Bionic nanofluidic ion-based patterned flexible sensing device and preparation method thereof

By constructing nanofluid ion channels in the carbon nanotube array and performing functional molecular modification, the mechanical and temperature responsiveness of the bionic nanofluid ion-based patterned flexible sensing device is achieved, and the problem of insufficient sensitivity and stability in the prior art is solved, and the high-efficiency and low-energy-consuming sensing effect is achieved.

CN119714372APending Publication Date: 2025-03-28XIAMEN UNIV
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Patent Information

Application Number
CN202311261194.6
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2023-09-27
Publication Date
2025-03-28

AI Technical Summary

Technical Problem

The existing flexible ion skin devices based on carbon nanotubes still need to be optimized in terms of sensitivity, stability and cost.

Method used

Using a bionic nanofluid ion-based patterned flexible sensing device, mechanical responsiveness and temperature responsiveness are achieved by constructing nanofluid ion channels in a carbon nanotube array and using a combination of functionalized molecular modification and electrolyte solution.

Benefits of technology

Reversible on-off state regulation of ion transport under the action of multiple external fields is realized, and the sensing signal is enhanced, with high sensitivity, good stability and low cost.

✦ Generated by Eureka AI based on patent content.

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Abstract

The invention discloses a bionic nanofluidic ion-based patterned flexible sensing device and a preparation method thereof, the flexible sensing device comprises a patterned carbon nanotube-based nanofluidic ion channel flexible high-molecular polymer film, an electrolyte solution is arranged in a nanofluidic ion channel, the nanofluidic ion channel is modified by functional molecules, and the nanofluidic ion channel is a flexible high-molecular polymer film. The inner diameter of the bionic nanofluidic ion channel ranges from 1 nm to 100 nm, and the nanofluidic ion-based flexible sensing device has mechanical responsiveness, humidity responsiveness and the like.
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Description

Technical Field

[0001] The invention belongs to the field of micro-nano processing technology and bionic nanofluidic ionology, and relates to a bionic nanofluidic ion-based patterned flexible sensing device and a preparation method thereof. Background Art

[0002] In 2021, the Nobel Prize in Physiology or Medicine was awarded to researchers for their contributions to the discovery of temperature and touch receptors. Sensation is the process by which organisms determine the properties of the environment under external factors such as heat, cold and external force. When mechanical stress or temperature acts on the touch receptors on the biological membrane, it will cause the response and synergy of multiple ion gates such as ligand gating, mechanical gating, voltage gating, and temperature gating. Through the transmembrane transmission of ions, a series of encoded action potentials are generated to transmit the stimulation signal to the brain, which is used for the perception of dynamic force, static force and temperature.

[0003] The ultra-efficient processing, storage, and transmission of sensory information by organisms are produced through the synergistic effect of ion channels. Simulating the biological sensory information processing process has brought new inspiration to sensor technology. As carriers, ions have incomparable advantages over electrons: ① Ion current will not produce electrons and holes that cancel each other out, making information transmission more stable during life activities; ② The diversity of ion types can simulate more layers of sensory signals with rich content, providing more possibilities for designing flexible bionic sensory membrane materials with different response mechanisms; ③ The mass of ions is much greater than that of electrons, so they can resist the interference of greater electric field noise; ④ The signal integration system based on electron transport consumes a lot of energy, while the energy consumption of the entire process of biological receptors receiving, processing, and transmitting sensory information to the brain is only a few fJ / spike, which is much less than that of electronic devices. The development of bionic flexible electronic skin materials with ions as signal carriers is expected to achieve high efficiency, low energy consumption, and high integration.

[0004] Carbon nanotubes are one-dimensional nanomaterials with excellent performance. Due to their structural differences, they can exhibit metallic or semiconductor properties. They are one of the strongest materials known so far, have good flexibility, and have extremely high carrier mobility of about 15,000 cm·V. -1 ·s -1 , with extremely strong electronic effect and very good thermal conductivity. In addition, carbon nanotubes have high fracture strength and are not easily damaged when bent, making them ideal materials for flexible devices. Although there has been some research on flexible ion skin based on carbon nanotube ion channels, it is still in its initial stage, and the device sensitivity, stability, and cost need to be optimized. Summary of the invention

[0005] The main purpose of the present invention is to provide a bionic nanocurrent ion-based patterned flexible sensing device.

[0006] The technical solution adopted by the present invention to solve its technical problem is:

[0007] The purpose of the present invention is to provide a bionic nanocurrent ion-based patterned flexible sensing device and a preparation method thereof.

[0008] In order to achieve the above purpose, the technical solution of the present invention is:

[0009] A bionic nanofluidic ion-based patterned flexible sensing device comprises a patterned carbon nanotube-based nanofluidic ion channel flexible high molecular polymer membrane, wherein the nanofluidic ion channel has an electrolyte solution, the nanofluidic ion channel is modified by functionalized molecules, and the inner diameter of the bionic nanofluidic ion channel is between 1nm and 100nm.

[0010] Optionally, the nanoflow ion-based flexible sensing device has mechanical responsiveness and temperature responsiveness.

[0011] Optionally, the functionalized molecule of the bionic nanoflow ion channel is at least one of poly (N-isopropylacrylamide), polydopamine, polyacrylic acid, polyethylenedioxythiophene, polystyrene sulfonic acid, and polyallylamine hydrochloride.

[0012] Optionally, the ion species in the bionic nanocurrent ion channel may be any one or more of KCl (potassium chloride), NaCl (sodium chloride), MgCl2 (magnesium chloride), etc.

[0013] Optionally, the ion concentration in the bionic nanoflow ion channel is between 0.1 mmol / L and 1.0 mol / L.

[0014] Another object of the present invention is to provide a method for preparing a biomimetic nanofluidic ion-based patterned flexible sensing device, comprising the following steps:

[0015] Step 1: obtaining a photoresist substrate and performing patterning on the photoresist substrate; growing a carbon nanotube array in a growth area on the patterned photoresist substrate;

[0016] Step 2: Compounding and curing the carbon nanotube array with a flexible polymer, and then ultra-thinly slicing the composite to obtain a precisely patterned carbon nanotube array flexible film;

[0017] Step 3: Grafting polymer molecular brushes into the nanoflow ion channels of the carbon nanotube array to obtain pH-sensitive carbon nanotube arrays with precise patterning of functionalized nanoflow ion channels;

[0018] Step 4: Assemble and integrate the functionalized nanocurrent ion channel with the flexible electrode and use it as part of the circuit to obtain a bionic nanocurrent ion-based patterned flexible sensing device.

[0019] Optionally, in step one, the non-growth area is protected by an adhesion layer and a vapor deposition layer.

[0020] Optionally, in step 2, the flexible polymer includes any one of epoxy resin, polyimide, polycarbonate, and polyaniline.

[0021] Optionally, in step three, the grafting method includes any one of a plasma gasification grafting method, an atom transfer radical polymerization method, and an in-situ interfacial polymerization method.

[0022] Optionally, in step three, the grafted polymer molecular brush includes at least one of poly (N-isopropylacrylamide), polydopamine, polyacrylic acid, polyethylenedioxythiophene, polystyrene sulfonic acid, and polyallylamine hydrochloride.

[0023] The present invention provides a bionic nanofluidic ion-based patterned flexible sensing device, which mainly comprises the following steps: using micro-nano processing lithography technology in combination with chemical vapor deposition, embedding and packaging, ultra-thin sectioning and other technologies to modify the growth substrate of a carbon nanotube array, screen development conditions, improve and optimize condition parameters such as vapor deposition of metal particles, and obtain a precisely patterned carbon nanotube-based nanofluidic ion channel flexible high molecular polymer film, wherein the nanofluidic ion channel has an electrolyte solution, and further using methods such as physical and chemical grafting, through reasonable design of the geometric shape and pattern distribution of the nanofluidic ion channel and modification of the nanofluidic ion channel with functional molecules on the inner surface, to construct a nanofluidic ion-based flexible sensing device with a series of responsiveness such as mechanical response, temperature response, and humidity response.

[0024] The bionic nanocurrent ion-based patterned flexible sensing device can regulate the ion transport under multiple external fields through reversible on-off states. The signal logic gate is designed to integrate the nanocurrent ion channel sensing signals to achieve graphical distribution of tactile information such as pressure and temperature, thereby achieving signal-enhanced high-efficiency, low-energy consumption and high-sensitivity sensing.

[0025] Optionally, the precision patterned substrate obtained by the micro-nano processing technology and the like can be evenly spin-coated with a 1 μm to 50 μm thick UV positive or negative photoresist.

[0026] Optionally, the precision patterned substrate obtained by the micro-nano processing technology and the like may have an adhesion layer made of one of metals Ti (titanium), Cr (chromium), etc., with a thickness between 2nm and 5nm, which does not fall off or decompose in a high-temperature chamber.

[0027] Optionally, the inorganic metal / non-metal nanolayer of the precision patterned substrate obtained by the micro-nano processing technology and the like can be any one of Au (gold), Pt (platinum), Cu (copper), Si3N4 (silicon nitride), etc., which does not affect the catalytic reaction in the high-temperature chamber in the subsequent chemical vapor deposition reaction.

[0028] Optionally, the inorganic metal / non-metal nanolayer thickness of the precision patterned substrate obtained by the micro-nano processing technology and the like is between 20 nm and 100 nm.

[0029] Optionally, the inner diameter of the bionic nanoflow ion channel is between 5 nm and 100 nm, and its nano-space confinement effect on ions should be relatively strong.

[0030] Optionally, the high molecular polymer for constructing the flexible membrane may be any one of epoxy resin, polyimide, polycarbonate, polyaniline, etc., which has certain flexibility and deformability after polymerization and curing.

[0031] Optionally, the biomimetic nanofluidic ion channel has active sites, and functional molecule modification can be performed by any one of plasma vaporization grafting, atom transfer radical polymerization, in-situ interfacial polymerization, and the like.

[0032] Optionally, the functionalized molecules of the biomimetic nanoflow ion channel can be any one or more of poly (N-isopropylacrylamide), polydopamine, polyacrylic acid, polyethylenedioxythiophene, polystyrenesulfonic acid, polyallylamine hydrochloride, etc., which can carry positive or negative charges, inducing the surface charge density of the nanoflow ion channel to change with changes in external environmental stimuli.

[0033] Optionally, the bionic nanofluidic ion-based patterned flexible sensing device can further change external stimuli such as pH, temperature, stress, light, magnetic field, electric field, etc. according to the selection of functional molecule types to achieve signal enhanced sensing.

[0034] The present invention triggers the controllable structural deformation of the carbon nanochannel through the deformation of the flexible membrane, and regulates ion transmission by means of the geometric structure change of the nanochannel, thereby detecting the changes in electrical signals caused by stress, temperature, etc., and measuring deformation or sensing external pressure stimulation. Through mechanisms such as nanofluid control, double electric layer construction, ion rectification ratio regulation, and further combined with flexible electrodes for integrated packaging, a flexible tactile sensor device with high sensitivity, good stability, and low cost for signal enhancement can be obtained. In the future, it will have important application prospects in the fields of human motion monitoring, human-computer interaction interface, brain-like computing, ionic skin, flexible wearable electronic devices, etc.

[0035] Beneficial effects of the present invention:

[0036] 1) The present invention is a patterned flexible sensing device based on bionic nanocurrent ions. The unique bionic sensing characteristics of the nanocurrent ion channel of the present invention simulate the ultra-efficient processing, storage and transmission of sensory information. The sensory information processing process is more similar to the working mode of living organisms and is more efficient.

[0037] 2) The present invention can work in a physiological solution system and has good biocompatibility, and has greater potential in the future fields of neuromorphic devices, brain-computer interfaces, wearable flexible devices, electronic skin, etc.

[0038] 3) The precise patterned construction method provided by the present invention has the characteristics of autonomous design and adjustment, and can realize different functions according to actual needs. It has greater flexibility in constructing the standardized area size of nanocurrent ion channels and in the process of constructing and beautifying electronic skin and wearable flexible devices.

[0039] 4) The principle of bionic sensing in the present invention is based on the confinement enhancement effect of ions in nanocurrent ion channels, and the enhancement of sensing signals is further achieved by changing the geometric shape of the nanocurrent ion channels. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

[0041] Figure 1 Test curves of the photoresist thickness of the carbon nanotube growth substrate and the thickness of the metal nanoparticle vapor deposition layer in the bionic nanocurrent ion-based patterned flexible sensing device.

[0042] Figure 2 Technical route of bionic nanoflow ion-based patterned flexible sensing devices.

[0043] Figure 3 Optical photograph of the flexible membrane in the bionic nanoflow ion-based patterned flexible sensing device.

[0044] Figure 4 The reaction process of carbon nanotube nanofluidic ion channels grafted with PNIPAAm polymer molecular brushes in bionic nanofluidic ion-based patterned flexible sensing devices.

[0045] Figure 5 By regulating the geometric structure of nanocurrent ion channels and changing external stimuli such as temperature, enhanced sensing of ion current signals can be achieved.

[0046] Figure 6 Standardized area size of nanoflow ion channels constructed in bionic nanoflow ion-based patterned flexible sensing devices.

[0047] Figure 7 The independent variables such as geometric structure and external pH stimulation are digitally encoded and substituted into the neural network model for dependent variable calculation.

[0048] Figure 8 Test curve of unfunctionalized nanoflow ion-based patterned flexible sensing device. DETAILED DESCRIPTION

[0049] Example 1

[0050] First, a silicon wafer with a dense silicon dioxide layer (300nm) on the surface is cut into 2cm×2cm, placed in a coating machine, and a UV positive photoresist is spin-coated at 2500rpm for 60s. After two spin coatings, it is placed at 110℃ and baked for 5 minutes to obtain a photoresist substrate with a thickness of about 2.50μm. A pre-designed standard circular pattern is exposed under ultraviolet light using a photolithography machine. The exposed photoresist coating is placed in a tetramethylammonium hydroxide solution for development, and a patterned photoresist growth substrate is obtained after baking. The patterned photoresist growth substrate obtained by the above method is first subjected to 3nm metal Cr particle evaporation as an adhesion layer, and then Pt particle evaporation is performed to obtain a metal Pt particle evaporation layer of about 100nm to protect the non-growth area (such as Figure 1 As shown). After that, the growth substrate was ultrasonically cleaned with anhydrous ethanol for 10 minutes until the carbon nanotube array growth area (silicon dioxide layer) was exposed. Using toluene as a carbon source and ferrocene as a catalyst, high-temperature chemical vapor deposition was performed in an argon atmosphere to prepare a carbon nanotube array precision patterned nanoflow ion channel with an inner diameter of about 10 nm. The process is as follows Figure 2 shown.

[0051] The flexible polymer epoxy resin was compounded with the precision patterned carbon nanotube array and polymerized and cured. The above-mentioned composite was paraffin frozen and embedded, and ultrathin sections were used to obtain flexible films of precision patterned carbon nanotube arrays of different thicknesses ( Figure 3), further subjected to plasma etching treatment, and ultrasonic cleaning with hydrochloric acid and ultrapure water. Afterwards, a polymer molecular brush is grafted into the nanoflow ion channel of the carbon nanotube array. In this method, the initiating group needs to be introduced into the substrate surface in advance, and then, under the action of the initiator and the catalyst, the polymerized monomer is polymerized and grown in situ on the surface to form a polymer molecular brush. The polymer molecular brush obtained by this method is more uniform and has a higher grafting density. This method requires a multi-step chemical reaction in the nanoflow ion channel of the carbon nanotube. First, the oxygen-containing functional group is modified in the nanoflow ion channel using a low-temperature plasma in an oxygen atmosphere, and then reacted with 5% γ-aminopropyltriethoxysilane (APTES) to introduce an amino group. The surface of the amino-treated carbon nanochannel membrane is reacted with 10 ml of dichloromethane, 200 μl of triethylamine, and 500 μl of 2-bromoisobutyryl bromide to fix the initiator on the surface. Subsequently, a reaction system of 600 mg N-isopropylacrylamide (NIPAAm), 200 μL pentamethyldiethylenetriamine (PMDTA), 9 mg cuprous bromide (CuBr), and methanol / water (volume ratio of 1, 20 mL) was subjected to surface-initiated atom transfer radical polymerization. CuBr was used as an inhibitor of the chain reaction to make the polymer monomers grow in situ on the film surface to form polymer molecular brushes, and obtain temperature-sensitive carbon nanotube arrays with precisely patterned functionalized nanofluidic ion channels, such as Figure 4 shown.

[0052] Afterwards, the functionalized nanofluidic ion channels of the carbon nanotube array with precise patterning were assembled and integrated with flexible electrodes as part of the circuit to obtain a biomimetic nanofluidic ion-based patterned flexible sensing device. At the same time, an electrochemical workstation was used to collect ion currents in real time in a 1 mmol / L KCl solution through electrodes, and the geometric structure of the nanofluidic ion channels was further regulated and external stimuli such as temperature were changed to achieve signal enhancement sensing ( Figure 5 ).

[0053] Example 2

[0054] First, a silicon wafer with a dense silicon dioxide layer (300nm) on the surface was cut into 2cm×2cm, placed in a coating machine, and a UV positive photoresist was spin-coated at 2500rpm for 60s. After two spin coatings, it was placed at 110℃ and baked for 5 minutes to obtain a photoresist substrate with a thickness of about 2.50μm. A pre-designed standard circular pattern was exposed under ultraviolet light using a photolithography machine. The exposed photoresist coating was placed in a tetramethylammonium hydroxide solution for development, and a patterned photoresist growth substrate was obtained after baking. The patterned photoresist growth substrate obtained by the above method was first subjected to 3nm metal Cr particle evaporation as an adhesion layer, and then Au particle evaporation was performed to obtain a metal Au particle evaporation layer of about 100nm to protect the non-growth area. After that, the growth substrate was ultrasonically cleaned with anhydrous ethanol for 10 minutes until the carbon nanotube array growth area (silicon dioxide layer) was exposed. Using toluene as a carbon source and ferrocene as a catalyst, high-temperature chemical vapor deposition was carried out in an argon atmosphere to prepare a carbon nanotube array precision patterned nanoflow ion channel with an inner diameter of about 10 nm.

[0055] The flexible polymer epoxy resin is compounded with the precision patterned carbon nanotube array in a certain ratio and polymerized and cured. The above-mentioned composite is paraffin frozen and embedded, and ultrathin sections are used to obtain precision patterned carbon nanotube array flexible films with different standardized circular areas ( Figure 6 ), further subjected to plasma etching treatment, and ultrasonic cleaning with hydrochloric acid and ultrapure water. Afterwards, a polymer molecular brush is grafted into the nanoflow ion channel of the carbon nanotube array. In this method, the initiating group needs to be introduced into the substrate surface in advance, and then, under the action of the initiator and the catalyst, the polymerized monomer is polymerized and grown in situ on the surface to form a polymer molecular brush. The polymer molecular brush obtained by this method is more uniform and has a higher grafting density. This method requires a multi-step chemical reaction in the nanoflow ion channel of the carbon nanotube. First, the oxygen-containing functional group is modified in the nanoflow ion channel using a low-temperature plasma in an oxygen atmosphere, and then reacted with 5% γ-aminopropyltriethoxysilane (APTES) to introduce an amino group. The surface of the amino-treated carbon nanochannel membrane is reacted with 10 ml of dichloromethane, 200 μl of triethylamine, and 500 μl of 2-bromoisobutyryl bromide to fix the initiator on the surface. Subsequently, a reaction system of 600 mg of N-isopropylacrylamide (NIPAAm), 200 μL of pentamethyldiethylenetriamine (PMDTA), 9 mg of cuprous bromide (CuBr) and methanol / water (volume ratio of 1, 20 ml) was subjected to surface-initiated atom transfer radical polymerization. CuBr served as an inhibitor of the chain reaction, causing the polymer monomers to grow in situ on the film surface to form polymer molecular brushes, thereby obtaining temperature-sensitive carbon nanotube arrays with precisely patterned functionalized nanofluidic ion channels.

[0056] Afterwards, the functionalized nanocurrent ion channels with precise patterning of the carbon nanotube array were assembled and integrated with flexible electrodes and used as part of the circuit to obtain a bionic nanocurrent ion-based patterned flexible sensing device. At the same time, an electrochemical workstation was used to collect ion current in real time in a 10 mmol / L KCl solution through electrodes, and the geometric structure of the nanocurrent ion channels was further regulated and external stimuli such as temperature were changed to achieve signal enhanced sensing.

[0057] Example 3

[0058] First, a silicon wafer with a dense silicon dioxide layer (300nm) on the surface was cut into 2cm×2cm, placed in a coating machine, and a UV positive photoresist was spin-coated at 2500rpm for 60s. After two spin coatings, it was placed at 110℃ and baked for 5 minutes to obtain a photoresist substrate with a thickness of about 2.50μm. A pre-designed standard circular pattern was exposed under ultraviolet light using a photolithography machine. The exposed photoresist coating was placed in a tetramethylammonium hydroxide solution for development, and a patterned photoresist growth substrate was obtained after baking. The patterned photoresist growth substrate obtained by the above method was first subjected to 3nm metal Cr particle evaporation as an adhesion layer, and then Au particle evaporation was performed to obtain a metal Au particle evaporation layer of about 100nm to protect the non-growth area. After that, the growth substrate was ultrasonically cleaned with anhydrous ethanol for 10 minutes until the carbon nanotube array growth area (silicon dioxide layer) was exposed. Using toluene as a carbon source and ferrocene as a catalyst, high-temperature chemical vapor deposition was carried out in an argon atmosphere to prepare a carbon nanotube array precision patterned nanoflow ion channel with an inner diameter of about 10 nm.

[0059] The flexible polymer epoxy resin is compounded with the precision patterned carbon nanotube array in a certain proportion and polymerized and cured. The above-mentioned composite is paraffin frozen and embedded, and ultrathin sections are obtained to obtain precision patterned carbon nanotube array flexible membranes of different standardized circular areas, which are further treated with plasma etching and ultrasonically cleaned with hydrochloric acid and ultrapure water. After that, the polymer molecular brush is grafted in the nanoflow ion channel of the carbon nanotube array. In this method, the initiating group needs to be introduced into the substrate surface in advance, and then under the action of the initiator and the catalyst, the polymer monomer is polymerized and grown in situ on the surface to form a polymer molecular brush. The polymer molecular brush obtained by this method is more uniform and has a higher grafting density. This method requires multi-step chemical reactions in the nanoflow ion channel of the carbon nanotube. First, the oxygen-containing functional group is modified in the nanoflow ion channel using low-temperature plasma in an oxygen atmosphere, and then reacted with γ-aminopropyltriethoxysilane (APTES) to introduce amino groups. The surface of the amino-modified carbon nanochannel membrane reacts with 2-bromoisobutyryl bromide to fix the initiator on the surface. Subsequently, acrylic acid (AA), pentamethyldiethylenetriamine (PMDTA), cuprous bromide (CuBr) and methanol / water reaction system were subjected to surface-initiated atom transfer radical polymerization. CuBr served as an inhibitor of the chain reaction, causing the polymer monomers to grow in situ on the film surface to form polymer molecular brushes, thereby obtaining pH-sensitive carbon nanotube arrays with precisely patterned functionalized nanofluidic ion channels.

[0060] Afterwards, the functionalized nanofluidic ion channels of the carbon nanotube array with precise patterning were assembled and integrated with flexible electrodes as part of the circuit to obtain a biomimetic nanofluidic ion-based patterned flexible sensing device. At the same time, an electrochemical workstation was used to collect ion currents in real time in a 1 mmol / L KCl solution through electrodes. The geometric structure of the nanofluidic ion channels was further regulated and external stimuli such as pH were changed to achieve signal enhancement sensing. The independent variables such as the geometric structure and external pH stimulation were digitally encoded and substituted into the neural network model for dependent variable calculation ( Figure 7 ).

[0061] Comparative Example 1

[0062] First, a silicon wafer with a dense silicon dioxide layer (300nm) on the surface was cut into 2cm×2cm, placed in a coating machine, and a UV positive photoresist was spin-coated at 2500rpm for 60s. After two spin coatings, it was placed at 110℃ and baked for 5 minutes to obtain a photoresist substrate with a thickness of about 2.50μm. A pre-designed standard circular pattern was exposed under ultraviolet light using a photolithography machine. The exposed photoresist coating was placed in a tetramethylammonium hydroxide solution for development, and a patterned photoresist growth substrate was obtained after baking. The patterned photoresist growth substrate obtained by the above method was first subjected to 3nm metal Cr particle evaporation as an adhesion layer, and then Pt particle evaporation was performed to obtain a metal Pt particle evaporation layer of about 100nm to protect the non-growth area. After that, the growth substrate was ultrasonically cleaned with anhydrous ethanol for 10 minutes until the carbon nanotube array growth area (silicon dioxide layer) was exposed. Using toluene as a carbon source and ferrocene as a catalyst, high-temperature chemical vapor deposition was carried out in an argon atmosphere to prepare a carbon nanotube array precision patterned nanoflow ion channel with an inner diameter of about 10 nm.

[0063] The flexible polymer epoxy resin is compounded with the precision patterned carbon nanotube array in a certain ratio and polymerized and cured. The above-mentioned composite is paraffin frozen and embedded, and ultrathin sections are obtained to obtain flexible films of precision patterned carbon nanotube arrays of different thicknesses, which are further treated with plasma etching and ultrasonically cleaned with hydrochloric acid and ultrapure water.

[0064] Afterwards, the functionalized nanofluidic ion channels precisely patterned by the carbon nanotube arrays were assembled and integrated with flexible electrodes as part of the circuit to obtain a biomimetic nanofluidic ion-based patterned flexible sensing device. At the same time, an electrochemical workstation was used to collect ion currents in real time in a 1 mmol / L KCl solution through the electrodes to further regulate the geometric structure of the nanofluidic ion channels. There was no significant enhancement in the current sensing signal ( Figure 8 ).

[0065] The above description is only a preferred embodiment of the present invention, and therefore cannot be used to limit the scope of the present invention. That is, equivalent changes and modifications made according to the patent scope of the present invention and the contents of the specification should still fall within the scope of the present invention.

Claims

1. A bionic nanoflow ion-based patterned flexible sensing device, characterized in that: The invention comprises a patterned carbon nanotube-based nanoflow ion channel flexible high molecular polymer membrane, wherein the nanoflow ion channel has an electrolyte solution, the nanoflow ion channel is modified by functionalized molecules, and the inner diameter of the bionic nanoflow ion channel is between 1nm and 100nm.

2. The bionic nanoflow ion-based patterned flexible sensing device according to claim 1, characterized in that: The nanoflow ion-based flexible sensing device has mechanical responsiveness and temperature responsiveness.

3. The bionic nanoflow ion-based patterned flexible sensing device according to claim 1, characterized in that: The functionalized molecule of the bionic nanoflow ion channel is at least one of poly (N-isopropylacrylamide), polydopamine, polyacrylic acid, polyethylene dioxythiophene, polystyrene sulfonic acid and polyallylamine hydrochloride.

4. The bionic nanoflow ion-based patterned flexible sensing device according to claim 1, characterized in that: The ion types in the bionic nanocurrent ion channel include at least one of inorganic salts such as KCl, NaCl, and MgCl2.

5. The bionic nanoflow ion-based patterned flexible sensing device according to claim 1, characterized in that: The ion concentration in the bionic nanoflow ion channel is between 0.1 mmol / L and 1.0 mol / L.

6. A method for preparing a biomimetic nanofluidic ion-based patterned flexible sensing device, comprising the following steps: Step 1: obtaining a photoresist substrate and performing patterning on the photoresist substrate; growing a carbon nanotube array in a growth area on the patterned photoresist substrate; Step 2: Compounding and curing the carbon nanotube array with a flexible polymer, and then ultra-thinly slicing the composite to obtain a precisely patterned carbon nanotube array flexible film; Step 3: Grafting polymer molecular brushes into the nanoflow ion channels of the carbon nanotube array to obtain pH-sensitive carbon nanotube arrays with precise patterning of functionalized nanoflow ion channels; Step 4: Assemble and integrate the functionalized nanocurrent ion channel with the flexible electrode and use it as part of the circuit to obtain a bionic nanocurrent ion-based patterned flexible sensing device.

7. The preparation method according to claim 6, characterized in that: In step one, the non-growth area is protected by an adhesion layer and an evaporation layer.

8. The preparation method according to claim 6, characterized in that: In step 2, the flexible polymer includes any one of epoxy resin, polyimide, polycarbonate, and polyaniline.

9. The preparation method according to claim 6, characterized in that: In step three, the grafting method includes any one of plasma gasification grafting, atom transfer radical polymerization, and in-situ interfacial polymerization.

10. The preparation method according to claim 6, characterized in that: In step three, the grafted polymer molecular brush includes at least one of poly (N-isopropylacrylamide), polydopamine, polyacrylic acid, polyethylenedioxythiophene, polystyrene sulfonic acid, and polyallylamine hydrochloride.

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