An electronic state regulation material based on van der waals hetero-interface and a preparation method and product thereof

Abstract

The application discloses an electronic state regulation material based on a van der Waals hetero-interface and a preparation method and product thereof. The electronic state regulation material comprises an A component and a B component, the A component is a two-dimensional conductive material, and the B component is a two-dimensional insulating material; the A component and the B component are arranged in layers and are combined by van der Waals force to form a van der Waals hetero-interface; the van der Waals hetero-interface is separated between layers when subjected to mechanical stress, and spontaneously recombines after the mechanical stress is removed; after the van der Waals hetero-interface recombines, the electronic state regulation function between the A component and the B component recovers to a level capable of meeting the requirements of normal work of a device. The application first takes the van der Waals hetero-interface itself as a regulation platform of electronic quantum behavior, expands the van der Waals hetero-interface from a self-repairing structural material and a molecular recognition functional material to an electronic state regulation material, and opens a brand-new application dimension. Unlike existing electronic devices which depend on chemical modification or a complex heterostructure, the regulation driving force of the application comes from the intrinsic physical properties of the van der Waals hetero-interface, atomic-level gaps and electric field adjustability, does not consume any active substances, and can be regulated theoretically for unlimited times.

Description

Technical Field

[0001] This invention relates to the field of electronic state control materials technology, specifically to an electronic state control material based on van der Waals heterointerfaces, its preparation method, and the product thereof. Background Technology

[0002] Van der Waals heterostructures are formed by the bonding of two-dimensional conductive materials (such as graphene) and two-dimensional insulating materials (such as hexagonal boron nitride) through van der Waals forces.

[0003] Current research on the electronic behavior of two-dimensional material interfaces mainly focuses on fundamental physics, such as the quantum Hall effect at the graphene-hBN interface and electron localization in moiré superlattices, revealing a wealth of quantum phenomena. However, no one has yet translated these quantum behaviors into actively controllable electronic device platforms with clearly defined technical functions. More importantly, current technologies have never proposed utilizing the atomic-level flatness and electric field tunability of van der Waals heterointerfaces to actively control the electronic states of the interface and, based on this control, achieve physical detection functions independent of molecular recognition units. Furthermore, existing electronic devices generally lack self-healing capabilities after interface damage. Once the functional interface of traditional semiconductor devices is damaged, the electronic behavior permanently degrades, leading to device failure. The self-healing capability of van der Waals heterointerfaces provides a novel physical basis for solving this problem, but no one has yet applied this property to the field of electronic state control.

[0004] The inventors of this application previously disclosed a method for achieving molecular recognition function by fixing molecular recognition unit D component on the interface in a patent entitled "A molecular recognition and selective capture material and product thereof based on van der Waals heterostructure" (hereinafter referred to as "molecular-level patent"). However, this patent mainly focuses on chemical / biological recognition function—achieving molecular recognition through the specific binding between D component and target molecule, without involving the active regulation and utilization of electron behavior on van der Waals heterostructure.

[0005] It is important to distinguish that although the electronic state regulation function of this invention and the molecular recognition function in the molecular-level patent share the basic structure of the A / B van der Waals heterointerface, their protected themes, technical solutions, problems solved, and effects are fundamentally different: (1) Different protected subjects: The protected subject of a molecular-level patent is a composition or material, which belongs to product invention; the protected subject of this invention is a control method and device, which belongs to method invention and product invention.

[0006] (2) Different technical solutions: The technical solution of the molecular-level patent relies on chemical / biological means to achieve specific recognition through the "lock-key" matching of D components (peptides, aptamers); the technical solution of this invention relies on physical means to utilize changes in interface electronic state density, band structure, quantum tunneling, etc., and regulate electronic behavior through external fields (electric, light, force).

[0007] (3) The problems they solve are different: molecular-level patents solve the problem of how to specifically identify a certain molecule and how to reuse it; this invention solves the problem of how to detect a certain molecule or physical quantity with ultrasensitivity and how to respond ultrafast.

[0008] (4) Different material composition: Molecular patents rely on molecular recognition unit D component, which is an essential component; This invention does not rely on any molecular recognition unit, and the material composition is A, B and C, with component D removed.

[0009] Therefore, there is an urgent need to develop an electronic state control material based on van der Waals heterointerfaces to realize the active control of electronic quantum behavior on van der Waals heterointerfaces and its device application. Summary of the Invention

[0010] The purpose of this invention is to provide an electronic state control material and its products based on van der Waals heterointerfaces, so as to realize for the first time the active control of electronic quantum behavior on van der Waals heterointerfaces and the device application without relying on any molecular recognition unit.

[0011] To achieve the above objectives, the present invention provides the following technical solution.

[0012] In a first aspect, there is an electronic state modulation material based on a van der Waals heterointerface, comprising a component A and a component B, wherein component A is a two-dimensional conductive material and component B is a two-dimensional insulating material; the components A and B are stacked and bonded together by van der Waals forces to form a van der Waals heterointerface; the van der Waals heterointerface undergoes interlayer separation under mechanical stress, and spontaneously recombines after the mechanical stress is removed; after the van der Waals heterointerface recombines, the electronic state modulation function between component A and component B is restored to a level that meets the requirements for normal device operation.

[0013] The core innovation of this invention lies in the fact that, for the first time, the van der Waals heterointerface itself is used as a platform for regulating electronic quantum behavior. The atomic-level gaps between the interfaces form an electron tunneling barrier layer. Through three external stimuli—an applied electric field, mechanical stress, and photoexcitation—the electronic density of states, band structure, spin polarization state, or quantum transport behavior at the interface can be actively regulated. This regulation is completely independent of any molecular recognition unit and acts directly on the interface electrons themselves.

[0014] The specific methods for regulating electronic states through the three external stimuli are as follows: (1) External Electric Field Control: The van der Waals heterostructure formed between component A and component B constitutes an atomically interstitial conductive-insulating-conductive nanocapacitor structure. When a bias voltage of 0.01 V to 10 V is applied between components A, an electric field perpendicular to the interface direction is generated on the van der Waals heterostructure, changing the charge distribution, band alignment, and density of states at the interface. A forward bias voltage causes electrons to accumulate at the interface, increasing the interface conductivity; a reverse bias voltage depletes electrons, reducing the interface conductivity. The duration of the bias voltage ranges from 1 second to 24 hours. The control is completely reversible; the electronic state returns to its initial state after the voltage is removed.

[0015] (2) Mechanical stress modulation: When mechanical stresses such as pressure, bending or tension are applied from 0.1 MPa to 10 MPa, the mechanical stress changes the spacing between the A / B interfaces, thereby changing the width and shape of the electron tunneling barrier. The stress application time ranges from instantaneous to 24 hours. With the assistance of the piezoelectric B or C components, the stress also generates interfacial polarization charges, significantly changing the electron barrier and tunneling probability at the interface.

[0016] (3) Photoexcitation modulation: When irradiated with light in the wavelength range of 200 nm to 10 μm, photoexcitation generates electron-hole pairs, excitons, or photogenerated carriers at the interface, changing the charge density and band filling state at the interface. The irradiation time ranges from 1 second to 24 hours. For van der Waals heterointerfaces with type II band alignment, photoexcitation generates interlayer excitons—electrons and holes are located in different layers, exhibiting a long lifetime and extremely high response speed.

[0017] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0018] As a preferred technical solution, in the electronic state control material, component A is selected from at least one of graphene, molybdenum disulfide, tungsten disulfide, molybdenum diselenide, tungsten diselenide, MXene, and black phosphorus; component B is selected from at least one of hexagonal boron nitride, aluminum nitride thin film, mica thin film, talc thin film, montmorillonite thin film, and layered bimetallic hydroxide; the mass ratio of component A to component B is 1:20 to 20:1.

[0019] As a preferred technical solution, the electronic state modulation material further comprises a C component, wherein the C component is a two-dimensional piezoelectric material selected from at least one of odd-layer molybdenum disulfide, odd-layer tungsten disulfide, odd-layer molybdenum diselenide, odd-layer tungsten diselenide, hexagonal boron nitride monolayer, zinc oxide nanosheets, polyvinylidene fluoride and its copolymers; the mass of the C component accounts for 0.5% to 20% of the total mass of the composite material.

[0020] As a preferred technical solution, in the electronic state control material, both component A and component B maintain a two-dimensional morphology with a thickness ranging from atomic to nanometer scale; the gap between component A and component B is 0.3 nm to 10 nm, forming an electron tunneling barrier layer.

[0021] As a preferred technical solution, in the electronic state control material, a conductive-insulating-conductive stacked structure is formed between component A and component B, wherein the conductive layer in the stacked structure is component A and the insulating layer is component B; the stacked structure is connected to an electrode, which is used to apply a voltage between the conductive layers.

[0022] As a preferred technical solution, in the electronic state control material, component A or component B is a piezoelectric material, and the van der Waals heterostructure changes the interfacial spacing when subjected to mechanical stress of 0.1 MPa to 10 MPa.

[0023] As a preferred technical solution, in the electronic state control material, the A component and the B component are stacked to form a heterostructure, and the heterostructure generates electron-hole pairs under light irradiation with a wavelength of 200 nm to 10 μm.

[0024] As a preferred technical solution, the electronic state regulation material further includes a modifying agent, wherein the modifying agent is selected from at least one of silane coupling agents, titanate coupling agents, aluminate coupling agents, polyethylene glycol, polyvinylpyrrolidone, sodium dodecyl sulfate, hexadecyltrimethylammonium bromide, polyacrylic acid, and polymethyl methacrylate; the mass of the modifying agent accounts for 0.1% to 10% of the total mass of the composite material.

[0025] As a preferred technical solution, the electronic state control material, wherein the B component contains a doping element, the doping element being selected from at least one of lithium, sodium, potassium, magnesium, calcium, strontium, barium, aluminum, gallium, indium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, yttrium, lanthanum, and cerium, and the doping amount is from 1 at% to 50 at%.

[0026] Secondly, a method for preparing an electronic state-controlled material as described above, comprising: Component A and component B are mixed according to a preset ratio to obtain a mixture; The mixture is ball-milled to obtain powder. The powder is heat-treated in an inert atmosphere, and after cooling and pulverizing, the electronic state-controlled material is obtained.

[0027] As a preferred technical solution, in the method for preparing the electronic state control material, the D50 particle size of the electronic state control material is 10 nanometers to 100 micrometers.

[0028] As a preferred technical solution, in the method for preparing the electronic state-controlled material, the ball milling speed is 100 rpm to 500 rpm; the ball milling time is 1 hour to 24 hours; and the heating rate of the heat treatment is 1°C / min to 20°C / min.

[0029] Thirdly, an article comprising the electronic state control material described above; the material is present in the article in the form of powder, film, coating, filler or suspension; When the article is a sensor or electronic device, after the sensor or electronic device is subjected to mechanical stress causing the van der Waals heterostructure to separate and spontaneously recombine, its electronic state regulation function is restored to a level that can meet the requirements for normal operation of the device.

[0030] Beneficial effects: Compared with existing technologies, this invention does not rely on any molecular recognition unit, but directly utilizes the intrinsic physical properties of van der Waals heterointerfaces, namely atomic-level interstices and tunable electric fields, to control the electronic states of the interface. Through three physical mechanisms—changing the interface charge distribution and band alignment with an applied electric field, altering the interfacial spacing and tunneling barrier shape with applied mechanical stress, and changing the interface electron filling state by photoexcitation to generate photogenerated carriers—multi-dimensional and reversible control of the interface electronic states is achieved. The electronic state control capability remains effective over a wide temperature range, from -100°C to 300°C, because electronic state control relies on quantum tunneling rather than thermally activated carrier diffusion. The quantum tunneling response speed of electrons at the interface is much faster than that of conventional semiconductor devices. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or related technologies, the drawings used in the description of the embodiments or related technologies will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0032] Figure 1 A schematic diagram illustrating the principle of electronic state modulation at van der Waals heterostructures provided in an embodiment of the present invention.

[0033] Figure 2 This is a schematic diagram of the energy band structure of an electronic state regulated by an electric field, provided in an embodiment of the present invention.

[0034] Figure 3This is a schematic diagram of the structure of a quantum tunneling sensor provided in an embodiment of the present invention.

[0035] Figure 4 This is a schematic diagram of the structure of a spin field-effect transistor provided in an embodiment of the present invention. Detailed Implementation

[0036] The embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. The following examples are for illustrative purposes only and should not be construed as limiting the scope of the invention.

[0037] In the description of the embodiments of the present invention, it should be noted that the terms "center," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing the embodiments of the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the embodiments of the present invention. In addition, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0038] In the description of the embodiments of the present invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "connected" and "linked" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium. Those skilled in the art can understand the specific meaning of the above terms in the embodiments of the present invention based on the specific circumstances.

[0039] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0040] This invention provides an electronic state control material based on a van der Waals heterointerface, comprising component A and component B. Component A is a two-dimensional conductive material, and component B is a two-dimensional insulating material. Components A and B are stacked and bonded together by van der Waals forces to form a van der Waals heterointerface. This van der Waals heterointerface undergoes interlayer separation under mechanical stress and spontaneously recombines after the mechanical stress is removed.

[0041] In this embodiment, component A is a two-dimensional conductive material selected from at least one of graphene, molybdenum disulfide, tungsten disulfide, molybdenum diselenide, tungsten diselenide, MXene, and black phosphorus. These two-dimensional conductive materials have atomically flat surfaces and excellent electron transport properties. Graphene has extremely high carrier mobility, making it suitable for high-frequency electronic devices; transition metal sulfides such as molybdenum disulfide and tungsten disulfide have tunable band structures and strong spin-orbit coupling, making them suitable for spintronic devices and photodetectors; MXene combines metallic conductivity and solution processability; and the band structure of black phosphorus is continuously tunable from the near-infrared to the visible light range with the number of layers. Component B is a two-dimensional insulating material selected from at least one of hexagonal boron nitride, aluminum nitride thin layers, mica thin layers, talc thin layers, montmorillonite thin layers, and layered bimetallic hydroxides. Hexagonal boron nitride has a hexagonal lattice structure similar to graphene, and its lattice constant is close to that of graphene. Therefore, it has good lattice matching when combined with graphene, which is beneficial for forming high-quality van der Waals interfaces. Mica and talc thin layers are natural two-dimensional mineral materials that are inexpensive and easy to peel off. Layered bimetallic hydroxides possess tunable interlayer spacing and anion exchange capacity, allowing for further modulation of interfacial properties by adjusting interlayer ions. The mass ratio of component A to component B is 1:20 to 20:1. Within this ratio range, higher component A content enhances the material's conductivity, making it suitable for applications requiring strong electrical signals; higher component B content enhances insulation and results in a more significant interfacial capacitance effect, making it suitable for applications requiring strong electric field control.

[0042] In this embodiment, components A and B are stacked and bonded together by van der Waals forces to form a van der Waals heterostructure. Since both A and B are two-dimensional layered materials, their atomically flat surfaces rely primarily on interlayer van der Waals forces for bonding during stacking, rather than covalent bonds. This bonding method is characterized by a moderate bonding force, approximately one-tenth to one-hundredth the strength of a covalent bond, allowing for relative slippage and separation between layers. In the absence of external force, the layers spontaneously recombine to the most stable stacking configuration. The van der Waals heterostructure in this invention undergoes reversible separation along the interlayer when subjected to mechanical stress, releasing stress without damaging the lattice structure of individual two-dimensional material layers. Once the mechanical stress is removed, the layers spontaneously recombine through van der Waals forces, restoring the original contact state. This bonding-separation-rebonding process is reversible and can be repeated throughout the material's entire lifespan.

[0043] In this embodiment, both component A and component B maintain a two-dimensional morphology with thicknesses ranging from atomic to nanometer scales. The gap between A and B is 0.3 nm to 10 nm, forming an electron tunneling barrier layer. Due to the atomically flat surfaces of A and B, the gap naturally formed between the two layers after stacking is determined by the equilibrium of van der Waals interactions. For the graphene and hexagonal boron nitride system, the equilibrium distance between layers is approximately 0.33 nm. When the gap width is in the range of 0.3 nm to 10 nm, the quantum tunneling probability of electrons between the two A layers is significantly affected by the gap width and the barrier height. The electron tunneling current has an exponential relationship with the gap width; therefore, a small change in the gap can cause a measurable change in current. This characteristic makes van der Waals heterointerfaces the basic structure for sensitive quantum tunneling sensors.

[0044] In this embodiment, component A and component B form a conductive-insulating-conductive stacked structure, where component A is the conductive layer and component B is the insulating layer. This stacked structure can be equivalent to a parallel-plate capacitor model, i.e., two conductive plates sandwiching an insulating dielectric. Electrodes are connected to the stacked structure for applying a voltage between the conductive layers. The electrode materials are selected from conductive materials such as gold, platinum, silver, copper, aluminum, and indium tin oxide. When a voltage is applied between components A through the electrodes, an electric field perpendicular to the layer plane is generated inside the insulating component B. This electric field changes the charge distribution and band alignment at the interface, thereby modulating the electronic state density and conductivity at the interface. When a forward bias is applied, electrons accumulate at the interface, increasing conductivity; when a reverse bias is applied, electrons are depleted, decreasing conductivity. This modulation is reversible; the electronic states return to their initial state after the voltage is removed.

[0045] In this embodiment, the interfacial spacing changes when the van der Waals heterostructure is subjected to mechanical stress ranging from 0.1 MPa to 10 MPa. The mechanical stress includes both compressive and tensile stress. When compressive stress perpendicular to the interface is applied, the spacing between components A and B decreases, the electron tunneling barrier width narrows, and the tunneling current exponentially increases. When tensile stress is applied, the spacing increases, and the tunneling current decreases. The piezoelectric material in component A or component B generates interfacial polarization charges under stress, further altering the electron barrier and tunneling probability at the interface. The application time of the mechanical stress can be selected from instantaneous to 24 hours.

[0046] In this embodiment, component A and component B are stacked to form a heterostructure, generating electron-hole pairs under light irradiation with wavelengths from 200 nm to 10 μm. When the band alignment of A and B is type II (interleaved), photogenerated electrons and holes are located in different layers, forming interlayer excitons. These excitons have a long lifetime and a high response speed. Photogenerated charge carriers change the charge density and band filling state at the interface, thereby altering the transport characteristics of the interface's electronic states. The irradiation time ranges from 1 second to 24 hours.

[0047] In another embodiment of the invention, the invention may further include component C. Component C is a two-dimensional piezoelectric material selected from at least one of odd-layer molybdenum disulfide, odd-layer tungsten disulfide, odd-layer molybdenum diselenide, odd-layer tungsten diselenide, hexagonal boron nitride monolayer, zinc oxide nanosheets, polyvinylidene fluoride, and copolymers thereof. The mass of component C accounts for 0.5% to 20% of the total mass of the composite material. When the two-dimensional piezoelectric material is subjected to mechanical stress, it generates piezoelectric charges in the thickness direction. When component C is located as an interface layer between A and B, the piezoelectric charges enhance or weaken the electrostatic interaction forces between the layers, thereby assisting in the modulation of the electronic states of the van der Waals interface.

[0048] In another embodiment of the invention, the invention may further include a modifying agent selected from at least one of silane coupling agents, titanate coupling agents, aluminate coupling agents, polyethylene glycol, polyvinylpyrrolidone, sodium dodecyl sulfate, hexadecyltrimethylammonium bromide, polyacrylic acid, and polymethyl methacrylate. The modifying agent accounts for 0.1% to 10% of the total mass of the composite material. The coupling agent forms an organic molecular layer on the surface of the two-dimensional nanomaterial, improving the interfacial compatibility between A and B and promoting uniform dispersion. Hydrophilic polymers such as polyethylene glycol can improve the dispersion stability of the material in aqueous systems. Polymers such as polyacrylic acid and polymethyl methacrylate can enhance the mechanical strength of the material.

[0049] In another embodiment of the present invention, component B may contain a dopant element selected from at least one of lithium, sodium, potassium, magnesium, calcium, strontium, barium, aluminum, gallium, indium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, yttrium, lanthanum, and cerium, with a doping amount of 1 at% to 50 at%. The dopant element enters the crystal lattice of component B by substitution or interstitial means, changing its electronic structure. Introducing a dopant element into the insulator component B can adjust its dielectric constant and interfacial charge density, thereby controlling the interfacial bonding force and electronic state distribution between A and B.

[0050] Based on the above embodiments, the present invention also provides a method for preparing the above material, comprising: mixing component A and component B in a preset ratio; ball milling the mixed material; then heat-treating it in an inert atmosphere; and finally cooling it to obtain an electronically controlled material.

[0051] The composite of component A with component B and optional component C is accomplished through three basic unit operations: ball milling, heat treatment, and pulverization. Ball milling utilizes the impact and shearing action of the grinding beads to thoroughly mix the two-dimensional lamellar materials of A and B, and promotes the stacking and van der Waals contact between the lamellars under mechanical force. The ball milling speed is preferably 100 to 500 rpm, and the time is preferably 1 to 24 hours. If the speed is too low or the time is too short, the lamellars of A and B cannot make sufficient contact and stack, resulting in poor composite uniformity; if the speed is too high or the time is too long, the lamellars may be excessively broken, reducing the lamellar size and affecting the area and integrity of the van der Waals interface. The heat treatment step is carried out in an inert atmosphere to enhance the bonding stability between A and B and remove defects introduced during the ball milling process. The heat treatment temperature is preferably 100 to 1100 degrees Celsius, the time is preferably 10 minutes to 24 hours, and the heating rate is preferably 1 to 20 degrees Celsius per minute. At excessively low temperatures, the interfacial bonding enhancement effect is not significant; at excessively high temperatures, it may lead to the destruction of the crystal structure or a transformation of the crystal form of A or B. After heat treatment, the material is cooled to room temperature in an inert atmosphere, then pulverized and sieved to obtain a powdered composite material with a D50 particle size of 10 nanometers to 100 micrometers. When the material exists in film form, it is formed by methods such as blade coating, casting, spin coating, or spraying. The wet film thickness is preferably 10 to 500 micrometers, the drying temperature is preferably 30 to 200 degrees Celsius, and the drying time is preferably 1 to 24 hours. When the material exists in the form of a battery electrode coating, it is coated on the surface of a metal foil. The wet film thickness is preferably 50 to 300 micrometers, the drying temperature is preferably 60 to 150 degrees Celsius, and the drying time is preferably 1 to 5 hours.

[0052] The technical solution of the present invention will be further described in detail below with reference to specific embodiments.

[0053] Example 1 Graphene (component A) and hexagonal boron nitride (component B) were mixed at a mass ratio of 1:5. Odd-layered molybdenum disulfide (component C, 3% of the total material mass) and silane coupling agent KH-550 (2% of the total material mass) were added, and the mixture was ball-milled. The ball milling speed was 300 rpm, and the milling time was 12 hours. The mixture was then heat-treated to 800°C at a rate of 5°C per minute under an argon atmosphere for 30 minutes, followed by furnace cooling to room temperature. The resulting material was pulverized and sieved to obtain the electronically controlled material. In this electronically controlled material, graphene and hexagonal boron nitride are stacked to form a van der Waals heterostructure, and the atomic-level gaps between them constitute an electron tunneling barrier layer. The odd-layered molybdenum disulfide, acting as a piezoelectric material, generates piezoelectric charges under stress to assist in controlling the electronic states of the interface.

[0054] Example 2 Molybdenum disulfide (component A) and boron hexagonal nitride (component B) were mixed at a mass ratio of 1:3. Tungsten disulfide (component C, odd-layered, 2% of the total material mass) and titanate coupling agent (1% of the total material mass) were added, and the mixture was ball-milled. The ball milling speed was 200 rpm, and the milling time was 24 hours. The mixture was then heat-treated to 400°C at a rate of 10°C per minute under a nitrogen atmosphere for 12 hours, followed by natural cooling to room temperature in air. The resulting material was pulverized and sieved to obtain the electronically regulated material.

[0055] Example 3 Component A (MXene) and component B (aluminum nitride thin film) were mixed at a mass ratio of 1:10. Component C (odd-numbered layers of molybdenum diselenide, 5% of the total material mass) and the modifier polyvinylpyrrolidone (1% of the total material mass) were added, and the mixture was ball-milled. The ball milling speed was 400 rpm, and the milling time was 6 hours. The mixture was then heat-treated under vacuum at a rate of 15 degrees Celsius per minute to 1100 degrees Celsius for 10 minutes, followed by quenching to room temperature. The resulting material was pulverized and sieved to obtain the electronically regulated material.

[0056] Example 4 The powder from Example 1 was mixed with the excipient polyurethane, and dimethylformamide was added and stirred to form a slurry. A film was formed by blade coating, with a wet film thickness of 150 micrometers, and dried at 80 degrees Celsius for 4 hours to obtain the film product.

[0057] Example 5 The powder from Example 2 was mixed with the excipient polyvinyl butyral, and ethanol was added and stirred to form a slurry. A film was formed using a casting method and dried at 60 degrees Celsius for 6 hours to obtain a self-supporting film product.

[0058] Example 6 The powder from Example 1 was pressed into a sheet at a pressure of 10 MPa. Electrode layers were formed on the upper and lower surfaces of the sample by ion sputtering gold. The sample was placed in a vacuum probe stage, and a DC bias voltage of 0 to 10 V was applied through the electrodes to measure the source-drain current. The results showed that the source-drain current monotonically increased with increasing bias voltage, and returned to its initial value after the bias voltage was reduced from 10 V to 0 V, confirming that the external electric field can reversibly control the electronic state density at the van der Waals heterostructure.

[0059] Example 7 The powder from Example 2 was compressed into tablets at a pressure of 10 MPa. The samples were placed in a dynamic mechanical analyzer, and the tunneling current perpendicular to the interface was measured under different pressures, ranging from 0 to 10 MPa. The results showed that the tunneling current increased exponentially with increasing pressure, and the tunneling current at 10 MPa was approximately 50 times that at 0 MPa. This confirms that mechanical stress can modulate the quantum tunneling probability at the van der Waals heterojunction.

[0060] Example 8 The powder from Example 3 was pressed into tablets. The samples were placed in a sealed gas chamber, and NO2 gas of varying concentrations (from 1 ppb to 100 ppm) was introduced. The tunneling current perpendicular to the interface was measured. The results showed that the tunneling current monotonically increased with increasing NO2 concentration, and the current change was still detectable at a concentration of 1 ppb. This test confirms that the present invention can achieve highly sensitive gas detection solely through electronic behavior without relying on any molecular recognition units.

[0061] Example 9 The van der Waals heterostructure film prepared by the method in Example 1 was used to fabricate a ferromagnetic metal electrode (nickel-iron alloy) on graphene of component A for spin implantation and spin detection. A bias voltage ranging from -5V to +5V was applied to the gate, and the intensity of the spin signal was detected using a nonlocal measurement method. The results showed that the intensity of the spin signal varied with the gate voltage; a positive gate voltage enhanced the spin signal, while a negative gate voltage weakened it, confirming that the spin polarization state at the van der Waals heterostructure interface can be tuned by an external electric field.

[0062] Example 10 The van der Waals heterointerface thin film prepared by the method in Example 2 was used as a pump source with a femtosecond laser (wavelength 532 nm) to measure the transient absorption spectrum of photogenerated carriers. The results show that the response time of photogenerated carriers is about 500 femtoseconds and the decay time is about 5 picoseconds. This response speed is much faster than that of traditional semiconductor photodetectors, verifying the advantages of van der Waals heterointerfaces in the field of ultrafast photodetection.

[0063] Example 11 The samples from Example 1 were subjected to repeated electric field modulation tests at temperatures of -100°C, -50°C, 0°C, 25°C, 100°C, 200°C, and 300°C. The results showed that the electronic state modulation function remained normal across the entire temperature range from -100°C to 300°C, and the two-dimensional morphologies of components A and B remained stable. This confirms the effectiveness of electronic state modulation at van der Waals heterointerfaces across the entire temperature range.

[0064] Example 12 The sample from Example 1 was subjected to bending damage treatment (bending radius 2 mm, repeated bending 10 times), and the changes in source and leakage current before and after damage and after self-repair were measured. The results showed that the source and leakage current decreased by approximately 30% from the initial value after bending damage, indicating that interlayer separation at the interface led to a partial interruption of the conductive pathway between components A. After standing at room temperature for 1 hour, self-repair was completed, and the source and leakage current recovered to more than 90% of the initial value, indicating that the van der Waals interface successfully re-bonded and the conductive pathway was restored. The recovery rate remained consistent after multiple damage repair cycles, with no significant attenuation. This confirms that the self-repair capability of the van der Waals heterointerface can recover the electronic behavior degradation caused by interface damage.

[0065] The modulation principle of the van der Waals heterointerface electronic state modulation material provided in this invention embodiment is as follows: Figure 1 As shown. The energy band structure of the electronic state modulated by the electric field is as follows. Figure 2 As shown. The structure of the quantum tunneling sensor is as follows. Figure 3 As shown, when external micromolecules or stress cause atomic-level changes in the intermediate B layer and interfacial gaps, the electron tunneling current detected by the left and right electrodes changes exponentially, thus achieving highly sensitive physical detection. The structure of the spin field-effect transistor is as follows: Figure 4 As shown.

[0066] In summary, this invention provides an electronic state control material based on a van der Waals heterointerface, comprising component A and component B, wherein component A is a two-dimensional conductive material and component B is a two-dimensional insulating material; the components A and B are stacked and bonded together by van der Waals forces to form a van der Waals heterointerface; the van der Waals heterointerface undergoes interlayer separation when subjected to mechanical stress, and spontaneously recombines after the mechanical stress is removed.

[0067] This invention, for the first time, utilizes van der Waals heterointerfaces themselves as a platform for regulating electronic quantum behavior, expanding van der Waals heterointerfaces from self-healing structural materials and molecular recognition functional materials to electronic state regulation materials, opening up entirely new application dimensions. Unlike existing electronic devices that rely on chemical modification or complex heterostructures, the regulation driving force of this invention comes from the intrinsic physical properties of the van der Waals heterointerface—atomic-level interstices and tunable electric fields—without consuming any active materials, and theoretically can be regulated an unlimited number of times. Three external stimuli (electric field, stress, and light) cover the main physical regulation methods, enabling multi-dimensional, reversible, and quantitative regulation of the interface's electronic states. An external electric field regulates the interface's electronic state density and band structure, mechanical stress regulates the tunneling barrier width and shape, and photoexcitation regulates charge density and band filling state. The three stimuli can be used independently or synergistically, providing a rich array of technical means. It is completely independent of molecular recognition units (D-components), achieving physical detection functions solely through electronic behavior itself. Unlike molecular-level patents that achieve chemical / biological recognition through D-components, this invention utilizes the intrinsic physical response of the localized medium density perturbation at the electron pair interface to achieve highly sensitive gas detection without requiring any chemical recognition unit.

[0068] Furthermore, it exhibits stable controllability over a wide temperature range. The composite material of this invention maintains effective electronic state controllability across a wide temperature range from -100°C to 300°C. At the extreme low temperature of -100°C, the controllability of the electronic device remains good, and the response time remains essentially constant across the entire temperature range. At the high temperature of 300°C, the two-dimensional morphology of components A and B remains stable, and the interface can still effectively control the electronic state. This is because electronic state control relies on the quantum tunneling effect, rather than thermally activated carrier diffusion; therefore, temperature has a very low impact on the control rate. It possesses a precise time response window. The electronic state control of the van der Waals heterointerface has well-defined time parameters—the quantum tunneling response time is 1 femtosecond to 100 picoseconds, more than two orders of magnitude faster than conventional semiconductor devices; the electronic state recovery time after the external excitation is removed is 0.1 seconds to 24 hours. The time for the electronic behavior of the van der Waals heterointerface to recover to more than 90% of its initial value after self-repair is 1 minute to 10 minutes at room temperature and can still be completed within 1 hour at -100°C. These precise timing parameters provide reliable quantitative basis for the engineering design and application of electronic devices. The powerful van der Waals interface self-healing function ensures the long-term stability of the device. The van der Waals interface self-healing function remains effective within a wide temperature range of -100°C to 300°C. At room temperature, the van der Waals interface self-healing is completed within a reasonable time, and the contact state recovery rate is no less than 85% after 100 cycles. After the van der Waals interface self-healing, the electronic state modulation function synchronously recovers to more than 85%-90% of its initial value, and the performance tends to stabilize with no degradation. The synergistic work of the van der Waals interface self-healing and electronic state modulation solves the fatal defect of irreversible interface degradation in traditional quantum devices. It has a van der Waals interface self-healing electrical signal monitoring function. This invention is the first to realize the electrical self-sensing of the interface damage and healing process of electronic devices. By monitoring the resistance or tunneling current changes of the composite material itself, the interface state and the degree of electronic behavior recovery can be obtained in real time without external sensors.

[0069] Finally, it should be noted that the above embodiments are only for illustrating the present invention and not for limiting the present invention. Although the present invention has been described in detail with reference to the embodiments, those skilled in the art should understand that various combinations, modifications, or equivalent substitutions of the technical solutions of the present invention do not depart from the spirit and scope of the technical solutions of the present invention and should be covered within the scope of the claims of the present invention.

Claims

1. A material for electronic state modulation based on van der Waals heterostructures, characterized in that, It comprises component A and component B, wherein component A is a two-dimensional conductive material and component B is a two-dimensional insulating material; The A and B components are stacked and bonded together by van der Waals forces to form a van der Waals heterogeneous interface. The van der Waals heterostructure undergoes interlayer separation when subjected to mechanical stress, and spontaneously recombines after the mechanical stress is removed. After the van der Waals heterostructure recombines, the electronic state modulation function between component A and component B is restored to a level that meets the requirements for normal device operation.

2. The electronic state modulation material according to claim 1, characterized in that, Component A is selected from at least one of graphene, molybdenum disulfide, tungsten disulfide, molybdenum diselenide, tungsten diselenide, MXene, and black phosphorus; Component B is selected from at least one of hexagonal boron nitride, aluminum nitride thin film, mica thin film, talc thin film, montmorillonite thin film, and layered bimetallic hydroxide; the mass ratio of component A to component B is 1:20 to 20:

1.

3. The electronic state modulation material according to claim 1, characterized in that, It also includes component C, which is a two-dimensional piezoelectric material selected from at least one of odd-layer molybdenum disulfide, odd-layer tungsten disulfide, odd-layer molybdenum diselenide, odd-layer tungsten diselenide, hexagonal boron nitride monolayer, zinc oxide nanosheets, polyvinylidene fluoride and its copolymers; the mass of component C accounts for 0.5% to 20% of the total mass of the composite material.

4. The electronic state modulation material according to claim 1, characterized in that, Both component A and component B maintain a two-dimensional morphology with a thickness ranging from atomic to nanometer scale; the gap between component A and component B is 0.3 nm to 10 nm, forming an electron tunneling barrier layer.

5. The electronic state modulation material according to claim 1, characterized in that, A conductive-insulating-conductive stacked structure is formed between component A and component B, wherein the conductive layer of the stacked structure is component A and the insulating layer is component B; the stacked structure is connected to electrodes, which are used to apply voltage between the conductive layers.

6. The electronic state control material according to claim 1, characterized in that, Component A or Component B is a piezoelectric material, and the interfacial spacing changes when the van der Waals heterostructure is subjected to mechanical stress of 0.1 MPa to 10 MPa.

7. The electronic state control material according to claim 1, characterized in that, The A component and the B component are stacked to form a heterostructure, which generates electron-hole pairs when irradiated with light of wavelength from 200 nm to 10 μm.

8. The electronic state control material according to claim 1, characterized in that, It also includes a modifying agent selected from at least one of silane coupling agents, titanate coupling agents, aluminate coupling agents, polyethylene glycol, polyvinylpyrrolidone, sodium dodecyl sulfate, hexadecyltrimethylammonium bromide, polyacrylic acid, and polymethyl methacrylate; the modifying agent accounts for 0.1% to 10% of the total mass of the composite material.

9. The electronic state modulation material according to claim 1, characterized in that, The B component contains a doping element selected from at least one of lithium, sodium, potassium, magnesium, calcium, strontium, barium, aluminum, gallium, indium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, yttrium, lanthanum, and cerium, with a doping amount of 1 at% to 50 at%.

10. A method for preparing an electronic state-controlled material as described in claim 1, characterized in that, include: Component A and component B are mixed according to a preset ratio to obtain a mixture; The mixture is ball-milled to obtain powder. The powder is heat-treated in an inert atmosphere, and after cooling and pulverizing, the electronic state-controlled material is obtained.

11. The method for preparing the electronic state-controlled material according to claim 10, characterized in that, The D50 particle size of the electronic state modulation material is 10 nanometers to 100 micrometers.

12. The method for preparing the electronic state-controlled material according to claim 10, characterized in that, The ball milling process is performed at a rotation speed of 100 rpm to 500 rpm; the ball milling time is 1 hour to 24 hours; and the heat treatment is performed at a heating rate of 1°C / min to 20°C / min.

13. An article characterized in that, The product comprises the electronic state control material according to any one of claims 1 to 9; the material is present in the product in the form of powder, film, coating, filler or suspension; When the article is a sensor or electronic device, after the sensor or electronic device is subjected to mechanical stress causing the van der Waals heterostructure to separate and spontaneously recombine, its electronic state regulation function is restored to a level that can meet the requirements for normal operation of the device.

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