Ionoelectronic device and method of manufacturing and use thereof

Abstract

This invention discloses an ion-electronic device, its fabrication method, and its applications. The ion-electronic device comprises a polymer hydrogel matrix and an organic framework material embedded therein, including anion-selective framework materials and cation-selective framework materials. The ion-electronic device of this invention constructs a microstructure with a periodic electrostatic potential field, overcoming the problem of complex ion transport paths and reduced efficiency caused by the disordered microstructures of traditional ion conductors. The organic framework material simulates the function of the lattice potential field in a semiconductor within an organic molecular system. Through the spatial confinement effect of the ordered periodic structure and the synergistic effect of the electrostatic field, it can achieve highly selective transport of specific charged ions, thereby significantly improving the efficiency and selectivity of ion transport.

Description

Technical Field

[0001] This invention relates to the field of ion electronic materials technology, and in particular to an ion electronic device, its preparation method, and its application. Background Technology

[0002] Ion electronics, a rapidly emerging cutting-edge interdisciplinary field, focuses on utilizing the transport and interaction of ions to achieve functions beyond traditional electronic devices. By deeply integrating knowledge from materials science, physics, and bioengineering, ion electronics can construct innovative flexible device architectures with unique sensing and signal processing capabilities. This multidisciplinary foundation makes it a key driver for the development of next-generation technologies, particularly showing great potential in cutting-edge fields such as flexible electronic skin, human-computer interfaces, and neuromorphic computing. Ion-transfer-based ion electronic devices have attracted much attention due to their unique physicochemical properties. These properties mainly include: ultra-low power consumption, high functional integration, rich electrochemical regulation mechanisms, and excellent biocompatibility. These advantages give ion electronic devices a unique edge in building low-power, high-sensitivity biosensing systems and simulating biological information processing. Currently, this field has made significant progress, with increasingly diverse device architectures and continuously expanding functions. At the level of basic components, researchers have successfully developed key units such as ion diodes and ion transistors. These advances have laid a solid foundation for building more complex ion circuits and multifunctional systems, such as realizing basic logic circuit functions like NAND, OR, and NOT. In sensing applications, ion electronics has been used to fabricate highly sensitive electromechanical and biosensors with molecular recognition capabilities. Notably, the development of ion electronics draws heavily on biotechnology, with biomimetic principles serving as a significant source of inspiration. In recent years, biomimetic ion electrolytes for ion transport have emerged, and various biological structures with ion-electronic functions have been successfully constructed. For example, through the synergistic effect of polymer frameworks and ionic liquids, biomimetic synaptic devices capable of real-time modulation and recording of neural signals can be constructed. Furthermore, a biomimetic electronic skin with high precision and stability under micro-strain conditions has been developed using an architecture combining oriented carbon nanotube arrays and single-ion polymers. There are even studies designing ion field-effect transistors as biomimetic olfactory neurons, precisely controlling ion transport through gas absorption at the gate to achieve intelligent recognition. These examples collectively demonstrate that ion electronics, with its advantages of flexibility, biocompatibility, superior efficiency, and extremely low energy consumption, can realize complex functions such as sensory perception, neural signal transmission, and information processing, providing innovative solutions for the development of next-generation ion electronic devices. Despite the promising prospects of ion electronics in many fields, its inherent limitations stemming from physicochemical constraints continue to hinder its practical applications. Currently, most ion-electronic devices rely on modified charges within organic molecular networks to regulate ion-selective transport. However, this network structure itself suffers from inherent defects such as looseness, disorder, and inhomogeneity, making it difficult to achieve breakthroughs in key indicators like conductivity, rectification ratio, and stimulus response. Furthermore, the fabrication process often requires complex chemical modifications under harsh conditions, resulting in poor flexibility.These structural problems in materials and challenges in fabrication processes severely limit the overall performance of devices, thus hindering the realization and widespread application of high-performance ion-electronic devices. Specifically, these limitations include the following: First, the randomness and disorder of ion migration paths significantly increase the scattering probability of carrier transport, thereby reducing charge transport efficiency and exacerbating energy loss. In other words, the disordered microstructure of existing materials limits performance: current devices mainly rely on modified charges in organic molecular networks to regulate ion transport, but this network structure itself has inherent defects of being loose, disordered, and non-uniform. This microenvironment lacking long-range ordered structures results in significant scattering and tortuous paths for ions during transport, making it difficult to achieve breakthroughs in key performance indicators such as conductivity, rectification ratio, and stimulus response speed, thus failing to meet the demands of high-performance applications. Second, loosely charged organic chains cannot effectively repel ions of the same charge, leading to poor ion selectivity and rectification performance. Furthermore, weak chemical bonds make it difficult to firmly and stably coordinate ions, which not only significantly weakens the response performance of gate modulation but also causes problems such as hysteresis and threshold voltage drift. Furthermore, this chemical modification method lacks flexibility and typically requires cumbersome processing under harsh conditions: existing technologies often require complex chemical synthesis and post-processing to impart ionic selectivity to materials, such as grafting ionic groups onto the polymer backbone through multi-step covalent bonding reactions, or involving the use of toxic solvents and harsh reaction conditions (high temperature, high pressure, etc.). This preparation process is lengthy, has low yield, and is costly, making it difficult to achieve convenient, green, and low-cost device manufacturing, thus limiting its large-scale application. All these factors ultimately limit the performance and application range of these devices in precision circuit integration. In addition, there are difficulties in device integration and patterning, as well as a lack of diverse active devices and the ability to construct complex functions: existing ion-electronic devices are difficult to adapt to existing micro / nano fabrication processes such as photolithography or printing, resulting in poor film quality and insufficient mechanical stability. This makes it impossible to fabricate high-precision, patterned, and functionally diverse ion devices over large areas, and to construct highly integrated systems with complete electronic functions (such as multi-level logic and signal feedback), severely hindering the development of ion-electronic devices towards miniaturization and arraying. Furthermore, current research largely focuses on the fabrication of passive components such as single ion diodes, with a severe lack of research on active devices such as ion transistors capable of signal amplification and active switching. Due to the lack of an effective complementary integration strategy for P-type and N-type materials similar to those in semiconductors, existing technologies struggle to fabricate high-performance NPN or PNP ion transistors. This results in the inability to perform complex logic operations (such as AND, OR, and NOT gates) and signal amplification functions, limiting the application depth of ion electronic circuits in analog computing and digital logic processing.To address these challenges, researchers have explored various existing technological solutions, primarily focusing on the following material systems: Bipolar Ion Conducting Membranes (BPMs): These mainly involve constructing an interfacial PN junction and depletion layer by combining cation and anion selective layers, utilizing the interlayer liquid gaps to achieve ion rectification or stacking to construct transistors. They are also important materials in the field of electrochemistry. However, limitations in macroscopic size and liquid gaps, the complexity of membrane stacking processes, and poor structural stability restrict their applications and make integration difficult. Biomimetic Nanofluidic Devices: Biomimetic nanofluidic devices mainly rely on constructing nanoscale asymmetric conical ion channels with specific pore sizes and shapes on rigid substrates such as silicon using micro-nano fabrication techniques. However, due to the properties of rigid substrates and the limitations of dimensional control precision in micro-nano fabrication, physical geometry alone often cannot reproduce the complex functions of biological channels. Therefore, introducing charge modification has become a key strategy to compensate for these structural defects and optimize ion transport performance. This field simulates biological ion channels by controlling ion transport within a nanoscale confined space. Polyionic Liquid Devices: Polyionic liquid devices utilize polyionic liquids as ion conducting media. The core mechanism involves fixing anions in ionic liquids onto the molecular chain backbone through polymerization, while cations act as counterions, maintaining a free-migrating state. However, the development of such materials still faces many challenges: the scarcity of ionic liquid monomers and insufficient polymerization reactivity, coupled with the steric hindrance effect caused by the large size of the ions themselves, often make it difficult for the polymerization reaction to achieve ideal integrity, thus limiting the compactness of the polymer structure. Furthermore, the uneven distribution of internal ion pairs affects ion transport. These studies, through synergistic innovation in chemical modification and device fabrication, have promoted the development of ion electronics at the material, structural, and functional levels. However, they generally fail to fundamentally solve the problems of the inherent disorder of organic polymer chains, the loose structure of charged organic chains which cannot effectively repel ions of the same charge, resulting in generally poor ion selectivity and rectification performance of devices, and the lack of flexibility in chemical modification methods.

[0003] Therefore, there is an urgent need to develop a new type of ion-electronic device to fundamentally solve the problem of disorder in traditional materials. Summary of the Invention

[0004] To address the inherent defects of mainstream ion-electronic device technologies in the prior art stemming from the limitations of their material physicochemical properties—namely, the reliance on organic polymer chains to modify charges, leading to loose, random, disordered, and unstable electrostatic distribution—this invention proposes an ion-electronic device, its fabrication method, and its applications. By mimicking the self-assembled ordered structure of biological systems, an ion-electronic module with a micro-periodic architecture is constructed, fundamentally solving the disorder problem of traditional materials.

[0005] The present invention provides an ion electronic device comprising a polymer hydrogel matrix and an organic framework material embedded therein; The organic framework materials include anion-selective framework materials and cation-selective framework materials.

[0006] This invention utilizes a porous organic framework material with a regular structure to construct a periodic electrostatic potential field, whose physical landscape is similar to the lattice potential field in a semiconductor. By forming this potential field, the problem of "disordered networks" in existing technologies can be effectively solved. First, the spatial confinement effect and periodic electrostatic potential field generated by this ordered framework can precisely control and constrain ion transport behavior, thereby significantly improving ion transport efficiency, ion selectivity, and device rectification performance. Second, through the synergistic effect of stable fixed charges in the framework structure and mobile free ions within the channels, the thermodynamic stability and kinetic characteristics of the device are enhanced, effectively solving the hysteresis effect and threshold voltage drift problems common in traditional ion devices, and significantly improving the response speed of gate modulation. Furthermore, by flexibly controlling the charged functional groups within the framework channels (e.g., by introducing different types of ionic guests or modifying framework functional groups), cation or anion selective transport conductors with properties similar to semiconductor P-type and N-type, i.e., biomimetic semiconductor PN junctions, can be easily constructed. Therefore, the heterostructure design based on porous ordered framework materials proposed in this invention, which is composed of a polymer matrix and ordered framework materials embedded therein, which have cation selectivity and anion selectivity respectively, can simulate the rectification characteristics of semiconductors. This provides a stable, efficient and structurally tunable material platform and design paradigm for designing complex ionic electronic devices such as high-performance ionic diodes, ionic transistors and logic circuits.

[0007] Furthermore, the organic framework material is formed by the self-assembly of a framework precursor and periodic charged organic functional units. The anion-selective framework material is prepared by using a framework precursor and anion-charged functional units, while the cation-selective framework material is prepared by using a framework precursor and cation-charged functional units. The core of the organic framework material of this invention lies in constructing a three-dimensional ordered network with a periodic electrostatic potential field and spatial confinement effect. The cation-selective framework material (with anion groups / anion guests modified internally or on its surface) imparts cation selectivity, while the anion-selective framework material (with cation groups / cation guests modified internally or on its surface) imparts anion selectivity. This configuration creates an ionic heterojunction structure similar to a semiconductor PN junction. The nanopores or cavities of the framework material fix the charged functional groups in specific spatial positions, forming a regular electrostatic field distribution. This ordered structure is similar to the lattice arrangement in a crystalline solid, where the charged framework or counterion array simulates the ordered atomic array that confines valence electrons in a traditional semiconductor. Meanwhile, the dissociated cations and anions exhibit functional similarities to free electrons and holes in semiconductors, making them analogs to p-type and n-type semiconductor materials.

[0008] Furthermore, the periodic organic charged functional unit is any one of molecular ionic surfactants, ionic liquids, polyelectrolytes, or self-assembled biological macromolecules (such as DNA and proteins), and the charged functional unit can bind to the framework precursor and generate a fixed charge density.

[0009] Furthermore, the organic framework material is a planar structure stacked vertically or an inner-outer-core structure. The inner-outer-core structure is formed by one ionic framework material coating another ionic framework material to form a radial heterojunction. This structure is suitable for fibrous devices and can greatly increase the contact area and improve the response speed.

[0010] Furthermore, the loading of the organic framework material in the ion-electronic device is 5wt%-20wt%. By increasing the loading of the organic framework material with a periodic electrostatic potential field, the peak current and rectification ratio of the ion-electronic device can be significantly enhanced at the same voltage. This is attributed to the fact that the increased concentration of mobile ions promotes charge transport, and the electrostatic repulsion effect of the framework enhances the carrier transport path.

[0011] Furthermore, the organic framework material includes various topological forms such as two-dimensional layered structures, one-dimensional tubular structures (such as nanotubes and nanowire channels), zero-dimensional spherical structures (such as cage-like and polyhedral structures), or three-dimensional interpenetrating network structures. These structures of different dimensions can form periodic electrostatic potential fields through self-assembly, thereby achieving selective ion transport. At the same time, by controlling the charge properties and concentration of the precursor components, precise control of carrier concentration and energy level structure similar to semiconductor doping can be achieved.

[0012] Furthermore, the configuration of the ion electronic device can be based on semiconductor technology and designed as a gate-around structure, a fin field structure, or a one-dimensional linear array structure. For example, a cation-selective framework can be used as the core channel and an anion-selective framework can be used as the gate cladding layer. The ion flow can be controlled by a three-dimensional electric field to achieve a more efficient on / off ratio and lower power consumption.

[0013] Furthermore, the ion-electronic device can be grown directly on the surface of another framework using in-situ growth or vacuum filtration-assisted layer-by-layer self-assembly technology, achieving close physical contact and stacking between pure frameworks, eliminating interference from polymer binders, improving the trans-interface transport efficiency of ions, and solving the problem that relying on hydrogels as binders in the prior art may lead to increased interfacial impedance.

[0014] The present invention also provides a method for fabricating the aforementioned ion-electronic device, comprising the following steps: Synthetic organic framework materials: The framework precursor is cross-linked with anionic and cationic functional units respectively to obtain anionic selective framework materials and cationic selective framework materials. By utilizing intermolecular non-covalent or covalent interactions (including but not limited to electrostatic, host-guest, coordination and hydrogen bonding), charged functional units can be driven to self-assemble with the framework precursor to form ionic functional materials with specific microscopic topological order structures. Preparation of precursor solution: Dissolve polymer powder in deionized water, heat and stir until completely dissolved to obtain precursor solution 1; Doped organic framework materials: Anion-selective framework materials and cation-selective framework materials are mixed evenly with precursor solution 1 to obtain precursor solution 2 doped with anion-selective framework materials and precursor solution 3 doped with cation-selective framework materials. Freeze-forming and thawing: Precursor solution 2 or precursor solution 3 is injected into the mold until it is half full, and then frozen to allow the polymer molecular chains to form physical cross-links. After freezing, the mold is removed and thawed. Then another precursor solution is injected into the half-full mold until it is full, and then frozen. After freezing, the mold is removed and thawed to obtain the ion electronic device.

[0015] Furthermore, after the thawing step is completed, the freeze-thaw cycle can be repeated multiple times to enhance the crosslinking density and mechanical strength of the hydrogel.

[0016] Furthermore, the method for fabricating ion electronic devices is not limited to small-scale laboratory fabrication, but can be extended to roll-to-roll processing of large-area macroscopic thin films, or scaled down to in-situ assembly inside microfluidic chips, with the size range spanning from the micro-nano level to the macroscopic flexible thin film scale.

[0017] Furthermore, the framework precursor is any one of supramolecular organic frameworks, metal-organic frameworks, covalent organic frameworks, or hydrogen-bonded organic frameworks, and the selection of specific electronegative ions is achieved by respectively forming anionic / cationic organic frameworks.

[0018] The present invention also provides the application of the ion electronic device as an ion rectifier diode. Since the ion electronic device mainly achieves effective control of ions based on mechanisms such as electrostatic repulsion and double electric layer, the mechanism is applicable to ion heterojunctions constructed on porous ordered framework materials. Based on this, the ion electronic device of the present invention can be used as an ion rectifier diode. Its rectification mechanism and transmission characteristics are as follows. (1) Ion regulation function and mechanism: When there is no external electric field, the ordered framework structure (or fixed charge network) remains stable. Free ions are electrostatically bound by the fixed charge from the framework and maintain a quasi-ordered and uniform distribution around the framework structure. When a forward bias is applied, cations and anions migrate directionally to the electrode under the drive of the electric field. After the ions reach the electrode, they accumulate. The ion enrichment at the interface requires the electrode to increase the charge compensation, which is manifested as an increase in the current in the circuit. This is consistent with the double-layer model. Correspondingly, when a reverse bias is applied, anions and cations migrate to the other side of the device. At the same time, they are repelled by the electrostatic potential field of the framework layer with opposite charge. They are difficult to cross the junction region of the ion diode and cannot approach the opposite electrode. Therefore, the electric double layer in the electrode is thin and only a small amount of charge is needed to maintain the potential difference, thus a small current is observed.

[0019] (2) Rectification characteristics: IV scan tests were performed on the ion diodes, and the results showed significant asymmetry: the current increased exponentially under forward bias, while the current quickly saturated and cut off under reverse bias. This is consistent with the proposed working model. The current only increases significantly when the voltage exceeds a predetermined critical threshold voltage (e.g., about 0.2~1 V). This is because in a weak electric field (<threshold voltage), the electrostatic binding energy (or barrier) of the frame structure of the ion rectifier diode hinders the directional migration of ions. When the voltage exceeds this critical value, the external electric field can overcome this binding force and trigger the collective migration of ions. When the bias voltage increases from reverse bias (~-1.5 V) to 0 V and from 0 V to the threshold voltage, the current change is relatively small. When the bias voltage increases from the threshold voltage to 1.5 V, the current increases exponentially. However, when the bias voltage drops from 1.5 V to 0 V, the current initially decreases very slowly and then quickly drops to zero.

[0020] (3) Stability and Cyclic Performance The durability of ion-rectifying diodes was tested, and the rectification performance and quality changes of the diodes under sealed and unsealed conditions were recorded over 24 hours. The results showed that sealing effectively mitigated the evaporation of moisture from the hydrogel matrix, and the rectification ratio remained above 98% after 24 hours, demonstrating the influence of water content on the rectification ratio of ion-electronic devices. Furthermore, various types of rectifying diodes fabricated by changing the charged functional units in the ordered framework material (e.g., replacing different types of ion guests or modifying the framework functional groups) all exhibited forward conduction and reverse cutoff rectification characteristics in IV measurements and cyclic rectification tests. The IV curve of the diode fabricated using electrically neutral functional units did not show rectification characteristics, further confirming the heterojunction rectification effect based on different ion-selective ordered frameworks.

[0021] Furthermore, the ion electronic device of the present invention can extract energy from a salt concentration gradient by utilizing the rectification characteristics and ion selectivity of the heterojunction.

[0022] This invention also provides the application of the aforementioned ion-electronic device in the fabrication of ion piezoelectric diodes. To further explore the application potential of the device, this invention proposes an ion piezoelectric sensing functional device (ion piezoelectric diode) based on ion-electronic devices. This ion piezoelectric diode achieves the regulation function of asymmetric ion migration and unidirectional conduction under pressure drive through a heterojunction structure, and generates a corresponding electrical signal output. The application mechanism is as follows: (1) Pressure sensing mechanism The working mechanism of the ion piezoelectric diode is that, in the initial state, counterions are distributed around the charged ordered framework. When subjected to external pressure, free ions confined in the framework channels or network migrate through the heterojunction, thereby generating a measurable potential difference across the device. When pressure is applied, the voltage / current signal increases instantaneously within 1 ms, and after the pressure is removed, the signal also returns to zero within 1 ms, demonstrating the fast response characteristics of this ion-type pressure sensor.

[0023] (2) Sensitivity and linearity analysis To quantitatively evaluate the pressure sensing capability of ion piezoelectric diodes, a systematic test was conducted using weights of different masses. The results showed that the output voltage was positively correlated with the applied pressure, indicating that the greater the pressure, the more severe the deformation of the polymer matrix, which in turn led to changes in the micro-geometry of the ordered framework structure. The greater the ion displacement, the more piezoelectric charge was generated.

[0024] Further pressures of 0 to 10 kPa were applied to the ion piezoelectric diode, and its voltage and current density responses were tested. The results demonstrate that the ion piezoelectric diode of this invention exhibits excellent high linearity sensing capability over a wide pressure range. In the low-pressure region, the current density and output voltage increase approximately linearly with pressure. During this stage, the pressure compresses the heterojunction interface region of the diode, causing the ion depletion region to narrow, thereby reducing the resistance of ions to cross the electrostatic barrier. As the pressure continues to increase, the current density and output voltage gradually approach saturation. At this point, the junction region is highly compressed, the width of the depletion region approaches its limit, and the migration rate of ions through the frame channels becomes a bottleneck, causing the current density growth rate to slow down and gradually reach saturation. Based on the unique synergistic effect of the periodic electrostatic potential field and heterojunction interface of this invention, the ion piezoelectric diode exhibits excellent pressure sensitivity and significant linear response characteristics over a wide pressure range. This invention utilizes ordered framework materials to precisely control ion transport behavior, successfully constructing an ion piezoelectric diode that combines high-sensitivity detection with high-linearity sensing capabilities. It achieves efficient energy conversion of mechanical pressure and unidirectional rectified output of electrical signals. This technical solution, which resolves the contradiction between sensitivity and linearity through microstructure design, significantly improves the detection accuracy of the device in complex environments, providing strong technical support for the development of flexible electronic devices, smart wearable devices, and biomedical sensing systems.

[0025] The present invention also provides the application of the aforementioned ion electronic device in the fabrication of ion transistors.

[0026] This invention also provides the application of the aforementioned ion-electronic device in the fabrication of logic circuits. The ion-electronic device of this invention can be integrated and applied at the system level. (1) Constructing complex circuits: Based on the heterostructure of the present invention, NPN or PNP type multilayer structures can be constructed to simulate Darlington transistors or complementary metal-oxide-semiconductor logic in electronic circuits, and realize complex logic operations of ion signals (such as full adders and flip-flops) and high-fidelity amplification of analog signals. (2) Flexible hybrid integration: The ion electronic device of the present invention can be combined with traditional silicon-based electronic devices or flexible thin film transistors (TFTs) through heterogeneous integration technology to construct an ion-electron hybrid signal processing system, utilizing the high sensitivity sensing of the front-end ion device and the high-speed processing capability of the back-end electronic device.

[0027] The present invention also provides the application of the aforementioned ion electronic device in the fabrication of signal amplifiers.

[0028] The present invention also provides the application of the aforementioned ion electronic device as a core electrode material for flexible ion supercapacitors or in storing mechanical or biological energy.

[0029] The present invention also provides the application of the aforementioned ion electronic device in neuromorphic and brain-like computing: utilizing the hysteresis characteristics of ion migration as artificial synapses to simulate short-term and long-term plasticity, it is used to construct brain-like neuromorphic networks and perform computational tasks such as pattern recognition and associative memory.

[0030] Furthermore, the ion electronic device can be fabricated into a micron-scale patterned array by photolithography, 3D printing or template method, or a large-scale integrated pixel array can be constructed to build a high-resolution ion sensing array or artificial retina.

[0031] This invention also provides an application of organic framework materials in the fabrication of ion rectifier diodes, ion piezoelectric diodes, ion transistors, logic circuits, or signal amplifiers; The organic framework materials include anion-selective framework materials and cation-selective framework materials; The anion-selective framework material is prepared by using a framework precursor and anion-charged functional units, and the cation-selective framework material is prepared by using a framework precursor and cation-charged functional units.

[0032] Furthermore, the organic framework material obtains ionic electronic devices by embedding it into a polymer hydrogel matrix.

[0033] This invention constructs an ion heterojunction diode (ion rectifier diode) based on an organic framework material and a polymer hydrogel matrix. This diode combines a first-type ordered framework with cation selectivity and a second-type ordered framework with anion selectivity to form a heterostructure similar to a semiconductor PN junction. Utilizing the electrostatic field generated by the fixed charges within the framework, this device can effectively regulate the directional migration and interface enrichment of ions. Based on this ion rectifier diode, an ion piezoelectric diode utilizes the coupling mechanism of the built-in electric field of the heterojunction and pressure-induced ion directional migration to achieve the direct conversion of mechanical energy into electrical energy. In addition, other derivative functional devices can be obtained based on this ion heterojunction diode, including but not limited to ion transistors, logic circuits, and signal amplifiers. These devices are characterized by multi-layer heterojunction stacking or multi-unit diode circuit integration, forming a complex ion-electronic system with active control capabilities. By using the dynamic modulation of ion transport channels by the electric field and the gradient control of carrier concentration, the logical operation, fast switching, and high-rate signal amplification functions of ion signals are realized.

[0034] In summary, compared with the prior art, the present invention achieves the following technical effects: (1) The ion electronic device provided by the present invention constructs a microstructure with a periodic electrostatic potential field, which overcomes the problem of the disorder of the microstructure of traditional ion conductors leading to complex ion transport paths. The organic framework material simulates the function of the lattice potential field in the semiconductor in the organic molecular system. It can achieve high selective transport of specific ions through the spatial confinement effect of the ordered periodic structure and the synergistic effect of the electrostatic field, thereby significantly improving the efficiency and selectivity of ion transport. (2) The ion electronic device provided by the present invention can achieve flexible control and optimization of device performance by adjusting the pore structure of the frame and the charged functional unit; (3) The ion electronic device provided by the present invention successfully prepared a central framework, cation conductor and anion conductor similar to intrinsic, P-type and N-type semiconductors by introducing surfactants or functional units with opposite charges. It also breaks through the limitation that traditional ion conductors can only build a single PN junction heterojunction and can be flexibly doped and controlled, providing a basis for the functionalization of ion devices. (4) The ion electronic device provided by the present invention, when used as an ion heterojunction diode, achieves a high rectification ratio and millisecond-level fast response, and effectively solves the problems of severe hysteresis, slow response speed and threshold voltage drift of traditional ion devices. (5) The ion electronic device provided by the present invention can be used to prepare ion piezoelectric diodes with both self-powered sensing and unidirectional conduction functions. It realizes the efficient conversion of mechanical energy into electrical energy by utilizing the built-in electric field of the heterojunction, and exhibits excellent linear response characteristics in a wide pressure range, simplifying the structure of the sensing system. (6) The ion electronic device provided by the present invention can be further developed into ion transistors, logic gates (AND, OR, NOT) and signal amplifiers based on ion heterojunctions. It realizes logic operation and signal amplification by controlling the ion concentration gradient by electric field, thus expanding the application potential of ion electronic devices in the fields of analog signal processing and digital logic computing. (7) The molecular self-assembly strategy of the ion electronic device provided by the present invention is mild, and the device (such as the hydrogel-based system) has excellent flexibility and biocompatibility, which overcomes the problem of poor biointerface compatibility of traditional rigid electronic devices, and is particularly suitable for wearable devices and biomedical sensing fields. (8) The ion electronic device provided by the present invention can realize highly sensitive tactile perception and real-time deformation monitoring in the field of electronic skin; its logic operation characteristics based on ion migration and rectification meet the requirements of neuromorphic computing for low power consumption and high parallel information processing, providing a new idea for building brain-like intelligent chips. In addition, the soft interface characteristics of the device effectively solve the modulus mismatch problem between traditional rigid electrodes and biological tissues, and are expected to realize high-fidelity transmission and bidirectional interaction of neural signals in the field of brain-computer interface, promoting the development of bio-integrated electronics technology. Attached Figure Description

[0035] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0036] Figure 1 This is a schematic diagram of the ion electronic device prepared in Example 1 of the present invention; Figure 2 This is a synthesis route diagram of the anionic framework material and the cationic framework material in Example 1 of the present invention; Figure 3 This is a microscopic image of the organic framework material of Example 1 of the present invention; Figure 4 This is a schematic diagram of the double-layer principle of Embodiment 1 of the present invention; Figure 5 These are IV scans of ion rectifier diodes with different organic framework material doping levels according to Embodiment 1 of the present invention. Figure 6 (a) is a graph showing the change in mass ratio of two sets of ion diodes of the same specification under sealed and unsealed conditions within 24 hours compared to the initial state in Embodiment 1 of the present invention; (b) is a graph showing the change in rectification ratio of two sets of ion diodes of the same specification under sealed and unsealed conditions within 24 hours compared to the initial state in Embodiment 1 of the present invention; (c) is a schematic diagram of the sealed and unsealed ion electronic devices in Embodiment 1 of the present invention; (d) is a graph showing the change in forward and reverse current of the ion diode under unsealed conditions within 24 hours in Embodiment 1 of the present invention; (e) is a schematic diagram of the cojunction diode structure in Embodiment 1 of the present invention; (f) is an IV scan diagram of the cojunction diode in Embodiment 1 of the present invention. Figure 7 This is a schematic diagram of the ion pressure diode according to Embodiment 1 of the present invention. Detailed Implementation

[0037] To enable those skilled in the art to better understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

[0038] Example The present invention will be further illustrated below with reference to specific embodiments and comparative embodiments. The following specific embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the following embodiments, and are not in particular limited to the types of raw materials used in the following specific embodiments.

[0039] I. The sources of raw materials for the examples and comparative examples are as follows: Unless otherwise specified, all raw materials used in the examples and comparative examples are commercially available.

[0040] II. Performance Testing Methods (1) Material structure characterization: The ordered structure of the self-assembled framework material was observed by optical / fluorescence microscopy, and the formation of the inclusion structure was verified by infrared spectroscopy.

[0041] (2) Rectification ratio test: The device was tested using a linear sweep voltammetry (LSV) method with an electrochemical workstation. A specific voltage sweep range was set, and the current-voltage (IV) characteristic curve of the device was recorded. The forward current (I) at a specific voltage point was selected. + ) and reverse current (I According to the formula R=|I + / I - | Calculate the rectification ratio.

[0042] (3) Sensitivity test: An electrochemical workstation was used in conjunction with a mechanical loading device for testing. Under a constant bias voltage, a pressure load that continuously varied from low to high (covering a wide pressure range) was applied to the device. The current response signal under different pressures was recorded in real time using the chronoamperometry (I-t) mode of the electrochemical workstation. The characteristic curve was plotted with pressure as the abscissa and the relative current change rate (ΔI / I0) as the ordinate. The slope of the curve was calculated to obtain the sensitivity. At the same time, linear regression fitting was performed on the data within the wide pressure range to calculate the linear correlation coefficient (R). 2 This demonstrates that the device possesses excellent high linearity sensing capabilities over a wide pressure range.

[0043] Example 1 Example 1 describes the preparation of an ion-electronic device, comprising the following steps: Synthesis of organic framework materials (layered structure): Sodium dodecyl sulfate (SDS) (10 wt%) was dissolved in water as a cation selector, and trimethylammonium dodecyl bromide (DTAB) (10 wt%) was dissolved in water as an anion selector. These were then reacted with β-cyclodextrin (β-CD) (20 wt%) (the molar ratio of charged functional units to cyclodextrin was 1:2) to prepare ion-selective functional materials SDCD (cation-selective framework material, SDS@2β-CD) and DTCD (anion-selective framework material, DTAB@2β-CD). Preparation of precursor solution: Polyvinyl alcohol (PVA) powder was dissolved in deionized water and heated and stirred until completely dissolved to obtain PVA aqueous solution (15 wt%). Doping with organic framework materials: The pre-synthesized SDS@2β-CD and DTAB@2β-CD organic framework materials were added to PVA aqueous solution and mixed evenly to obtain precursor solution 2 of doped anion-selective framework material and precursor solution 3 of doped cation-selective framework material (mass ratio of 1:1, and the mass ratio of overall organic framework material to ion-electronic device of 1:5). Freeze-thaw process: PVA precursor solution 2 is injected into the mold until it is half full, and then frozen at -20°C to allow the PVA molecular chains to form physical cross-links. After freezing, the mold is removed and thawed. Then, precursor solution 3 is injected into the mold until it is full, and frozen at -20°C to allow the PVA molecular chains to form physical cross-links. After freezing, the mold is removed and thawed. The above freeze-thaw operation is repeated to finally obtain the ion electronic device. Figure 1 This is a schematic diagram of the ion electronic device prepared in Example 1. Intermolecular forces drive this three-dimensional ordered arrangement. In infrared spectroscopy analysis, the appearance of characteristic peaks (such as peaks corresponding to the coordinated vibration of hydrogen bonds) indicates the formation of an ordered structure, which explains the changes in the self-assembled structure at the microscopic level. Figure 2 This is a synthesis route diagram of the anionic framework material and the cationic framework material in Example 1. By combining charged functional units with framework precursors with regular topological structures, and assembling them using coordination bonds, hydrogen bonds or host-guest interactions, functional composite materials with ion selectivity are prepared. Figure 3 The image shows a microscopic image of the organic framework material in Example 1. The microscopic image directly confirms the layered (or other regular topological) microstructure, which exhibits obvious ordered features at the microscale. This ion electronics research based on universal ordered framework materials provides new material design ideas for flexible electronics and implantable bioelectronics that need to interact with biological interfaces. Figure 4 This is a schematic diagram of the double-layer principle in Example 1; Figure 5 IV scans of ion rectifier diodes with different organic framework material doping levels in Example 1; Figure 6(a) shows the mass change of two sets of identical ion diodes in sealed and unsealed states over 24 hours compared to their initial state; (b) shows the rectification ratio change of two sets of identical ion diodes in sealed and unsealed states over 24 hours compared to their initial state; (c) shows schematic diagrams of sealed and unsealed ion electronic devices; (d) shows the forward and reverse current changes of an ion diode in unsealed state over 24 hours; (e) shows a schematic diagram of a junction diode structure; and (f) shows the IV scan results of a junction diode. Figure 7 This is a schematic diagram of the ion pressure diode in Example 1; Based on the general system of ion electronic devices based on a porous organic framework constructed in Example 1, an exemplary solution for ion rectifier diode rectification and ion piezoelectric sensing applications based on this periodic electrostatic potential field framework is proposed: (1) Using the ion-electronic device as an ion rectifier diode: Perform IV scan testing on the ion diode (e.g. Figure 5 The results showed significant asymmetry: the current increased exponentially under forward bias, while it rapidly saturated and cut off under reverse bias, consistent with the proposed working model. Experiments revealed that the current only increased significantly when the voltage exceeded a predetermined critical threshold voltage (e.g., approximately 0.2–1 V). This is because, in a weak electric field (< threshold voltage), the electrostatic binding energy (or barrier) of the framework structure of the ion rectifier diode hinders the directional migration of ions. Only when the voltage exceeds this critical value can the external electric field overcome this binding force and trigger collective ion migration. The current change was relatively small when the bias voltage increased from reverse bias (~-1.5 V) to 0 V and from 0 V to the threshold voltage. When the bias voltage increased from the threshold voltage to 1.5 V, the current increased exponentially. However, when the bias voltage decreased from 1.5 V to 0 V, the current initially decreased very slowly and then rapidly dropped to zero. (2) The ion electronic device was used in the ion piezoelectric diode: Fast response characteristic test: When a pressure of 10 kPa was applied, the voltage / current signal increased instantaneously to 8.65 mV within 1 ms. After the pressure was removed, the signal also returned to zero within 1 ms, which showed the fast response characteristic of the ion pressure sensor. Pressure sensing capability test: System tests were conducted using weights of different masses (10 g and 20 g). The results showed that the output voltage was positively correlated with the applied pressure. The stable output was approximately 4.8 mV under a 10 g load, and increased to approximately 7.9 mV under a 20 g load, an increase of 3.1 mV. This indicates that the greater the pressure, the more severe the deformation of the polymer matrix, which in turn leads to changes in the micro-geometry of the ordered framework structure. The greater the ion displacement, the more piezoelectric charge is generated. Further, pressures of 0 to 10 kPa were applied to the ion piezoelectric diode and its voltage and current density responses were tested. The results demonstrated that the ion piezoelectric diode of Example 1 has excellent high linearity sensing capability over a wide pressure range. In the low pressure region (0-2 kPa), the current density and output voltage increased approximately linearly with pressure, from 0 to 38.4 μA / cm² and 22.4 mV, respectively. During this stage, the pressure compresses the heterojunction interface region of the diode, resulting in a narrower ion depletion region, thereby reducing the resistance of ions to pass through the electrostatic barrier. As the pressure continues to increase (2-10 kPa), the current density and output voltage gradually approach saturation, increasing from 38.4 μA / cm² and 22.4 mV to 35.1 μA / cm² and 42.7 mV, respectively. At this point, the junction region is highly compressed, the width of the depletion region is close to its limit, and the migration rate of ions through the framework channels becomes a bottleneck, causing the current density growth rate to slow down and gradually reach saturation. Systematic tests were conducted on the electrical characteristics, environmental stability, and pressure sensing performance of the ion diode and ion piezoelectric diode based on the ion electronic device of Example 1. The results show that the device can achieve a rectification ratio of up to 31.36 under a bias voltage of 3.0 V, with a response time as low as 1 ms, and exhibits excellent linear response (voltage sensitivity of 22.4 mV / kPa) in the pressure range of 0-2 kPa. At the same time, after 24 hours of sealing test and 30 cycles of test, the device exhibits good environmental stability (rectification ratio remains above 98%). Therefore, the experiment confirms the effectiveness and feasibility of the ion rectification mechanism based on ordered framework heterojunction and the application of ion piezoelectric sensing proposed in this invention.

[0044] Example 2 Example 2 describes the preparation of an ion-electronic device, comprising the following steps: Synthesis of organic framework materials (structure of sulfonate-functionalized zirconium-based metal-organic framework UiO-66-SO3H): Using ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([EMIM][TFSI], 100 wt%) as a cation selector and polydiallyldimethylammonium chloride (PDDA aqueous solution, 20 wt%) as an anion selector, composite reactions were carried out with UiO-66-SO3H (framework precursor) to prepare cation-selective MOF materials and anion-selective MOF materials; Preparation of precursor solutions: Dissolve the ionic liquid [EMIM][TFSI] in acetonitrile solvent to prepare an ionic liquid solution (20 wt%); dissolve PDDA in deionized water to prepare a PDDA aqueous solution (10 wt%). Doping with organic framework materials: The pre-synthesized cationic selective MOF material is added to the ionic liquid solution, and the anionic selective MOF material is added to the PDDA aqueous solution and mixed evenly; the mixing mass ratio of organic framework material to solution is 1:4, thus obtaining slurry 2 doped with anionic selective MOF material and slurry 3 doped with cationic selective MOF material; Molding: Pour slurry 2 into the mold until it is half full, heat it at 60°C to evaporate the solvent to a semi-dry state, then continue to pour slurry 3 into the mold until it is full, and vacuum dry it again at 60°C until the solvent is completely removed, finally obtaining the ion electronic device.

[0045] Example 3 Example 3 describes the preparation of an ion-electronic device, comprising the following steps: Synthesis of organic framework materials (layered hydrogen-bonded organic frameworks): Using an ionic liquid electrolyte containing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) (a mixture of [EMIM][TFSI] and LiTFSI in a mass ratio of 1:3) as a cation selector and a molecularly ionic surfactant, dodecyltrimethylammonium bromide (DTAB aqueous solution, 10 wt%), as an anion selector, these materials were composited with layered hydrogen-bonded organic frameworks (framework precursors) to prepare cation-selective HOF materials and anion-selective HOF materials. Preparation of precursor solution: Lithium salt LiTFSI was dissolved in ionic liquid [EMIM][TFSI] to prepare an ionic liquid electrolyte with a concentration of 1 mol / L; Doping with organic framework materials: The pre-synthesized HOF materials were added to the above precursor solutions, ultrasonically dispersed and stirred evenly; the mixing mass ratio of HOF materials to solutions was 1:4, thus obtaining suspension 2 of anion-selective HOF materials and suspension 3 of cation-selective HOF materials. Molding: Pour slurry 2 into the mold until it is half full, heat it at 60°C to evaporate the solvent to a semi-dry state, then continue to pour slurry 3 into the mold until it is full, and vacuum dry it again at 60°C until the solvent is completely removed, finally obtaining the ion electronic device.

[0046] Example 4 Example 4 describes the preparation of an ion-electronic device, comprising the following steps: Synthesized organic framework materials with a two-dimensional imine-linked covalent organic framework structure: using polystyrene sulfonic acid (PSS aqueous solution, 20 wt%) as a cation selector and polydiallyldimethylammonium chloride (PDDA aqueous solution, 20 wt%) as an anion selector, they were respectively solution-composite with two-dimensional imine-linked covalent organic frameworks (framework precursors) to prepare cation-selective COF materials and anion-selective COF materials; Preparation of precursor solutions: Polystyrene sulfonic acid (PSS) was dissolved in deionized water to prepare a PSS aqueous solution (5 wt%); polydiallyl dimethyl ammonium chloride (PDDA) was dissolved in deionized water to prepare a PDDA aqueous solution (5 wt%). Doping with organic framework materials: The pre-synthesized HOF materials were added to the two precursor solutions mentioned above, ultrasonically dispersed and stirred evenly; the mixing mass ratio of HOF materials to solutions was 1:4, thus obtaining suspension 2 of anion-selective HOF materials and suspension 3 of cation-selective HOF materials. Molding: Suspension 2 is injected into the mold to half full, and then allowed to stand under vacuum to remove bubbles. Then, suspension 3 is injected into the mold to full full, and vacuum degassing and standing are performed again. Finally, a stable composite layered structure is formed through physical confinement to obtain an ion electronic device.

[0047] Example 5 The difference between Example 5 and Example 1 is that the mass ratio of the overall organic framework material to the ion-electronic device in the step of doping organic framework material is 1:20.

[0048] Example 6 The difference between Example 6 and Example 1 is that the mass ratio of the overall organic framework material to the ion-electronic device in the step of doping organic framework material is 1:10.

[0049] Table 1. Performance Effects of the Examples

[0050] This invention utilizes the fixed-charge electrostatic field of an ordered framework structure to bind, constrain, guide, regulate, stimulate response, and repel free ions. It can be combined with heterojunction interface engineering to achieve precise control of ion transport paths and efficient conversion of mechanical energy into electrical energy. By constructing a microstructure with a periodic electrostatic potential field, it overcomes the core technical bottlenecks of traditional ion conductors, such as low ion transport efficiency, poor selectivity, and response lag caused by the complex ion transport paths and loose networks due to the disordered microstructure. Furthermore, the obtained ion electronic device has a high rectification ratio and excellent high linearity sensing capability over a wide pressure range.

[0051] This invention utilizes intermolecular self-assembly interactions (including but not limited to host-guest, coordination, and hydrogen bonding forces) to construct a microscopically ordered framework structure with a periodic electrostatic potential field. This structure, serving as the core functional carrier, uses its fixed charge electrostatic field to strongly bind, constrain, guide, and stimulate free ions, fundamentally overcoming the uncertainty of ion transport paths in disordered networks. Based on this framework, this invention further constructs an ion heterojunction diode capable of asymmetric ion transport through interface engineering, endowing the device with highly efficient rectification characteristics similar to a semiconductor PN junction. Furthermore, utilizing the coupling mechanism between the heterojunction's built-in electric field and external forces, an ion piezoelectric diode with both self-powered and unidirectional conduction functions is developed. Benefiting from the standardized control of ion paths by the periodic electrostatic potential field, the obtained device achieves a significantly high rectification ratio, millisecond-level fast response, and excellent high linearity sensing capability over a wide pressure range, thus solving the technical challenge of existing devices that struggle to balance sensitivity and linearity.

[0052] The above description is only a preferred embodiment of the present invention and is 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 within the protection scope of the present invention.

Claims

1. An ion-electronic device, characterized in that, This includes a polymer hydrogel matrix and an embedded organic framework material; The organic framework materials include anion-selective framework materials and cation-selective framework materials.

2. The ion electronic device according to claim 1, characterized in that, The organic framework material is loaded into the ion-electronic device at a rate of 5wt%-20wt%.

3. The method for preparing the ion-electronic device according to any one of claims 1-2, characterized in that, Includes the following steps: Synthesizing organic framework materials: The framework precursor is mixed and crosslinked with anionic and cationic functional units respectively to obtain anionic selective framework materials and cationic selective framework materials. Preparation of precursor solution: Dissolve polymer powder in deionized water, heat and stir until completely dissolved to obtain precursor solution 1; Doped organic framework materials: Anion-selective framework materials and cation-selective framework materials are mixed evenly with precursor solution 1 to obtain precursor solution 2 doped with anion-selective framework materials and precursor solution 3 doped with cation-selective framework materials. Freeze-forming and thawing: Inject precursor solution 2 or precursor solution 3 into the mold until it is half full, and then freeze it. After freezing, remove the mold and thaw it. Then inject another precursor solution into the mold until it is full, and then freeze it. After freezing, remove the mold and thaw it to obtain the ion electronic device.

4. The preparation method according to claim 3, characterized in that, The framework precursor is any one of supramolecular organic frameworks, metal-organic frameworks, covalent organic frameworks, or hydrogen-bonded organic frameworks, and the selection of specific electronegative ions is achieved by forming anionic / cationic organic frameworks respectively.

5. The application of the ion electronic device according to any one of claims 1-2 as an ion rectifier diode.

6. The application of the ion electronic device according to any one of claims 1-2 in the fabrication of ion piezoelectric diodes.

7. The application of the ion-electronic device according to any one of claims 1-2 in the fabrication of ion transistors.

8. The application of the ion electronic device according to any one of claims 1-2 in the fabrication of logic circuits.

9. The use of the ion electronic device according to any one of claims 1-2 in the fabrication of a signal amplifier.

10. The application of an organic framework material in the fabrication of ion rectifier diodes, ion piezoelectric diodes, ion transistors, logic circuits, or signal amplifiers, characterized in that, The organic framework materials include anion-selective framework materials and cation-selective framework materials; The anion-selective framework material is prepared by using a framework precursor and anion-charged functional units, and the cation-selective framework material is prepared by using a framework precursor and cation-charged functional units.

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