprayer to obtain a liquid film layer. This layer was then polymerized at 60 °C. After polymerization, the gel was immersed in ultrapure water for 48 h. After swelling, a porous hydrogel C with a thickness of 0.2 mm was obtained.

[0073] Finally, the device was assembled. A polished copper plate was used as the bottom electrode. The N-type semiconductor hydrogel (A) solidified on the bottom electrode was placed at the bottom layer. 2 ml of 15 wt.% AAm and 0.3 wt.% HMPP solution was dropped onto (A) to wet only the surface. Then, the intrinsic layer hydrogel (C) was attached to (A) and slight pressure was applied to remove air bubbles. A small amount of 15 wt.% AAm and 0.3 wt.% HMPP solution was then dropped onto (C). The P-type semiconductor hydrogel (B) was attached to (C). The above operation was repeated, i.e., the middle absorbing layer was arranged in the order BCABCA from top to bottom. Then, it was irradiated under a UV light source for 2 min to make the hydrogel layers bond tightly. The total thickness of the hydrogel layer was 1.2 mm. Finally, carbon paper was attached to the P-type layer and slight pressure was applied to ensure interface contact.

[0074] Example 8

[0075] PIN-structured multilayer semiconductor hydrogel electromagnetic wave modulation device and its fabrication method

[0076] First, an N-type semiconductor hydrogel was prepared by mixing a 5 mg / mL PNDI-T / DMSO solution and magnetically stirring it at 60 °C for 3 h. Then, 15 wt.% AAm, 0.4 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred until completely dissolved. The PNDI-T / DMSO solution was slowly added dropwise to the monomer solution at a volume ratio of 1:8 while simultaneously magnetically stirring. After stirring, the solution was sonicated for 10-20 min. The dispersed solution was then loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 100 μL / h, the airflow velocity was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto the bottom electrode using an ultrasonic sprayer to obtain a liquid film layer, which was then polymerized at 60 °C until gel formation. The formed gel was immersed in ultrapure water for 24 hours, with the water changed every 4 hours. Then, the gel was immersed in a DMSO / ultrapure water mixture in sequence, with volume ratios of 3:1, 1:1, and 1:3, for 2 hours each time. After swelling, an N-type semiconductor hydrogel A with a thickness of 0.5 mm was obtained.

[0077] Then, a P-type semiconductor hydrogel was prepared by mixing a 10 wt.% P3HT solution with magnetic stirring for 1 h. A 10 wt.% DMSO solution was slowly added to the P3HT dispersion and magnetically stirred for 30 min. 15 wt.% AAm, 0.8 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred for 10 min. The P3HT / DMSO mixed solution was slowly added dropwise to the monomer solution at a volume ratio of 1:8 and magnetically stirred for 30 min. After stirring, the solution was sonicated for 40 min. The dispersed solution was loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 100 μL / h, the airflow velocity was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto a custom template using an ultrasonic sprayer to obtain a liquid film layer, which was then polymerized at 60 °C until gel formation. The formed gel was immersed in ultrapure water for 24 hours, with the water changed every 4 hours; then the gel was immersed in an aqueous solution containing 5% DMSO for 6 hours, and after swelling, a P-type semiconductor hydrogel B with a thickness of 0.5 mm was obtained.

[0078] The intrinsic porous hydrogel was prepared by dissolving 15 wt.% AAm, 1 wt.% MBAA, and 20 wt.% NaCl in ultrapure water, adding 0.3 wt.% APS, and stirring until completely dissolved. The solution was loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The solution was propelled at a rate of 100 μL / h, the airflow velocity was 15 m / s, and the distance from the nozzle to the receiving plate was 15 cm. The solution was sprayed onto a custom template using an ultrasonic sprayer to obtain a liquid film layer. This layer was then polymerized at 60 °C. After polymerization, the gel was immersed in ultrapure water for 48 h. After swelling, a porous hydrogel C with a thickness of 0.5 mm was obtained.

[0079] Finally, the device was assembled. A polished copper plate was used as the bottom electrode. The N-type semiconductor hydrogel (A) solidified on the bottom electrode was placed at the bottom layer. 2 ml of 15 wt.% AAm and 0.3 wt.% HMPP solution was dropped onto (A) to wet only the surface. Then, the intrinsic layer hydrogel (C) was attached to (A) and slight pressure was applied to remove air bubbles. A small amount of 15 wt.% AAm and 0.3 wt.% HMPP solution was then dropped onto (C). The P-type semiconductor hydrogel (B) was attached to (C). The above operation was repeated, i.e., the middle absorbing layer was BCA from top to bottom. Then, it was irradiated under a UV light source for 2 min to make the hydrogel layers bond tightly. The total thickness of the hydrogel layer was 1.5 mm. Finally, carbon paper was attached to the P-type layer and slight pressure was applied to ensure interface contact.

[0080] Example 9

[0081] PIN-structured multilayer semiconductor hydrogel electromagnetic wave modulation device and its fabrication method

[0082] First, an N-type semiconductor hydrogel was prepared by mixing a 5 mg / mL PNDI-T / DMSO solution and magnetically stirring it at 60°C for 3 h. Then, 15 wt.% AAm, 0.4 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred until completely dissolved. The PNDI-T / DMSO solution was slowly added dropwise to the monomer solution at a volume ratio of 1:8 while magnetically stirring. After stirring, the solution was sonicated for 10-20 min. The solution was poured into a mold and polymerized at 60°C until gel formation. The formed gel was immersed in ultrapure water for 24 h, with the water changed every 4 h. Then, the gel was sequentially immersed in a DMSO / ultrapure water mixture at volume ratios of 3:1, 1:1, and 1:3, for 2 h each time. After swelling, an N-type semiconductor hydrogel A with a thickness of 1 mm was obtained.

[0083] Then, a P-type semiconductor hydrogel was prepared by mixing a 10 wt.% P3HT solution with magnetic stirring for 1 h. A 10 wt.% DMSO solution was slowly added to the P3HT dispersion, and the mixture was magnetically stirred for 30 min. 15 wt.% AAm, 0.8 wt.% MBAA, and 0.35 wt.% APS were added to ultrapure water and stirred for 10 min. The P3HT / DMSO mixture was slowly added dropwise to the monomer solution at a volume ratio of 1:8, and the mixture was magnetically stirred for 30 min. After stirring, the mixture was sonicated for 40 min. The solution was poured into a mold and polymerized at 60℃ until gel formation. The formed gel was immersed in ultrapure water for 24 h, with the water changed every 4 h. Then, the gel was immersed in an aqueous solution containing 5% DMSO for 6 h, and after swelling, a 1 mm thick P-type semiconductor hydrogel B was obtained.

[0084] The intrinsic layer porous hydrogel was prepared by dissolving 15 wt.% AAm, 1 wt.% MBAA and 20 wt.% NaCl in ultrapure water, adding 0.3 wt.% APS, stirring until completely dissolved, pouring the solution into a mold and polymerizing at 60℃. After polymerization, the gel was immersed in ultrapure water for 48 h and swollen to obtain a porous hydrogel C with a thickness of 1 mm.

[0085] Finally, the device was assembled. A polished copper plate was used as the bottom electrode. An N-type semiconductor hydrogel (A) was placed on the bottom electrode, and 2 ml of 15 wt.% AAm and 0.3 wt.% HMPP solution was added to (A) to wet only the surface. Then, the intrinsic layer hydrogel (C) was attached to (A) and slight pressure was applied to remove air bubbles. A small amount of 15 wt.% AAm and 0.3 wt.% HMPP solution was added to (C), and a P-type semiconductor hydrogel (B) was attached to (C). The above operation was repeated, i.e., the middle absorbing layer was BCA from top to bottom. Then, it was irradiated under a UV light source for 2 min to make the hydrogel layers bond tightly. The total thickness of the hydrogel layer was 3 mm. Finally, carbon paper was attached to the P-type layer and slight pressure was applied to ensure interface contact.

Claims

1. A PIN-structured semiconductor hydrogel electromagnetic wave modulation device and its fabrication method, characterized in that... P-type and N-type semiconductor polymers were incorporated into a hydrogel network using this method to form P-type semiconductor hydrogels and N-type semiconductor hydrogels, respectively. These hydrogels were then assembled into a PIN-structured multilayer absorber, ultimately constructing an electromagnetic wave control device. Its features include the following: (1) The PIN-type semiconductor hydrogel electromagnetic wave modulation device as described in claim 1, characterized in that: the top electrode is made of loose and porous carbon material, such as carbon felt, which allows electromagnetic waves to be incident efficiently; the bottom electrode is made of a polished thin metal plate, such as a nickel plate, which reflects unabsorbed electromagnetic waves and forms multiple reflection paths; the middle layer is made of prepared P-type, I-type and N-type semiconductor hydrogels, which are assembled in sequence into a PIN structure multilayer absorber. The electromagnetic wave modulation device is assembled according to a sandwich-like configuration, and the device can dynamically control the strength and frequency band of electromagnetic wave absorption by adjusting the voltage. (2) The method for preparing the PIN-type semiconductor hydrogel electromagnetic wave modulation device as described in claim 1, characterized in that it includes the following steps: Step 1: Synthesis of N-type semiconductor hydrogels 1) Dissolve the N-type semiconductor polymer polynaphthalene dicarboxylate (PNDI-T) in dimethyl sulfoxide (DMSO) to prepare solutions with different concentration gradients. Stir the solutions at 60°C for 3 h using a magnetic stirrer until completely dissolved. 2) Dissolve a certain amount of acrylamide (AAm) in ultrapure water as a hydrogel monomer solution, add crosslinking agent N,N'-methylenebisacrylamide (MBAA) and thermal initiator ammonium persulfate (APS), and stir until completely dissolved; 3) The PNDI-T / DMSO mixed solution and the acrylamide monomer solution were divided into three groups according to different volume ratios. The solution obtained in step 1) was slowly added dropwise to the monomer solution while stirring with a magnetic stirrer. After stirring, the mixed solution was placed in an ultrasonic cleaner for ultrasonication for 10-20 minutes to further disperse the polymer. 4) The dispersed solution was loaded into a 10 ml syringe with a needle diameter of 0.3 mm. The film thickness was changed by controlling the solution injection speed and spray volume. The airflow speed was 15 m / s, the distance from the nozzle to the receiving plate was 15 cm, and the temperature of the receiving plate was adjusted to 60℃. The solution was sprayed onto the bottom electrode using an ultrasonic sprayer, and in-situ polymerization was achieved at 60℃ to obtain an N-type semiconductor hydrogel film layer. 5) Immerse the formed gel in ultrapure water for 24 hours, changing the water every 4 hours; then immerse the gel sequentially in DMSO / ultrapure water mixtures of different volume ratios, soaking for 2 hours each time, to obtain N-type semiconductor hydrogel A; Step 2: Synthesis of P-type semiconductor hydrogels 1) Water-soluble poly(3-hexylthiophene) (P3HT) nanoparticles of different mass fractions were added to ultrapure water and magnetically stirred for 1 h. 10 wt.% DMSO solution was slowly added to the P3HT dispersion while magnetically stirring for 30 min. 2) Dissolve a certain amount of acrylamide (AAm) in ultrapure water as a hydrogel monomer solution, add crosslinking agent N,N'-methylenebisacrylamide (MBAA) and thermal initiator ammonium persulfate (APS), and stir until completely dissolved; 3) The P3HT / DMSO mixed solution and the acrylamide monomer solution were divided into three groups according to different volume ratios. The P3HT / DMSO dispersion obtained in 1) was slowly added to the solution in 2), and magnetic stirring was performed for 30 min. After stirring, the solution was ultrasonically treated for 40 min. 4) Load the solution from 3) into a 10 ml syringe with a needle diameter of 0.3 mm. Control the solution propulsion speed and spray volume to change the film thickness. The airflow speed is 15 m / s, the distance from the nozzle to the receiving plate is 15 cm, and the temperature of the receiving plate is adjusted to 60℃. Use an ultrasonic sprayer to spray the solution onto a customized template and achieve in-situ polymerization at 60℃ to obtain a P-type semiconductor hydrogel film layer. 5) The formed gel was immersed in ultrapure water for 24 hours, with the water changed every 4 hours; then the gel was immersed in aqueous solutions of different concentrations of DMSO for 6 hours to obtain P-type semiconductor hydrogel B; (5) Preparation of the i-layer porous hydrogel: 1) Dissolve a certain amount of AAM, MBAA, and NaCl in ultrapure water, add APS, stir until completely dissolved, place the solution in a mold and polymerize at 60℃. After polymerization, immerse the gel in ultrapure water for 48 h to obtain the intrinsic layer porous hydrogel C. (6) Assembly of PIN-type semiconductor hydrogel electromagnetic wave modulation device: 1) Using a polished copper plate as the bottom electrode, place the N-type semiconductor hydrogel (A) solidified on the bottom electrode at the bottom layer, add 2 ml of AAm and HMPP solution to (A) to wet only the surface, then attach the intrinsic layer hydrogel (C) to (A) and apply slight pressure to remove air bubbles; then add a small amount of 15 wt.% AAm and 0.3 wt.% HMPP solution to (C), attach the P-type semiconductor hydrogel (B) to (C), and repeat the above operation, i.e. the middle absorbing layer is BCA in the order from top to bottom, and then place it under a UV light source for 2 min to make the hydrogel layers bond tightly; finally attach the carbon paper to the P-type layer and apply slight pressure to ensure interface contact.

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