CN117279487A - Method for preparing memristor by electrochemical anodic oxidation - Google Patents

Method for preparing memristor by electrochemical anodic oxidation Download PDF

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CN117279487A
CN117279487A CN202311164341.8A CN202311164341A CN117279487A CN 117279487 A CN117279487 A CN 117279487A CN 202311164341 A CN202311164341 A CN 202311164341A CN 117279487 A CN117279487 A CN 117279487A
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memristor
metal layer
bottom electrode
anodic oxidation
oxidation
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郭新
金天
化帅斌
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011—Manufacture or treatment of multistable switching devices
    • H10N70/021—Formation of switching materials, e.g. deposition of layers
    • H10N70/028—Formation of switching materials, e.g. deposition of layers by conversion of electrode material, e.g. oxidation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/20—Multistable switching devices, e.g. memristors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/841—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/881—Switching materials
    • H10N70/883—Oxides or nitrides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/881—Switching materials
    • H10N70/883—Oxides or nitrides
    • H10N70/8833—Binary metal oxides, e.g. TaOx
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N79/00—Integrated devices, or assemblies of multiple devices, comprising at least one solid-state element covered by group H10N70/00

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Abstract

The invention relates to a method for preparing a memristor by electrochemical anodic oxidation, and belongs to the technical field of semiconductor devices and electrochemistry. Firstly, a bottom electrode and a metal layer of a memristor are obtained on a substrate, then a part to be oxidized is put into an electrolytic cell, voltage stimulation is applied for a certain time, the part of the metal layer far away from the bottom electrode is oxidized into metal oxide, and the oxidation degree of the oxidized part of the metal layer is distributed in a gradient manner; and then obtaining a top electrode, and finally preparing the volatile and nonvolatile memristor with good consistency and stable circulation. The invention provides a method for oxidizing a resistive layer of a memristor by electrochemical anodic oxidation to generate a dense oxide layer with oxygen vacancies distributed in a gradient manner. The method can improve the preparation efficiency of the memristor; the preparation method is simplified, and the uniformity of memristor resistance change behaviors and the uniformity of the memristor array can be greatly improved.

Description

Method for preparing memristor by electrochemical anodic oxidation
Technical Field
The invention belongs to the technical field of semiconductor devices and electrochemistry, and particularly relates to a method for preparing a memristor by electrochemical anodic oxidation.
Background
The memristor was first prepared by the hewlett packard laboratory since 2008, which demonstrates that the vast prospect of memristors has been focused by scientists worldwide after the existence of the proposed "fourth passive basic circuit element" by the Cai Shaotang professor.
Memristors have also become a research hotspot in information storage and brain-like computation in recent years. The human brain is composed of about 10 11 Individual neuron passes 10 15 The synapses are connected with each other to form a complex neural network with integrated information storage and calculation functions. And inspired by the brain, scientists have proposed artificial neural networks of different models. While the basic units in the neural network, namely neurons and synapses, can replace CMOS devices formed by tens of transistors and capacitors through a single memristor, so that related functions of the CMOS devices are simulated. Thus, we can achieve integration of higher density synapses or neuron arrays by using memristor arrays, ultimately improving the computation and energy efficiency of artificial neural networks.
Often, the preparation and testing of a single memristor have low requirements on the uniformity and homogeneity of devices, but if a certain-scale memristor array is required to be manufactured on a single silicon wafer, each memristor device is required to have repeatable and similar resistance change behaviors, so that the array can be better regulated and controlled, or the array is used for calculation. The process of directly growing the film on the sample by utilizing the physical deposition technology generally has higher cost, energy consumption and higher environmental conditions such as vacuum degree, atmosphere and the like, and oxygen vacancy defects in the prepared metal oxide film are randomly distributed, so that the conductive filament memristor has larger randomness in the resistance change process, and the resistance change behavior is more variable in the resistance change process of the device due to random conduction of the conductive filament under the stimulation of electric bias. The metal layer is oxidized by the electrochemical anodic oxidation method, so that the requirements of vacuum degree and atmosphere condition are eliminated, the energy consumption is small, and meanwhile, the oxide film which is more compact, better in uniformity, gradient in oxidation degree and higher in quality can be obtained. Because of the nature of the oxide film which is formed by the method and has the gradient property of decreasing the oxidation degree from the surface to the bottom electrode, the conductive filaments are more prone to conduct under the same oxidation degree area, so that the resistance change behavior of the device is more consistent. The method for preparing the device can improve the uniformity and consistency of the device, saves time and labor more than the physical method, can realize a memristor array with higher density, and has great significance in realizing the function of a related neural network.
Disclosure of Invention
The invention aims to provide a method for preparing a memristor resistance change layer by electrochemistry, which comprises the steps of carrying out partial oxidation on a metal layer by using an electrochemistry method to obtain a metal oxide layer, and finally preparing a memristor with a cross structure, wherein the memristor has stable resistance change, good consistency and good uniformity, so that the technical problem of poor stability, consistency and uniformity of the memristor in the prior art is solved.
According to an object of the present invention, there is provided a method for manufacturing a memristor by means of electrochemical anodic oxidation, comprising the steps of:
(1) Photoetching and developing a bottom electrode pattern on a substrate by using a photoetching technology, and depositing a bottom electrode;
(2) Photoetching and developing patterns of the metal layer on the bottom electrode obtained in the step (1), and then depositing the metal layer;
(3) Taking the sample obtained in the step (2) as an anode, taking an inert metal electrode as a cathode, and performing anodic oxidation in electrolyte to oxidize the part of the metal layer far away from the bottom electrode into metal oxide, wherein the oxidation degree of the oxidized part of the metal layer is in gradient distribution;
(4) And (3) photoetching and developing a top electrode pattern on the metal oxide obtained in the step (3), and depositing a top electrode to prepare the memristor with the cross electrode structure.
Preferably, the thickness of the metal layer in step (2) is greater than 60nm and less than 300nm;
if the anodic oxidation voltage in the step (3) is 15-60V and the anodic oxidation time is 60-240s, the oxidation degree is high, and the obtained memristor is an electron conduction volatile memristor; if the voltage of the anodic oxidation in the step (3) is 10-25V and the time of the anodic oxidation is 10-25s, the oxidation degree is low, and the obtained memristor is a nonvolatile memristor with oxygen vacancy filament conduction.
Preferably, in step (2), the metal layer is tantalum, titanium, niobium, hafnium or zinc.
Preferably, the electrolyte in the step (3) is an acid, alkali or salt solution, and the concentration range is 0.05-2M/L.
Preferably, the bottom electrode is platinum, palladium or gold, and the thickness of the bottom electrode is 20-50nm.
Preferably, the bottom electrode is platinum, gold, ruthenium or palladium and the top electrode has a thickness of at least 50nm.
Preferably, the deposition methods in step (1), step (2) and step (4) are each independently selected from physical magnetron sputtering or atomic layer deposition.
Preferably, in the step (1), the bottom electrode is a bottom electrode array; the metal layer in the step (2) is a metal layer array; the top electrode in the step (4) is a top electrode array.
According to another aspect of the invention, a memristor or a memristor array prepared by the method is provided.
In summary, compared with the prior art, the above technical solution contemplated by the present invention can at least obtain the following beneficial effects:
(1) The invention provides a method for preparing a memristor oxide layer by electrochemical anodic oxidation. Compared with the traditional physical mode for preparing the oxide layer, the method does not need severe vacuum degree and atmosphere conditions or high energy consumption, can prepare the metal oxide layer with lower energy consumption and time cost, and improves the efficiency of preparing the memristor device.
(2) The preparation method can regulate and control the thickness, oxidation degree and other properties of the oxide layer film by regulating and controlling the oxidation voltage, oxidation time and the type and concentration of electrolyte solution in the anodic oxidation process. The oxidation process in the present invention oxidizes only a portion of the upper layer of the oxidized metal layer and does not completely change the metal layer into an oxidized layer, thereby retaining a portion of the underlying metal. According to the regulation and control of the oxidation degree of the oxidation layer by the oxidation process such as the oxidation time, the invention can obtain the nonvolatile memristor when the oxidation degree is lower, and obtain the volatile memristor when the oxidation degree is higher.
(3) The preparation method is suitable for preparing various memristors with metal oxides as the resistance change layers, has strong universality, and is also suitable for preparing large-scale memristor arrays.
(4) The memristor prepared by the method is more compact in oxide layer, smoother in surface and gradually and uniformly reduced in oxidation degree from top to bottom, so that migration of ions or vacancies of the memristor is more concentrated in the same area in the resistance change process, and macroscopic resistance change of the device is consistent. The consistency of memristor devices can be improved, the resistance change behavior of the memristor devices is improved, and the regulation and the calculation of the memristor arrays are facilitated. Thus, the application of the method on the neural network has wider prospect.
(5) According to the preparation method provided by the invention, memristor devices with different performances can be prepared by simply regulating and controlling the solubility and the type of electrolyte, the oxidation time, the oxidation voltage and other parameters. The upper metal layer is partially oxidized and the lower portion remains metal. The memristor with nonvolatile energy can be prepared to simulate the related functions of synapses when the oxidation degree of the upper metal is low, and the memristor with volatile energy can be prepared to simulate the related functions of neurons when the oxidation degree of the upper metal is high.
(6) The method can enable the memristor to have more consistent resistance change behavior, and is more beneficial to realizing large-scale integration of the memristor array.
Drawings
FIG. 1 is a schematic diagram of the vertical and horizontal structures of a memristor in the method of the present disclosure.
FIG. 2 is a schematic diagram of an array of memristors in the method of the present disclosure.
Fig. 3 is a simplified schematic diagram of an anodic oxidation platform of the present invention.
FIG. 4 is a graph comparing I-V cycle tests of tantalum oxide-based memristors obtained by physical magnetron sputtering with comparative example 1 of the present invention and tantalum oxide-based memristors obtained by anodic oxidation of example 1.
FIG. 5 is a simulated synaptic plasticity curve of a memristor of example 1 obtained by the present disclosure.
FIG. 6 is an I-V characteristic of a titanium oxide-based non-volatile memristor obtained in example 2.
FIG. 7 is an I-V characteristic and a conductance pulse response plot of the tantalum oxide-based volatile memristor obtained in example 3.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
According to the method for preparing the memristor by utilizing the electrochemical anodic oxidation, the oxidation layer of the memristor is prepared by utilizing the electrochemical oxidation method, so that the density and uniformity of the resistance change layer are improved. Meanwhile, the oxidation degree of the oxidation layer is gradually reduced from top to bottom, and for a nonvolatile memristor, the formation and fracture positions of oxygen vacancy filaments are constant in the resistance change process, so that better consistency is obtained; the memristor adopts a classical sandwich structure on a vertical structure, namely a structure that two layers of electrodes sandwich a resistive layer, adopts a crossed electrode structure on a horizontal direction, and is mutually perpendicular to a bottom electrode and a top electrode under plane projection.
The preparation method comprises the following specific steps:
(1) Cleaning a silicon wafer substrate with silicon oxide on the surface and drying, so as to obtain a surface suitable for film growth;
(2) Depositing a bottom electrode pattern: photoetching a bottom electrode pattern on a substrate by using a photoetching technology, and regrowing an electrode film;
(3) Preparing a metal layer: firstly, photoetching patterns of a metal resistance change layer on a sample, and then depositing a metal layer with a certain thickness;
(4) Preparing an oxide layer: placing a sample in an anode, placing an inert metal electrode in a cathode, and placing the sample in electrolyte together to apply voltage stimulation for a certain time to obtain metal oxide with a certain thickness;
(5) Preparing a top electrode: and photoetching a top electrode pattern on the sample, depositing a top electrode, and preparing the memristor with the cross electrode structure.
In some embodiments, in step (1), the specific step of cleaning is: and sequentially placing the silicon wafer substrate into acetone, alcohol and deionized water, respectively ultrasonically cleaning for 15 minutes, circulating for three times, and finally drying by using nitrogen.
In some embodiments, the patterns in the steps (2), (3) and (5) are developed by using a photolithography technique, and the electrode film is prepared by using a deposition technique such as physical magnetron sputtering or atomic layer deposition technique after photolithography.
In some embodiments, the bottom electrode composition in step (2) is a 3-5nm titanium metal layer and a 20-50nm platinum metal layer; wherein titanium can be replaced by tungsten and other materials with better adhesion with silicon wafers, and platinum can be replaced by palladium, gold and other inert noble metals.
In some embodiments, in the step (3), the metal layer material deposited by physical magnetron sputtering or atomic layer deposition may be a metal having a resistive effect of oxides such as tantalum, titanium, niobium, hafnium, zinc, etc., and the deposition thickness should be greater than 60nm and less than 300nm, so as to prepare the oxide layer by anodic oxidation.
In some embodiments, in the step (3), a process of depositing a metal layer film by using a magnetron sputtering technology is specifically: mounting metal layer target (such as metal tantalum target) on the chamber target source, and controlling vacuum degree of the chamber at 2×10 -6 Below Torr, in order toSputtering for 20-100 minutes to obtain a metal layer (such as tantalum metal layer) with a thickness of at least 60 nm.
In some embodiments, in the step (4), the oxide layer is obtained by depositing a metal film in advance, placing the metal film on a power anode by an electrochemical anodic oxidation method, and oxidizing the metal film in an electrolyte together with an inert metal cathode by applying electrical stimulation. The memristors with different volatile energies can be prepared by different coordination of the concentration and the type of the electrolytic cell solution, the oxidation voltage and the oxidation time. Oxidation is easy to generate an oxide film with more complete oxidation under a large voltage and a long time, so that a volatile device with tunneling effect is prepared, and oxygen vacancies generated under a small voltage or a short time are more, so that a nonvolatile device with oxygen vacancy filament conduction is formed. For example, in a 0.5M phosphoric acid solution, oxidation of 60nm tantalum metal for 10-25s at 10-25V oxidation voltage may yield a non-volatile memristor, while oxidation of 60-240s at 25-60V oxidation voltage may yield a volatile memristor.
In some embodiments, the electrochemical anodic oxidation method is adopted, specifically: the anodic oxidation electrolytic cell is acid, alkali or salt solution, and the concentration range is 0.05-2M/L; the oxidized metal can be metal with resistance change effect of oxides of tantalum, titanium, niobium, hafnium, zinc and the like, the inert electrode can be platinum, gold, palladium, ruthenium, graphite and the like, the oxidation voltage is 10-50V, and the oxidation time is 10-120s.
In some embodiments, the top electrode in the step (5) is formed of an inert metal layer, and may be formed of platinum, gold, ruthenium, palladium, or the like. And the top electrode thickness is at least 50nm to prevent the step effect from causing circuit opening.
According to the memristor, the metal oxide layer with gradient oxidation degree and uniform surface can be obtained, and the obtained resistive layer is more uniform and has more uniform resistive behavior; compared with the existing common deposition method, the method does not need severe vacuum conditions, atmosphere conditions and the like, and can be used for preparing memristor devices and arrays in a method with lower cost and higher energy efficiency, so that memristors with higher consistency are obtained.
The following are specific examples
Example 1
The embodiment provides a preparation method for preparing a non-volatile tantalum oxide-based memristor with a cross structure by using an electrochemical anodic oxidation method, and fig. 1 is a schematic diagram of vertical and horizontal structures of the memristor in the method of the present invention, with Top Electrode (TE) as a Top Electrode, bottom Electrode (BE) as a Bottom Electrode, and Resistive Layer (RL) as a Resistive Layer. FIG. 2 is a schematic diagram of an array of memristors in the method of the present disclosure.
The method comprises the following steps:
cleaning a silicon wafer substrate: putting the silicon wafer into acetone, ethanol and deionized water for one time, respectively ultrasonically cleaning for 15 minutes, circulating for 3 times, and drying by a nitrogen gun for later use;
preparing a bottom electrode: after a bottom electrode pattern is obtained on a substrate by using a photoetching development technology, placing a sample on a tray of a magnetron sputtering cavity, respectively mounting a titanium target and a platinum target on a target source of the cavity, pumping the background vacuum degree of the cavity to be less than 2 multiplied by 10 < -6 > Torr, introducing argon with the purity of 99.999% as working gas, and sputtering the gas with the sputtering pressure of 3mTorrSputtering to a thickness of 5nm, and then +.>Sputtering deposition is carried out to obtain a platinum metal layer with the thickness of 20nm, and then degumming treatment is carried out to obtain a bottom electrode;
preparing a tantalum metal layer: after a pattern of a resistance change layer is obtained on a sample by using a photoetching development technology, the sample is placed on a tray of a magnetron sputtering cavity, a tantalum target is installed on a target source of the cavity, the background vacuum degree of the cavity is pumped to be less than 2 multiplied by 10 < -6 > Torr, argon with the purity of 99.999% is introduced as working gas, and the sputtering pressure is 3mTorr so as to obtain the target materialSputtering for 20 minutes to obtain a tantalum metal film with the thickness of 60 nm;
preparation of a tantalum oxide layer: and fixing the sample by using a conductive clamp, and connecting the sample with the positive electrode of a power supply to form an anode. And connecting the inert platinum metal net electrode with a power supply negative electrode to form a cathode, putting the cathode and the anode together in a phosphoric acid solution with the concentration of 0.5M, and stirring the electrolyte at the rotating speed of 350r/s by using an electric stirring rod. After the cell conditions were set, the sample was oxidized with a voltage of 18-20V for 18-20s to partially oxidize the previously deposited tantalum metal layer and obtain a tantalum oxide layer of about 30 nm. And taking out the sample after the oxidation is finished, and performing degumming treatment to obtain the complete resistive layer electrode. A schematic diagram of the anodic oxidation electrolytic cell device is shown in fig. 3;
preparing a top electrode: after a top electrode pattern is obtained on a substrate by using a photoetching development technology, placing a sample on a tray of a magnetron sputtering cavity, mounting a platinum target on a target source of the cavity, pumping the background vacuum degree of the cavity to be less than 5 multiplied by 10 < -6 > Torr, introducing argon with the purity of 99.999% as working gas, and sputtering the sample at the air pressure of 3mTorr to obtain the target materialSputtering and depositing to obtain a platinum metal layer with the thickness of 40nm, and then degumming to obtain a top electrode;
comparative example 1
The comparative example was prepared by the same method as in example 1 except that after step (2), a tantalum oxide resistive layer was directly deposited by using a magnetron sputtering method, after the resistive layer was prepared, after the top electrode pattern was developed by photolithography, metal tantalum and platinum were sequentially deposited to complete the preparation of the top electrode, specifically:
preparing a resistance change layer: after a pattern of a resistance change layer is developed by photoetching a sample, the pattern is placed on a tray of a magnetron sputtering cavity, a tantalum oxide target material is arranged on a target source of the cavity, and the background vacuum degree of the cavity is pumped to be less than 2 multiplied by 10 -6 Torr, introducing argon with the purity of 99.999% as working gas, sputtering air pressure of 3mTorr, and sputtering a tantalum oxide target by using radio frequency with the sputtering rate ofDepositing for 7 minutes to obtain a tantalum oxide film with the thickness of at least 20nm, and then performing degluing treatment.
Preparing a top electrode: after a top electrode pattern is obtained on a substrate by using a photoetching development technology, placing a sample on a tray of a magnetron sputtering cavity, mounting tantalum and platinum targets on a target source of the cavity, and carrying out background vacuum degree on the cavityPumping to less than 5×10 -6 Introducing argon gas with purity of 99.999% as working gas into the reactor, wherein the sputtering pressure is 3mTorrSequentially sputtering and depositing to obtain tantalum with the thickness of 30nm and a platinum metal layer with the thickness of 20nm, and then degumming to obtain the top electrode.
Memristors of comparative example 1 and comparative example 1 were analyzed:
FIG. 4 is a graph comparing I-V cycle tests of tantalum oxide-based memristors obtained by physical magnetron sputtering with tantalum oxide-based memristors obtained by anodic oxidation of example 1 of comparative example 1 of the present disclosure. By way of comparison, the 100 cycle profile of the device of example 1 is significantly more consistent than the 50 cycle profile of the device of comparative example 1. It can be seen that the uniformity of the memristor device with the same material type of the resistive layer prepared by the electrochemical anodic oxidation method is higher than that of the device obtained by the traditional magnetron sputtering method.
FIG. 5 is a simulated synaptic plasticity curve of a tantalum oxide-based memristor obtained in example 1 of the present disclosure. As can be seen from fig. 5, the device prepared can well mimic some of the functions of synapses.
Example 2
The embodiment provides a preparation method for preparing a nonvolatile titanium oxide-based memristor with a cross structure by using an electrochemical anodic oxidation method, which comprises the following steps:
cleaning a silicon wafer substrate: step (1) in the same manner as in example 1
Preparing a bottom electrode: step (2) in the same manner as in example 1
Preparing a titanium metal layer: after a pattern of a resistance change layer is obtained on a sample by using a photoetching development technology, the sample is placed on a tray of a magnetron sputtering cavity, a titanium target is arranged on a target source of the cavity, and the background vacuum degree of the cavity is pumped to be less than 2 multiplied by 10 - 6 Introducing argon gas with purity of 99.999% as working gas into the reactor, wherein the sputtering pressure is 3mTorrSputtering for 50 minutes to obtain a titanium metal film with the thickness of 60 nm;
preparing a titanium oxide layer: the cell set-up was the same as in step (4) of example 1, and after the cell condition set-up was completed, the sample was subjected to oxidation with a voltage of 18V for 15s, so that the upper portion of the titanium metal layer was oxidized, and a titanium oxide layer was obtained, and the lower portion remained in the Ti metal layer. And taking out the sample after the oxidation is finished, and performing degumming treatment to obtain the complete resistive layer electrode.
Preparing a top electrode: step (5) in the same manner as in example 1
FIG. 6 is an I-V characteristic of a titanium oxide-based memristor obtained in example 2. The titanium oxide memristor prepared through experiments has stable resistance variation behavior.
Example 3
The embodiment provides a preparation method for preparing a volatile tantalum oxide-based memristor with a cross structure by using an electrochemical anodic oxidation method, which comprises the following steps of
Cleaning a silicon wafer substrate: step (1) in the same manner as in example 1
Preparing a bottom electrode: step (2) in the same manner as in example 1
Preparing a tantalum metal layer: after a pattern of a resistance change layer is obtained on a sample by using a photoetching development technology, the sample is placed on a tray of a magnetron sputtering cavity, a tantalum target is arranged on a target source of the cavity, and the background vacuum degree of the cavity is pumped to be less than 2 multiplied by 10 - 6 Introducing argon gas with purity of 99.999% as working gas into the reactor, wherein the sputtering pressure is 3mTorrSputtering for 40 minutes to obtain a tantalum metal film with the thickness of 120 nm;
preparation of a tantalum oxide layer: the cell configuration was the same as in step (4) of example 1, and after the cell condition configuration was completed, the sample was oxidized with a voltage of 30V for 120 seconds, so that the upper portion of the tantalum metal layer was oxidized to obtain a tantalum oxide layer, and the oxidation degree was high. And taking out the sample after the oxidation is finished, and performing degumming treatment to obtain the complete resistive layer electrode.
Preparing a top electrode: step (5) in the same manner as in example 1
FIG. 7 is a graph of the I-V characteristics and conductance retention under pulse for the tantalum oxide memristor obtained in example 3. Wherein in a negative scan, this corresponds to applying a positive voltage to the top electrode. From the graph, the tantalum oxide memristor prepared in the embodiment 3 has stable volatile resistance behavior, and the electric conduction can automatically recover to an initial state in a short time after pulse adjustment.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (10)

1. A method for preparing a memristor by electrochemical anodic oxidation, comprising the following steps:
(1) Photoetching and developing a bottom electrode pattern on a substrate by using a photoetching technology, and depositing a bottom electrode;
(2) Photoetching and developing patterns of the metal layer on the bottom electrode obtained in the step (1), and then depositing the metal layer;
(3) Taking the sample obtained in the step (2) as an anode, taking an inert metal electrode as a cathode, and performing anodic oxidation in electrolyte to oxidize the part of the metal layer far away from the bottom electrode into metal oxide, wherein the oxidation degree of the oxidized part of the metal layer is in gradient distribution;
(4) And (3) photoetching and developing a top electrode pattern on the metal oxide obtained in the step (3), and depositing a top electrode to prepare the memristor with the cross electrode structure.
2. The method of fabricating a memristor by electrochemical anodization of claim 1, wherein the thickness of the metal layer in step (2) is greater than 60nm and less than 300nm;
if the anodic oxidation voltage in the step (3) is 15-60V and the anodic oxidation time is 60-240s, the oxidation degree is high, and the obtained memristor is an electron conduction volatile memristor; if the voltage of the anodic oxidation in the step (3) is 10-25V and the time of the anodic oxidation is 10-25s, the oxidation degree is low, and the obtained memristor is a nonvolatile memristor with oxygen vacancy filament conduction.
3. The method of fabricating a memristor by electrochemical anodization of claim 1 or 2, wherein in step (2), the metal layer is tantalum, titanium, niobium, hafnium, or zinc.
4. The method for fabricating a memristor by electrochemical anodization of claim 1, wherein the electrolyte in the step (3) is an acid, base or salt solution with a concentration ranging from 0.05 to 2M/L.
5. The method of fabricating a memristor by electrochemical anodization of claim 1, wherein the bottom electrode is platinum, palladium or gold, and the bottom electrode has a thickness of 20-50nm.
6. The method of fabricating a memristor by electrochemical anodization of claim 1, wherein the bottom electrode is platinum, gold, ruthenium or palladium and the top electrode is at least 50nm thick.
7. The method for fabricating a memristor by electrochemical anodization of claim 1, wherein the deposition methods in step (1), step (2) and step (4) are each independently selected from physical magnetron sputtering or atomic layer deposition.
8. The method of fabricating a memristor by electrochemical anodization of claim 1, wherein the bottom electrode in step (1) is a bottom electrode array; the metal layer in the step (2) is a metal layer array; the top electrode in the step (4) is a top electrode array.
9. Memristors prepared by the method of any one of claims 1-7.
10. The memristor array prepared by the method of claim 8.
CN202311164341.8A 2023-09-11 2023-09-11 Method for preparing memristor by electrochemical anodic oxidation Pending CN117279487A (en)

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