CN109545960B - Memristor with continuously variable conductance and preparation method and application thereof - Google Patents

Memristor with continuously variable conductance and preparation method and application thereof Download PDF

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CN109545960B
CN109545960B CN201811346835.7A CN201811346835A CN109545960B CN 109545960 B CN109545960 B CN 109545960B CN 201811346835 A CN201811346835 A CN 201811346835A CN 109545960 B CN109545960 B CN 109545960B
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memristor
electrode
crystal material
dimensional atomic
atomic crystal
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CN109545960A (en
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章晓中
尹思琪
熊成悦
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Tsinghua University
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    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801Constructional details of multistable switching devices
    • H10N70/841Electrodes
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011Manufacture or treatment of multistable switching devices

Abstract

The invention discloses a memristor with continuously variable conductance, and a preparation method and application thereof, and belongs to the technical field of microelectronics. The memristor is characterized in that an active electrode and an inert electrode are arranged on the surface of a two-dimensional atomic crystal material at intervals, wherein the two-dimensional atomic crystal material is a single-crystal two-dimensional atomic crystal material with semiconductor characteristics, and a semi-insulating atomic-level smooth surface is provided for migration of metal cations of the active electrode under an electric field, so that the metal cations migrate to form a conductive filament, and the conductance of the memristor is continuously variable; the preparation method is simple, economical and easy to implement; the memristor can be applied to simulating the learning and memory behaviors of the fruit flies.

Description

Memristor with continuously variable conductance and preparation method and application thereof
Technical Field
The invention belongs to the technical field of microelectronics, and particularly relates to a memristor with continuously variable conductance, and a preparation method and application thereof.
Background
In 1971, the professor zeisure of zeitle predicted that there were fourth basic circuit elements in addition to resistance, capacitance, inductance, characterizing the relationship between charge q and magnetic flux ψ, based on the symmetry of the circuit, and named memristor. The resistance value of the memristor can change along with the change of the current or voltage value flowing through the memristor, namely, the memristor has a memory function on the charge and the magnetic flux flowing through the device. The Hewlett packard company publishes work in Nature in 2008, the device preparation conforming to the memristor theory is realized for the first time, and the research of the memristor is followed by a new development trend.
The cation migration type memristor is an important type of memristor and generally consists of an active metal electrode (silver, copper and the like), an inert metal electrode (platinum, gold and the like) and a dielectric material (a fast ion conductor, an oxide, an organic matter and the like) sandwiched between the active metal electrode and the inert metal electrode. Under the action of an electric field, metal cations formed by oxidation of the active metal electrode migrate in the dielectric material to form conductive filaments, and the conductivity value of the device is changed by connection and breakage of the conductive filaments. A common problem in the cation migration type memristor is that the conductive filament may cause a sudden increase in device conductance at the instant of formation of the insulating dielectric layer, which does not meet the requirement of continuous variation of memristor conductance with the applied electric field in brain-like simulation.
Disclosure of Invention
The invention aims to provide a memristor with continuously variable conductance, and a preparation method and application thereof, and the specific technical scheme is as follows:
a memristor with continuously variable electric conductance is provided with an active electrode and an inert electrode at intervals on the surface of a two-dimensional atomic crystal material.
The spacing distance between the active electrode and the inert electrode is 100 nm-500 nm.
The active electrode is made of silver or copper, and the inert electrode is made of platinum, gold, tungsten or palladium.
The thickness of the two-dimensional atomic crystal material is 0.6 nm-50 nm, wherein the minimum thickness of the two-dimensional atomic crystal material can also be the thickness of a single-layer two-dimensional atomic crystal material.
The two-dimensional atomic crystal material is a single-crystal two-dimensional atomic crystal material with semiconductor characteristics, and provides a semi-insulating atomic-level smooth surface for migration of metal cations of the active electrode under an electric field.
The two-dimensional atomic crystal material is transition metal chalcogenide or black phosphorus; wherein the transition metal chalcogenide is molybdenum disulfide, tungsten disulfide, molybdenum diselenide or tungsten diselenide.
The two-dimensional atomic crystal material is produced by a mechanical lift-off method, a chemical vapor deposition method (CVD), or a chemical vapor transport method (CVT).
The two-dimensional atomic crystal material takes thermal silicon oxide, aluminum oxide or glass as a substrate, wherein the thermal silicon oxide substrate is a substrate on which an insulating silicon dioxide layer is generated on the surface of a silicon substrate by a thermal oxidation method.
The preparation method of the memristor with continuously variable conductance comprises the following steps:
(1) transferring the prepared two-dimensional atomic crystal material to a substrate, and annealing;
(2) preparing an active electrode with a preset pattern on the surface of a two-dimensional atomic crystal material;
(3) preparing an inert electrode with a preset pattern at a position on the surface of the two-dimensional atomic crystal material, which is 100 nm-500 nm away from the active electrode.
The annealing treatment in the step (1) comprises the following steps: under vacuum degree of 2.0X 10-6mbar, 300 ℃ for 1.5 hours.
The preparation method of the active electrode or the inert electrode with the preset pattern comprises the following steps: presetting a pattern on the surface of a two-dimensional atomic crystal material by an ultraviolet lithography method and an electron beam lithography method, then growing an active electrode or an inert electrode by magnetron sputtering and an electron beam evaporation method, and finally removing photoresist and stripping.
The memristor or prepared by the preparation method can be applied to simulating the learning and memory behaviors of the fruit flies.
The invention has the beneficial effects that:
(1) the memristor provided by the invention is a cation migration type memristor, and utilizes the characteristic that metal cations of an active electrode migrate on the surface of a two-dimensional atomic crystal material with semiconductor characteristics under an electric field to form a conductive filament consisting of continuously distributed and fine metal nano particles, and realizes that the conductance can be continuously changed along with the change of an external electric field through the planar structure of the active electrode/the two-dimensional atomic crystal/the inert electrode.
(2) The characteristic that the conductance of the memristor provided by the invention can be continuously changed along with the number of pulses can be utilized to realize the simulation of the learning and memory behaviors of the fruit flies.
Drawings
FIG. 1 is a memristor structure with continuously variable conductance provided by the present invention;
fig. 2 is a graph illustrating continuous control of device conductance of the silver/molybdenum disulfide/platinum planar memristor prepared in example 1 under continuous positive (a) and negative (b) pulse voltages, respectively;
fig. 3 is a microstructure of the silver/molybdenum disulfide/platinum planar structure memristor prepared in example 1 under a scanning electron microscope before (a) and after (b) applying a voltage;
fig. 4 shows continuous control of device conductance of the silver/tungsten disulfide/platinum planar memristor prepared in example 2 under continuous positive (a) and negative (b) pulse voltages, respectively;
fig. 5 shows the microstructure of the silver/tungsten disulfide/platinum planar memristor prepared in example 2 under a scanning electron microscope before (a) and after (b) applying a voltage;
FIG. 6 is a graph of the change in conductance of a silver/silicon dioxide/platinum planar structure memristor in comparative example 1 under continuous positive pulses;
fig. 7 is a comparison of the conductance change of the silver/molybdenum disulfide/platinum plane structure memristor (b) prepared in example 1 and the drosophila memory level (a) under the same number of electric pulses and electric pulse intensity.
Detailed Description
The invention provides a memristor with continuously variable conductance, a preparation method and an application thereof, and the invention is further explained by combining an embodiment and a drawing.
Fig. 1 is a schematic diagram of a structure of a memristor with continuously variable conductance provided by the present invention, the memristor structure of the present invention is a planar structure with an active electrode/two-dimensional atomic crystal/inert electrode on a substrate, that is, a two-dimensional atomic crystal material with semiconductor characteristics is used as a dielectric to provide a semi-insulating atomic-level smooth surface for metal cations in the active electrode, so as to achieve continuously variable conductance; wherein the active electrode and the inert electrode are both arranged on the surface of the two-dimensional atomic crystal material and are spaced at a distance of 100 nm-500 nm.
Example 1
The silver/molybdenum disulfide/platinum plane structure memristor is prepared according to the following steps:
(1) stripping a thin layer of molybdenum disulfide from a molybdenum disulfide crystal by a mechanical stripping method with an adhesive tape and transferring the molybdenum disulfide onto a thermal silicon oxide substrate at 2.0X 10-6Annealing treatment under mbar vacuum at 300 ℃, wherein the annealing heat preservation time is 1.5 h;
(2) preparing active electrode silver with a preset pattern: finding a molybdenum disulfide thin layer under an optical microscope, presetting the shape of an active silver electrode on the molybdenum disulfide thin layer by an ultraviolet lithography method, then depositing the active electrode silver by a magnetron sputtering method, and finally removing photoresist and stripping to obtain the active electrode silver;
(3) preparing inert electrode platinum with a preset pattern: presetting the shape of inert electrode platinum on the molybdenum disulfide thin layer at a position 200nm away from the active silver electrode by using an electron beam lithography method, depositing the inert electrode platinum by using a magnetron sputtering method, and finally removing the photoresist and stripping to obtain the inert electrode platinum.
FIG. 2 shows the continuous regulation and control of the conductance of the prepared silver/molybdenum disulfide/platinum planar structure memristor under continuous positive and negative pulse voltages respectively, wherein a in FIG. 2 is the change situation of the conductance of the memristor under a series of continuous positive pulses (+2V/200ms) along with the number of pulses, and b in FIG. 2 is the change situation of the conductance of the memristor under a series of continuous negative pulses (-2V/200ms) along with the number of pulses. It can be seen from a of fig. 2 that the memristor conductance can continuously increase with the increase of the number of positive-going pulses, and it can be seen from b of fig. 2 that the memristor conductance continuously decreases with the increase of the number of negative-going pulses.
Fig. 3 is a microstructure of the silver/molybdenum disulfide/platinum planar memristor prepared in example 1 under a scanning electron microscope before and after voltage is applied; wherein a of fig. 3 is a microstructure of a silver/molybdenum disulfide/platinum planar structure memristor before application of a voltage; as can be seen from a of the attached figure 3, the active electrode silver and the inert electrode platinum are respectively positioned at two ends of the molybdenum disulfide, and the flat edges of the electrodes are clear. A voltage source is connected between a silver electrode and a platinum electrode of a memristor with a silver/molybdenum disulfide/platinum planar structure, a forward voltage is applied to one side of the silver electrode, the platinum electrode is grounded, the microstructure of the silver electrode is observed under a scanning electron microscope, as shown in b of the attached figure 3, a conductive filament formed by migration of active electrode silver on the surface of two-dimensional atomic crystal molybdenum disulfide can be seen, namely, under the action of an electric field, the active electrode material silver migrates on the surface of the molybdenum disulfide along the direction of the electric field, a conductive filament formed by a series of quasi-continuous fine silver nanoparticles as shown in b of the attached figure 3 is formed, and further the conductance of the memristor can be continuously changed along with an external electric field.
Example 2
The silver/tungsten disulfide/platinum plane structure memristor is prepared according to the following steps:
(1) stripping tungsten disulfide thin layer from tungsten disulfide crystal by mechanical stripping method with adhesive tape, transferring to thermal silicon oxide substrate, and stripping at 2.0 × 10-6mbar vacuum, 300 ℃ annealing treatment, annealing and heat preservationThe time is 1.5 h;
(2) preparing active electrode silver with a preset pattern: finding a tungsten disulfide thin layer under an optical microscope, presetting the shape of an active silver electrode on the tungsten disulfide thin layer by an ultraviolet lithography method, then depositing the active electrode silver by a magnetron sputtering method, and finally removing photoresist and stripping to obtain the active electrode silver;
(3) preparing inert electrode platinum with a preset pattern: and presetting the shape of inert electrode platinum on the tungsten disulfide thin layer at a position 380nm away from the active silver electrode by using an electron beam lithography method, depositing the inert electrode platinum by using a magnetron sputtering method, and finally removing the photoresist and stripping to obtain the inert electrode platinum.
Fig. 4 is a diagram illustrating continuous control of device conductance of the silver/tungsten disulfide/platinum planar memristor prepared in example 2 under continuous positive and negative pulse voltages, respectively; wherein a of fig. 4 is a condition that the conductance of the memristor under a series of continuous positive-going pulses (+3V/200ms) changes with the number of pulses, and b of fig. 4 is a condition that the conductance of the memristor under a series of continuous negative-going pulses (-3V/200ms) changes with the number of pulses. It can be seen from a of fig. 4 that the conductance of the device can continuously increase with increasing number of positive-going pulses, and from b of fig. 4 that the conductance of the device continuously decreases with increasing number of negative-going pulses.
Fig. 5 is a microstructure of the silver/tungsten disulfide/platinum planar memristor prepared in example 2 under a scanning electron microscope before and after voltage is applied; wherein a of fig. 5 is a microstructure of a silver/tungsten disulfide/platinum planar structure memristor before application of a voltage; as can be seen from a of figure 5, the silver of the active electrode and the platinum of the inert electrode are positioned at two ends of the tungsten disulfide, and the flat edges of the electrodes are clear. A voltage source is connected between a silver electrode and a platinum electrode of the memristor with the silver/tungsten disulfide/platinum planar structure, forward voltage is applied to one side of the silver electrode, the platinum electrode is grounded, the microstructure of the silver electrode is observed under a scanning electron microscope, and as shown in b of the attached figure 5, a conductive filament formed by migration of silver of an active electrode on the surface of two-dimensional atomic crystal tungsten disulfide can be seen; that is, under the action of an electric field, silver, which is an active electrode material, migrates on the surface of tungsten disulfide along the direction of the electric field, so that a conductive filament composed of a series of quasi-continuous fine silver nanoparticles as shown in b of fig. 5 is formed, and further, the conductance of the memristor is continuously changed along with the change of an external electric field.
Comparative example 1
The two-dimensional atomic crystal in example 1 was replaced with insulating silicon dioxide having a thickness of about 300nm, and the preparation procedure was as follows.
(1) Preparing silicon dioxide with the thickness of 300nm on an n-type silicon wafer by adopting a thermal oxidation method;
(2) preparing active electrode silver with a preset pattern: presetting the shape of an active silver electrode on the silicon dioxide layer by an ultraviolet lithography method, then depositing the active silver electrode by a magnetron sputtering method, and finally removing the photoresist and stripping to obtain the active silver electrode;
(3) preparing inert electrode platinum with a preset pattern: presetting the shape of the inert electrode platinum on the silicon dioxide layer at a position 200nm away from the active silver electrode by using an electron beam lithography method, depositing the inert electrode platinum by using a magnetron sputtering method, and finally removing the photoresist and stripping to obtain the inert electrode platinum.
Fig. 6 shows that the conductance of the silver/silicon dioxide/platinum planar memristor prepared in comparative example 1 under a series of forward pulses (+5V/200ms) changes along with the number of the forward pulses, and it can be seen that the conductance of the silver/silicon dioxide/platinum device changes abruptly along with the increase of the number of the pulses. Comparing the change of the conductance of the silver/molybdenum disulfide/platinum planar structure memristor along with the number of forward pulses in fig. 2 a of example 1 with the change of the conductance of the silver/tungsten disulfide/platinum planar structure memristor along with the number of forward pulses in fig. 4 a of example 2, it can be seen that when the dielectric layer material is insulating silicon dioxide, the conductance of the memristor is abrupt change along with the increase of the number of pulses. Therefore, the surface of the transition metal chalcogenide two-dimensional atomic crystal is used as the material of the intermediate medium layer, so that the continuity of the memristor conductance changing along with the number of pulses can be obviously enhanced.
Example 3
The silver/molybdenum disulfide/platinum planar structure memristor prepared in the embodiment 1 is applied to the simulation of the learning and memory behaviors of fruit flies, as shown in the attached figure 7;
the fruit flies can generate memory for the stimulation pulses under the electric stimulation, and the process of generating the memory by the fruit flies under the electric stimulation is called the learning behaviors of the fruit flies. Fig. 7 a shows the memory level of the drosophila as a function of the number and intensity of the electric pulses, and it can be seen that the memory level of the drosophila increases significantly as the number and intensity of the electric pulses increase. Fig. 7 b is a graph showing the change of the conductance of the silver/molybdenum disulfide/platinum planar memristor prepared in example 1 with the number of electric pulses and the intensity of the electric pulses. Comparing fig. 7 a with fig. 7 b, it is obvious that the trend of the change of the conductance of the silver/molybdenum disulfide/platinum plane structure memristor prepared in example 1 along with the number and intensity of electric pulses is consistent with the learning behavior trend of fruit flies, and the silver/molybdenum disulfide/platinum plane structure memristor can be well applied to the simulation of the learning behavior of fruit flies.

Claims (8)

1. A memristor with continuously variable conductance is characterized in that an active electrode and an inert electrode are arranged on the surface of a two-dimensional atomic crystal material at intervals, and the two-dimensional atomic crystal material takes thermal silicon oxide, aluminum oxide or glass as a substrate;
the active electrode is made of silver or copper, and the inert electrode is made of platinum, gold, tungsten or palladium;
the two-dimensional atomic crystal material has semiconductor characteristics and is transition metal chalcogenide or black phosphorus;
the memristor is a cation migration type memristor, metal cations of an active electrode migrate on the surface of a two-dimensional atomic crystal material with semiconductor characteristics under an electric field to form a conductive filament consisting of continuously distributed fine metal nano-particles, and the continuous change of the conductance along with the change of an external electric field is realized through the planar structure of the active electrode/the two-dimensional atomic crystal/the inert electrode.
2. The memristor with continuously variable conductance according to claim 1, wherein the active electrode and the inert electrode are separated by a distance of 100nm to 500 nm.
3. The memristor with continuously variable conductance according to claim 1, wherein the two-dimensional atomic crystal material has a thickness of 0.6nm to 50 nm.
4. The memristor of claim 1, wherein the transition metal chalcogenide is molybdenum disulfide, tungsten disulfide, molybdenum diselenide, or tungsten diselenide.
5. The memristor with continuously variable conductance according to claim 1, wherein the two-dimensional atomic crystal material is prepared by a mechanical lift-off method, a chemical vapor deposition method, or a chemical vapor transport method.
6. A method of making a memristor with continuously variable conductance according to any of claims 1 to 5, comprising the steps of:
(1) transferring the prepared two-dimensional atomic crystal material to a substrate, and annealing;
(2) preparing an active electrode with a preset pattern on the surface of a two-dimensional atomic crystal material;
(3) preparing an inert electrode with a preset pattern at a position on the surface of the two-dimensional atomic crystal material, which is 100 nm-500 nm away from the active electrode.
7. The manufacturing method according to claim 6, wherein the annealing treatment in the step (1) is: under vacuum degree of 2.0X 10-6mbar, 300 ℃, heating for 1.5 hours; the preparation method of the active electrode or the inert electrode with the preset pattern comprises the following steps: presetting a pattern on the surface of a two-dimensional atomic crystal material by an ultraviolet lithography method or an electron beam lithography method, then growing an active electrode or an inert electrode by a magnetron sputtering method or an electron beam evaporation method, and finally removing photoresist and stripping.
8. The application of the memristor as in any one of claims 1 to 5 or the memristor prepared by the preparation method as in any one of claims 6 to 7 is characterized in that the memristor is applied to simulate the learning and memory behaviors of fruit flies.
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CN111009609B (en) * 2019-12-24 2022-06-07 华中科技大学 Superlattice memristor functional layer material, memristor unit and preparation method of superlattice memristor functional layer material
CN113437216B (en) * 2021-07-06 2023-04-07 武汉理工大学 Memristor based on electron-ion mixed conductor and preparation method thereof

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Gate-tunable memristive phenomena mediated by grain boundaries in single-layer MoS2;Vinod K. Sangwan, et al.;《NATURE NANOTECHNOLOGY》;20150406;第10卷;page 403–406 & SUPPLEMENTARY INFORMATION *

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