Memristor with biomimetic synaptic structure and preparation method thereof

Abstract

The present invention provides a memristor with a biomimetic synaptic structure and a preparation method thereof, belonging to the technical field of memristors. The memristor with a biomimetic synaptic structure comprises: two opposing electrodes; a crown ether-doped two-dimensional material film layer located between the electrodes; and a polyelectrolyte hydrogel layer located on the crown ether-doped two-dimensional material film layer. When a voltage is applied to the electrodes, an oxidation reaction occurs on the electrode on the polyelectrolyte hydrogel layer to produce metal transport ions. The metal transport ions pass through the polyelectrolyte hydrogel layer and reach the crown ether-doped two-dimensional material film layer. Based on the binding action between the crown ether molecules in the crown ether-doped two-dimensional material film layer and the metal transport ions, a selective electrical response to the metal transport ions is achieved, resulting in the memristor exhibiting a conductance value related to the type of metal transport ions.

Description

Technical Field

[0001] The present invention belongs to the technical field of memristors, and in particular relates to a memristor with a biomimetic synaptic structure and a preparation method thereof. Background Art

[0002] The separation of processors and memory in traditional electronic computer architectures leads to the von Neumann bottleneck, where frequent data communication between processing and memory units significantly reduces processing speed and energy efficiency. However, the synaptic structure in the human brain integrates processing and memory units based on ionic conduction, significantly reducing energy consumption while enabling efficient parallel processing of complex information. This has led to the development of high-performance synaptic components that mimic biological synaptic structures. Memristors are electronic components whose resistance changes with time and voltage. Their dynamically variable resistance and non-volatile conductivity enable memory and learning functions similar to those of biological synapses, making them ideal components for biomimetic synapses in brain-inspired computing.

[0003] While current memristors are typically electronic devices, nature largely relies on ions for energy-efficient information processing. Ions are biologically selected as information carriers to generate and transmit signals. The diverse nature and chemical properties of ions endow living systems with powerful encoding and parallel computing capabilities. Therefore, developing memristors with multi-ion selectivity, using ions as information carriers, is crucial for future neuromorphic devices capable of low-energy, multi-data parallel encoding and computing.

[0004] There are currently many strategies for designing ionic memristor structures. Here we focus on double-layer memristors, which are currently mainly composed of gel and membrane.

[0005] Double-layer hydrogel memristors utilize heterojunction structures to achieve high rectification ratios (the highest reported is 158.64, achieved by doping the hydrogel with porphyrin additives to alter the gel's charge properties). These devices exhibit diode characteristics and can be used to construct circuits that function as logic gates. Some double-layer hydrogel ion diode devices can achieve biological synaptic-like functions (such as EPSCs), but their multi-ion selectivity, retention time, sensitivity to varying pulse voltages, and energy consumption require further exploration. Summary of the Invention

[0006] In response to the above technical problems, the present invention provides a memristor with a biomimetic synaptic structure and a preparation method thereof, in order to at least partially solve the above technical problems. The specific technical solutions provided by the present invention are as follows.

[0007] As an embodiment of one aspect of the present invention, a memristor with a biomimetic synapse structure is provided, comprising:

[0008] two electrodes disposed opposite to each other; and

[0009] a crown ether-doped two-dimensional material film layer located between the electrodes and a polyelectrolyte hydrogel layer located on the crown ether-doped two-dimensional material film layer;

[0010] Among them, when voltage is applied to the electrode, an oxidation reaction occurs at the electrode on the polyelectrolyte hydrogel layer to produce metal transport ions. The metal transport ions pass through the polyelectrolyte hydrogel layer to reach the crown ether-doped two-dimensional material film layer. Based on the binding effect between the crown ether molecules and the metal transport ions in the crown ether-doped two-dimensional material film layer, a selective electrical response to the metal transport ions is achieved, so that the memristor exhibits a conductivity value related to the type of metal transport ions.

[0011] As an embodiment of another aspect of the present invention, a method for preparing the above-mentioned memristor is provided, comprising:

[0012] Adding crown ether molecules and two-dimensional materials into water, mixing them evenly and forming a film to obtain a crown ether-doped two-dimensional material film;

[0013] adding the gel material to the polyelectrolyte aqueous solution and stirring thoroughly until the gel material is gelled to obtain a polyelectrolyte hydrogel;

[0014] After the polyelectrolyte hydrogel is stacked on the surface of a two-dimensional layered material film and placed between two oppositely arranged electrodes, a memristor with a biomimetic synaptic structure is obtained.

[0015] Based on the above technical solution, in a memristor with a biomimetic synaptic structure and its preparation method provided by the present invention, electrodes, polyelectrolyte hydrogel, and crown ether-doped two-dimensional material are used to simulate the presynaptic membrane, synaptic cleft, and postsynaptic membrane structures in a biological synapse, respectively. The electrodes on the polyelectrolyte hydrogel layer simulate the presynaptic membrane, the polyelectrolyte hydrogel layer simulates the synaptic cleft, and the crown ether-doped two-dimensional material film layer simulates the postsynaptic membrane. The metal transport ions provided by the electrodes through oxidation reactions simulate neurotransmitters, successfully preparing a memristor with a biomimetic synaptic structure. The memristor with a biomimetic synaptic structure provided by the present invention provides metal transport ions through electrode oxidation reactions, and the polyelectrolyte hydrogel layer provides a transmission channel for the metal transport ions to be transmitted to the crown ether-doped two-dimensional material film layer. The crown ether molecules bind to the metal transport ions, thereby generating a memristive curve. The overall conductance of the memristor is adjustable by applying a voltage to control the migration of the metal transport ions in and out of the crown ether-doped two-dimensional material film layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 A three-dimensional schematic diagram of a memristor according to the overall inventive concept of an embodiment of the present invention;

[0017] Figure 2 This is a volt-ampere curve diagram of the memristor in Example 1 of the present invention;

[0018] Figure 3 is a pulse amplitude-dependent plasticity diagram of the memristor in Example 1 of the present invention;

[0019] Figure 4 is a retention time curve diagram of the memristor in Example 1 of the present invention;

[0020] Figure 5 This is a picowatt-level energy consumption diagram of the memristor in Example 1 of the present invention;

[0021] Figure 6 Schematic diagram of a logic gate circuit constructed based on the memristor in Example 1 of the present invention;

[0022] Figure 7 for Figure 6 The result diagram of the logic gate circuit operation shown;

[0023] Figure 8 This is a volt-ampere curve diagram of the memristor in Example 2 of the present invention;

[0024] Figure 9 volt-ampere curves of the memristors in Examples 1, 3, and 4 of the present invention;

[0025] Figure 10 is a volt-ampere curve diagram of the memristor in Example 5 of the present invention;

[0026] Figure 11 This is a curve diagram of the peak current change of the memristor in Example 5 of the present invention.

[0027] The symbols are explained as follows:

[0028] 100: memristor;

[0029] 1, 4: electrodes;

[0030] 2: polyelectrolyte hydrogel layer;

[0031] 3: Crown ether doped two-dimensional material film layer. DETAILED DESCRIPTION

[0032] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings.

[0033] The development of double-layer membrane structure ion memristors is mainly achieved by combining a solid polyelectrolyte layer and a porous layered membrane. The solid polyelectrolyte layer provides ion transmission, and the porous layered membrane acts as an ion receptor. By applying voltage to regulate the migration of ions in the polyelectrolyte layer in the receptor membrane, adjustable conductivity and non-volatile conductivity are achieved. Specifically, the memristor curve and biological synapse-like functions such as biological-level retention time (ms-s), low operating voltage (5mV), and low energy consumption (16.7fW) are shown. Since the memristor heterostructure has rectification ratio performance, further circuit construction can also realize logic gate functions. Since the transmission ions in current reports come from the polyelectrolyte layer, the device ion selectivity is mostly for ions of the same group, such as alkali metal ions Li + 、Na + and halogen ions Cl - Br - , I - , while there are relatively few reports on the selectivity for element ions of different groups.

[0034] Therefore, the present invention provides a memristor with a biomimetic synaptic structure, which realizes a selective electrical response to the metal transport ions based on the binding effect of crown ether molecules and metal transport ions in the crown ether-doped two-dimensional material film layer, so that the memristor exhibits a conductance value related to the type of metal transport ions, which is crucial for realizing more powerful encoding and parallel computing capabilities of the memristor.

[0035] Figure 1 Schematic diagram of a memristor according to the overall inventive concept of an embodiment of the present invention.

[0036] According to the overall inventive concept of the present invention, Figure 1 As shown, a memristor 100 with a biomimetic synaptic structure is provided, comprising: two oppositely arranged electrodes 1 and 4; a crown ether-doped two-dimensional material film layer 3 located between the electrodes 1 and 4; and a polyelectrolyte hydrogel layer 2 located on the crown ether-doped two-dimensional material film layer 3.

[0037] Among them, when voltage is applied to electrodes 1 and 4, electrode 1 on the polyelectrolyte hydrogel layer 2 undergoes an oxidation reaction to produce metal transport ions, and the metal transport ions pass through the polyelectrolyte hydrogel layer 2 to reach the crown ether-doped two-dimensional material film layer 3. Based on the binding effect between the crown ether molecules and the metal transport ions in the crown ether-doped two-dimensional material film layer 3, a selective electrical response to the metal transport ions is achieved, so that the memristor 100 exhibits a conductivity value related to the type of metal transport ions.

[0038] In the memristor with a biomimetic synaptic structure according to an embodiment of the present invention, electrodes 1 and 4, a polyelectrolyte hydrogel layer 2, and a crown ether-doped two-dimensional material film layer 3 are used to simulate the presynaptic membrane, synaptic cleft, and postsynaptic membrane structures in a biological synapse, respectively. Electrode 1 on the polyelectrolyte hydrogel layer 2 simulates the presynaptic membrane, the polyelectrolyte hydrogel layer 2 simulates the synaptic cleft, and the crown ether-doped two-dimensional material film layer 3 simulates the postsynaptic membrane. The metal transport ions provided by the electrodes through an oxidation reaction simulate neurotransmitters, successfully fabricating a memristor with a biomimetic synaptic structure. The biomimetic synaptic structure memristor provided by the present invention provides metal transport ions through an electrode oxidation reaction, and the polyelectrolyte hydrogel layer provides a transmission channel for the metal transport ions to be transmitted to the crown ether-doped two-dimensional material film layer. The crown ether molecules bind to the metal transport ions, thereby generating a memristive curve. By applying a voltage to control the migration of the metal transport ions in and out of the crown ether-doped two-dimensional material film layer, the overall conductance of the memristor can be adjusted.

[0039] According to an embodiment of the present invention, the crown ether-doped two-dimensional material film layer 3 is formed of a two-dimensional material doped with crown ether molecules. The two-dimensional material includes at least one of graphene oxide and MXene. The crown ether molecules include at least one of 4'-aminobenzo-15-crown-5-ether, 4'-aminobenzo-18-crown-6-ether, and aza-12-crown-4-ether.

[0040] In embodiments of the present invention, crown ether molecules, with their unique cyclic structure, selectively complex specific metal transport ions, enhancing the memristor's ion recognition capabilities and facilitating high-precision information storage in multi-ion systems. The metal transport ions are transported through the polyelectrolyte hydrogel layer into the crown ether-doped two-dimensional material film. Due to the varying binding interactions between the metal transport ions and the crown ether molecules, the metal transport ions migrate in varying amounts, resulting in varying conductance values ​​and enabling the memristor to selectively respond to signals from different metal transport ions. Furthermore, the polyelectrolyte hydrogel layer provides a liquid water-like transmission channel, increasing the metal transport ion transmission rate and, consequently, the memristor's response speed and operating efficiency.

[0041] The stacked or assembled two-dimensional material layers form a porous structure, providing storage sites for metal-transporting ions and forming a stable three-dimensional network of ion transport channels, ensuring that the metal-transporting ion transport channels are not easily collapsed or blocked during memristor operation. The two-dimensional material itself has excellent mechanical properties, which can enhance the overall strength and toughness of the crown ether-doped two-dimensional material film layer, resist the mechanical stress during memristor preparation and use, and improve the bonding between the film and other materials, extending the life of the memristor. Furthermore, the two-dimensional material has certain electrical properties that can interact with the crown ether and metal-transporting ions to influence the electrical behavior of the crown ether-doped two-dimensional material film layer. For example, it can participate in the charge transfer process as an electron acceptor or electron donor, affecting the conductivity and capacitance characteristics, and thus the resistance switching characteristics of the memristor. Its electrical properties are also adjustable, providing a way to optimize the electrical performance of the memristor.

[0042] According to an embodiment of the present invention, the polyelectrolyte hydrogel layer 2 is formed from a polyelectrolyte material and a gel material. The polyelectrolyte material includes at least one of polystyrene sulfonic acid, sodium polystyrene sulfonate, potassium polystyrene sulfonate, polyacrylic acid, sodium polyacrylate, potassium polyacrylate, polymethacrylic acid, sodium polymethacrylate, potassium polymethacrylate, polyethylene sulfonic acid, sodium polyethylene sulfonate, potassium polyethylene sulfonate, polyvinyl phosphoric acid, sodium polyethylene phosphate, and potassium polyethylene phosphate; the gel material includes at least one of a polysaccharide gel material, a polypeptide gel material, and an acrylic gel material. The polysaccharide gel material includes at least one of starch, cellulose, alginic acid, and hyaluronic acid chitosan; the polypeptide gel material includes at least one of collagen, poly-L-lysine, and poly-L-glutamic acid; and the acrylic gel material includes at least one of polyacrylic acid, polymethacrylic acid, polyacrylamide, and poly-N-polyacrylamide.

[0043] In embodiments of the present invention, the polyelectrolyte material itself possesses ion conductivity, providing a migration channel for metal transport ions. During memristor operation, metal transport ions can migrate along the molecular chains or internal structure of the polyelectrolyte material, thereby enabling charge transfer. This is crucial for achieving the memristor's electrical properties, such as resistance switching, and is one of the foundations for its proper function. The polyelectrolyte material can modulate the electrical properties of the polyelectrolyte hydrogel layer through its chemical structure and properties, affecting parameters such as capacitance and resistance. Different types of polyelectrolyte materials have different electrical properties. By selecting the appropriate polyelectrolyte material, the electrical performance of the memristor can be optimized, enabling stable resistance switching characteristics under specific voltage and current conditions. Within the polyelectrolyte hydrogel layer, the polyelectrolyte material and the gel material work synergistically, interacting with the gel material through chemical bonds or physical adsorption, creating a stable and well-functioning polyelectrolyte hydrogel layer structure, thereby contributing to the overall performance of the memristor.

[0044] Gel materials can form a three-dimensional network-like structure, providing physical support for the polyelectrolyte hydrogel layer and maintaining its shape and stability. Gel materials are also generally flexible, allowing the polyelectrolyte hydrogel layer to adapt well to external forces (such as pressure and bending that may be encountered during memristor fabrication, packaging, or actual use) without easily breaking or damaging, thus ensuring the integrity of the memristor structure. The network structure within the gel material can store a certain amount of ions and also provides additional channels and pathways for the transport of metal transport ions. This network, in conjunction with the ionic conductivity of the polyelectrolyte material, further promotes the migration of metal transport ions within the polyelectrolyte hydrogel layer, helping to improve the ion transport efficiency and overall performance of the memristor. Furthermore, gel materials can modulate certain physical and chemical properties of the polyelectrolyte hydrogel layer, such as its water absorption and moisture retention. A suitable gel material can ensure that the polyelectrolyte hydrogel layer maintains relatively stable performance under varying environmental conditions (such as humidity fluctuations), preventing performance degradation caused by environmental factors and thus extending the lifespan of the memristor.

[0045] According to an embodiment of the present invention, the thickness of the crown ether-doped two-dimensional material film layer 3 is 3-4 μm. The thickness of the crown ether-doped two-dimensional material film layer affects the length and density of the metal-transmitting ion transmission channels. A thinner crown ether-doped two-dimensional material film layer means that the metal-transmitting ion transmission channels are relatively shorter, facilitating the rapid passage of metal-transmitting ions and improving the response speed of the memristor. Furthermore, a thinner film layer has a relatively higher pore density (other things being equal), providing more transmission paths for metal-transmitting ions and further facilitating their transport. However, an excessively thin crown ether-doped two-dimensional material film layer may result in insufficient mechanical strength and be susceptible to damage during preparation or use, thus shortening the lifespan of the memristor. A crown ether-doped two-dimensional material film layer of appropriate thickness helps maintain good metal-transmitting ion selectivity and storage capacity. The thickness of the crown ether-doped two-dimensional material film layer affects the crown ether's selective complexation with metal-transmitting ions and the storage of metal-transmitting ions within the crown ether-doped two-dimensional material film. If it is too thick, the diffusion path of metal transport ions in the crown ether-doped two-dimensional material membrane layer will become longer, which will reduce the selectivity of metal transport ions and is not conducive to the effective storage of metal transport ions; if it is too thin, it will not provide enough space to achieve effective selective complexation and storage of metal transport ions.

[0046] According to an embodiment of the present invention, the thickness of the polyelectrolyte hydrogel layer 2 is 0.1-1 cm. A thinner polyelectrolyte hydrogel layer can allow metal transport ions to pass through more quickly because the migration path is relatively short and the resistance encountered is relatively small, thereby helping to improve the transmission efficiency of metal transport ions in the memristor, enabling the memristor to achieve a transition in resistance state in a shorter time, thereby improving the response speed. However, if it is too thin, it will not provide enough storage sites for metal transport ions, affecting the effective storage of metal transport ions and the stability of the electrical performance of the memristor. A polyelectrolyte hydrogel layer of appropriate thickness is crucial to maintaining stable electrical performance. An overly thick polyelectrolyte hydrogel layer will increase the resistance to metal transport ion transmission, making it difficult for current to pass through, thereby affecting the resistance switching characteristics of the memristor, making the resistance transition less sensitive or unstable. At the same time, being too thick will affect the interaction with the crown ether-doped two-dimensional material film layer and the electric field distribution of the entire device, which is not conducive to the normal operation of the memristor.

[0047] In the embodiments of the present invention, the thicknesses of the crown ether-doped 2D material layer and the polyelectrolyte hydrogel layer are matched. If the thickness ratio is not balanced, for example, the crown ether-doped 2D material layer is too thick or too thin relative to the crown ether-doped 2D material layer, the overall balance of the memristor structure will be disrupted, affecting the transmission and storage of metal transport ions between the two layers, thereby reducing the overall performance of the memristor.

[0048] As an embodiment of another aspect of the present invention, a method for preparing the above-mentioned memristor is provided, comprising:

[0049] Adding crown ether molecules and two-dimensional materials into water, mixing them evenly and forming a film to obtain a crown ether-doped two-dimensional material film;

[0050] adding the gel material to the polyelectrolyte aqueous solution and stirring thoroughly until the gel material is gelled to obtain a polyelectrolyte hydrogel;

[0051] After the polyelectrolyte hydrogel is stacked on the surface of a two-dimensional layered material film and placed between two oppositely arranged electrodes, a memristor with a biomimetic synaptic structure is obtained.

[0052] In an embodiment of the present invention, a crown ether-doped two-dimensional material film was prepared by a blending method, and a polyelectrolyte hydrogel was prepared by a hydrothermal method. The crown ether-doped two-dimensional material film and the polyelectrolyte hydrogel were stacked and placed in an electrode to produce a memristor with a biomimetic synapse structure. The method for preparing a memristor with a biomimetic synapse structure provided by the present invention features a simple preparation process, is easy to operate and implement, and requires minimal experimental equipment and conditions, making it suitable for large-scale deployment.

[0053] According to an embodiment of the present invention, the mass ratio of crown ether molecules to two-dimensional material is 1:0.3-2. When the ratio of crown ether molecules to two-dimensional material is not appropriate, the resistance variation range of the memristor becomes smaller or unstable. A high ratio of crown ether molecules can lead to excessive dispersion of the metal transport ions in the memristor, preventing the formation of a stable resistance state. A low ratio of crown ether molecules can hinder the migration of metal transport ions, making it difficult to achieve a good resistance state transition.

[0054] According to an embodiment of the present invention, the mass ratio of the polyelectrolyte material to the gel material is 1-5: 1. By changing the amount of polyelectrolyte added, the polyelectrolyte content in the polyelectrolyte hydrogel can be changed, thereby changing the ion transfer efficiency.

[0055] According to an embodiment of the present invention, the mass of the gel material is 2-5% of the mass of the water in the polyelectrolyte aqueous solution. A high proportion of gel material results in good strength and toughness, while a high proportion of water results in softness and elasticity but poor stability. A high proportion of gel material results in channels dominated by the hydrogel network, which hinders the movement of metal-transported ions but selectively adsorbs them. A high proportion of water facilitates the diffusion of metal-transported ions, but too high a proportion weakens their interaction with active sites. A high proportion of gel material results in a faster gelation process but is prone to unevenness, while a high proportion of water results in a slower gelation process.

[0056] Specifically, the present invention illustratively provides a specific method for preparing a polyelectrolyte hydrogel: 50-700 mg of sodium polystyrene sulfonate powder is added to a beaker, dissolved in 10-200 ml of deionized water, and stirred at room temperature until completely dissolved; 50-400 mg of agarose is added to the beaker, and heated and stirred at 60-95°C for about 3 hours or more until the agarose is completely dissolved and no obvious bubbles are present; the liquid in the beaker is poured into a culture dish, left at room temperature, and the liquid is cooled to form a sodium polystyrene sulfonate hydrogel.

[0057] Similarly, the present invention illustratively provides a specific method for preparing a crown ether-doped two-dimensional material film: weigh 5-200 mg of graphene oxide powder and 5-200 mg of 4'-aminobenzo-15-crown 5-ether powder, dissolve them in 10-200 ml of deionized water, stir for 1-3 days, and then place them in ultrasonic oscillation for more than 2 hours; vacuum filter for 1-3 days to obtain a crown ether-doped graphene oxide film.

[0058] The present invention is further illustrated below by examples and related test experiments. In the detailed description below, for ease of explanation, many specific details are set forth to provide a comprehensive understanding of the embodiments of the present invention. However, it is obvious that one or more embodiments can also be implemented without these specific details. Moreover, in the case of no conflict, the details in the following embodiments can be arbitrarily combined into other feasible embodiments. All instruments, consumables and reagents in the following examples, unless otherwise specified, can be obtained from commercial sources.

[0059] Example 1

[0060] In this embodiment 1, a memristor with a synaptic structure is prepared by the following steps.

[0061] First, crown ether-doped graphene oxide film was prepared by a blending method. The specific preparation steps are as follows.

[0062] 10 mg of graphene oxide powder and 5 mg of 4'-aminobenzo-15-crown 5-ether powder were weighed, dissolved in 50 ml of deionized water, stirred for 1 day, and then placed in ultrasonic oscillation for 5 hours; vacuum filtration was performed for 1 day to form a film.

[0063] Then, a sodium polystyrene sulfonate hydrogel layer was prepared by a hydrothermal method, and the specific preparation steps are as follows.

[0064] Add 700 mg of sodium polystyrene sulfonate powder to a beaker and dissolve it in 20 ml of deionized water. Stir at room temperature until completely dissolved. Add 300 mg of agarose to the beaker and heat at 90°C with stirring for about half an hour until the agarose is completely dissolved and no bubbles are visible. Pour the above liquid into a culture dish and let it stand at room temperature. The liquid will cool to form a sodium polystyrene sulfonate hydrogel.

[0065] Finally, the prepared 4'-aminobenzo-15-crown 5-ether doped graphene oxide film was stacked with sodium polystyrene sulfonate hydrogel, and zinc electrodes were sandwiched on both sides to obtain a memristor.

[0066] Figure 2 This is a volt-ampere curve of the memristor in Example 1 of the present invention.

[0067] like Figure 2 As shown in FIG. 1 , different voltages are applied to the memristor in Example 1 of the present invention to measure the cyclic voltammetry curve (IV curve) of the memristor. Figure 2As can be understood, the peak current increases with the number of scans, demonstrating that the memristor of this embodiment has adjustable conductance, that is, synaptic plasticity. When voltage is applied to the memristor of this embodiment and IV cyclic scanning is performed, the peak current increases significantly under forward voltage, demonstrating that the conductance of the memristor in this embodiment 1 is adjustable with the applied voltage, frequency, and time. The current spike does not change significantly under reverse voltage, demonstrating that the memristor of this embodiment has a significant rectification ratio. In a single IV scan, the current exhibits a figure-eight hysteresis curve, meeting the definition of a memristor.

[0068] Figure 3 Graph showing the pulse amplitude-dependent plasticity of the memristor in Example 1 of the present invention.

[0069] like Figure 3 As shown, in Example 1 of the present invention, 20 pulse voltage signals are applied to the memristor, with the amplitude of the pulse voltage as a variable. The device current response is different under different voltage amplitudes. Figure 3 The curve shown demonstrates that the voltage amplitude-dependent plasticity of the memristor of this embodiment is such that the memristor can recognize a minimum amplitude of 0.2V.

[0070] Figure 4 This is a retention time curve diagram of the memristor in Example 1 of the present invention.

[0071] like Figure 4 As shown, in Example 1 of the present invention, 10 pulse voltages with a pulse width of 10ms and an interval of 10ms are applied to the memristor, with an amplitude of 0.1-0.9V. In the figure, when the voltage is 0, the current slowly returns to the baseline, and the retention time is in the ms level. Figure 4 The curve shown demonstrates the non-volatility of the memristor conductance of this embodiment.

[0072] Figure 5 This is a picowatt-level energy consumption diagram of the memristor in Example 1 of the present invention.

[0073] like Figure 5 As shown in FIG1 , when a voltage of the same order of magnitude as the biological synaptic operating voltage (mV) is applied to the memristor in Example 1 of the present invention, the average power consumed by a single synaptic event is 44.5 pW (given by Ipeak×V). Figure 5 The curve shown demonstrates that the operating power (pW) of the memristor of this embodiment is of the same order of magnitude as that of the biological synapse.

[0074] Figure 6 Schematic diagram of a logic gate circuit constructed based on the memristor in Example 1 of the present invention, wherein the memristor in Example 1 of the present invention is used as Figure 6 The diode in Figure 7 for Figure 6 The diagram shows the operation results of the logic gate circuit.

[0075] like Figure 6-Figure 7 As shown in Figure 2, since the memristor heterostructure has a certain rectification ratio (3-50, related to the applied electric field history), according to Figure 6 As shown in the figure, a logic gate circuit is constructed, and two input signal variables are set, namely the input bias voltage and the switching state of the diode. Figure 7 The curves shown prove that the logic gate circuit constructed based on the memristor in Example 1 of the present invention realizes the functions of logic gates "OR" and "AND" under different bias voltages.

[0076] Example 2

[0077] In this embodiment 2, a memristor with a synaptic structure is prepared. The preparation method is the same as that in embodiment 1, except that the electrolyte material used in this embodiment 2 is polystyrene sulfonic acid. The specific preparation method is as follows.

[0078] Add 700 mg of polystyrene sulfonic acid powder to a beaker and dissolve it in 20 ml of deionized water. Stir at room temperature until completely dissolved. Add 300 mg of agarose to the beaker and heat and stir at 90°C for more than half an hour until the agarose is completely dissolved and no bubbles are obvious. Pour the liquid into a culture dish and let it stand at room temperature for half an hour. Then cool the liquid to form a polystyrene sulfonic acid hydrogel.

[0079] Figure 8 This is a volt-ampere curve diagram of the memristor in Example 2 of the present invention.

[0080] like Figure 8 As shown, a voltage is applied to the memristor to measure the cyclic voltammetry curve (IV curve) of the memristor in this embodiment 2, Figure 8 The curve shown shows that the memristor of this embodiment has memristive characteristics and adjustable conductance.

[0081] Example 3

[0082] In this embodiment 3, a memristor with a synaptic structure is prepared. The preparation method is the same as that in embodiment 1, except that the electrode material used in this embodiment 3 is an iron sheet.

[0083] Example 4

[0084] In this embodiment 4, a memristor with a synaptic structure is prepared. The preparation method is the same as that in embodiment 1, except that the electrode material used in this embodiment 4 is copper sheet.

[0085] Figure 9 1 is a volt-ampere curve diagram of the memristor in Example 1, Example 3 and Example 4 of the present invention.

[0086] like Figure 9 As shown in Figure 2, a voltage is applied to a memristor using different metal materials (iron, zinc, copper) as electrodes. Figure 9The IV curves shown illustrate the dependence of the hysteresis loop area on the type of active electrode, which enables selective transmission of ion signals.

[0087] Example 5

[0088] In this embodiment 5, a memristor with a synaptic structure is prepared. The preparation method is the same as that in embodiment 1, except that in this embodiment 5, a graphene oxide film is prepared by a vacuum filtration method.

[0089] Figure 10 is a volt-ampere curve diagram of the memristor in Example 5 of the present invention; Figure 11 This is a curve diagram of the peak current change of the memristor in Example 5 of the present invention.

[0090] like Figure 10-11 As shown, a voltage is applied to the memristor in Example 5 of the present invention to measure the cyclic voltammetry curve (IV curve) of the memristor. The test results show that the conductance change of the memristor in this embodiment is unstable and tends to saturation. Figure 11 The figure shows the peak current change value. After replacing it with crown ether doped graphene oxide film, a continuously enhanced conductivity signal can be observed ( Figure 2 ). It is proved that the doping of crown ether increases the interlayer spacing and ion storage sites of the two-dimensional material film, achieving an enhanced memory signal.

[0091] In summary, the polyelectrolyte hydrogel in the biomimetic synapse-like memristor provided by the present invention achieves pressure-, temperature-, and humidity-sensitive responses, facilitating interactive environmental sensing and information processing. The crown ether-doped two-dimensional material membrane employs a simple blending method to dope crown ether molecules into the channels between the two-dimensional materials. The different binding interactions of the crown ether molecules with different metal ions produce different conductance values, enabling the memristor to selectively respond to signals from different metal ions. The present invention generates metal transport ions through electrode oxidation reactions, achieving selective response to elements from different groups, providing a new approach to achieving multi-ion selective response in ionic memristors. By combining electrodes with the crown ether-doped two-dimensional material membrane, the crown ether molecules exhibit different binding abilities for different metal ions, enabling multi-ion selective response in the memristor. Furthermore, the biomimetic synapse-like memristor provided by the present invention exhibits memristive curves and various biological synaptic phenomena, such as biological-level retention time (ms), low operating voltage (0.2V), and low energy consumption (16.7fW). The heterogeneous structure of the biomimetic synaptic memristor provided by the present invention enables it to have a high rectification ratio. By constructing a circuit and setting two input signal variables, namely the input bias voltage and the switching state of the diode, the functions of the logic gates "OR" and "AND" are realized under different bias voltages, laying the foundation for the construction of future artificial nanofluidic neural networks.

[0092] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A memristor with a biomimetic synaptic structure, comprising: two electrodes arranged opposite to each other; as well as a crown ether-doped two-dimensional material film layer located between the electrodes and a polyelectrolyte hydrogel layer located on the crown ether-doped two-dimensional material film layer; When a voltage is applied to the electrode, an oxidation reaction occurs at the electrode on the polyelectrolyte hydrogel layer to produce metal transport ions. The metal transport ions pass through the polyelectrolyte hydrogel layer to reach the crown ether-doped two-dimensional material film layer. Based on the binding effect between the crown ether molecules in the crown ether-doped two-dimensional material film layer and the metal transport ions, a selective electrical response to the metal transport ions is achieved, so that the memristor exhibits a conductance value related to the type of the metal transport ions.

2. The memristor according to claim 1, wherein The crown ether-doped two-dimensional material film layer is formed by a two-dimensional material doped with crown ether molecules; The polyelectrolyte hydrogel layer is formed of a polyelectrolyte material and a gel material.

3. The memristor according to claim 2, wherein: The two-dimensional material includes at least one of graphene oxide and MXene; The crown ether molecule includes at least one of 4'-aminobenzo-15-crown-5-ether, 4'-aminobenzo-18-crown-6-ether, and aza-12-crown-4-ether.

4. The memristor according to claim 2, wherein The polyelectrolyte material comprises at least one of polystyrene sulfonic acid, sodium polystyrene sulfonate, potassium polystyrene sulfonate, polyacrylic acid, sodium polyacrylate, potassium polyacrylate, polymethacrylic acid, sodium polymethacrylate, potassium polymethacrylate, polyethylene sulfonic acid, sodium polyethylene sulfonate, potassium polyethylene sulfonate, polyvinyl phosphoric acid, sodium polyphosphate, and potassium polyvinyl phosphate; The gel material includes at least one of a polysaccharide gel material, a polypeptide gel material, and an acrylic gel material.

5. The memristor according to claim 4, wherein The polysaccharide gel material includes at least one of starch, cellulose, alginic acid, hyaluronic acid chitosan; The polypeptide gel material includes at least one of collagen, poly-L-lysine, and poly-L-glutamic acid; The acrylic gel material includes at least one of polyacrylic acid, polymethacrylic acid, polyacrylamide, and poly-N-polyacrylamide.

6. The memristor according to any one of claims 1 to 5, wherein: The thickness of the crown ether-doped two-dimensional material film layer is 3-4 μm; The thickness of the polyelectrolyte hydrogel layer is 0.1-1 cm.

7. A method for preparing a memristor according to any one of claims 1 to 6, comprising: Adding crown ether molecules and two-dimensional materials into water, mixing them evenly and forming a film to obtain a crown ether-doped two-dimensional material film; adding the gel material to the polyelectrolyte aqueous solution and stirring thoroughly until the gel material is gelled to obtain a polyelectrolyte hydrogel; After the polyelectrolyte hydrogel is stacked on the surface of the crown ether-doped two-dimensional material film, it is placed between two oppositely arranged electrodes to obtain a memristor with a biomimetic synaptic structure.

8. The method according to claim 7, wherein: The mass ratio of the crown ether molecule to the two-dimensional material is 1:0.3-2.

9. The method according to claim 7, wherein: The mass ratio of the polyelectrolyte material to the gel material is 1-5:

1.

10. The method according to claim 7, wherein: The mass of the gel material is 2-5% of the mass of water in the polyelectrolyte aqueous solution.

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