CN112687794A - Flexible memristor with self-repairing capability and preparation method - Google Patents
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- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims abstract description 44
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Abstract
The invention provides a flexible memristor with self-repairing capability and a preparation method thereof4‑MnSO4The weak acid solution is used as an electrolyte solution, and a structure capable of spontaneously generating electrochemical reaction is formed by oxidation/reduction reaction of ions in the solution on the manganese dioxide film, so that the resistance of the memristor is changed. According to the invention, the liquid electrolyte is used as a dielectric layer, and the memristive performance is realized by using the thin film layer of which the liquid electrolyte and the negative electrode are subjected to oxidation/reduction reaction, so that the reaction efficiency is increased by using the interface reaction, and the ion concentration can be adjusted according to different requirements, thereby realizing the adjustment of the memristive performance. The invention provides a preparation method of a liquid flexible memristor, which is easy to physically realize, simple in preparation process, stable in quality, high in cyclicity, low in cost and high in production efficiency.
Description
Technical Field
The invention relates to the field of application of micro-nano electronic devices and nonlinear circuits, in particular to a flexible memristor with self-repairing capability and a preparation method thereof.
Background
The memristor (memory resistor) is a fourth passive circuit element after a resistor, a capacitor and an inductor enter the mainstream electronic field, and is a passive circuit element related to magnetic flux and electric charge. As early as 1971, the international precursor to nonlinear circuit and cellular neural network theory, Leon Chua, theorically predicted the existence of memristors based on the logical integrity of the circuit theory. In 2008, a memristor prototype device is firstly experimentally constructed in a Hewlett packard laboratory, and the theory of Leon Chua about memristors is proved to attract strong attention worldwide. The memristor has novel nonlinear electrical properties, has the characteristics of high density, small size, low power consumption, non-volatility and the like, and is considered to be one of ideal schemes for developing a next-generation novel non-volatile storage technology. Therefore, it is a hot spot for research in the fields of information, materials, etc. In addition, the resistance change behavior of the memristor has high similarity with the biological neural plasticity, so that the memristor has potential in the aspects of developing neural synapse bionic devices, neuromorphic computers and the like.
The structure of the existing memristor is a sandwich structure formed by clamping a nano-scale double-layer titanium dioxide semiconductor thin film between two nanowires made of Pt in a published paper of Nature journal published by laboratory researchers of Hewlett packard company in 5 months 2008. The well-known memristor manufacturing model is actually a nonlinear resistor with a memory function. The resistance value can be changed by controlling the change of the current, and if the high resistance value is defined as '0', the low resistance value is defined as '1'. Such a resistance may perform the function of storing data. The acknowledged memristor manufacturing model is formed by sandwiching a nanoscale anoxic titanium dioxide film and a nanoscale neutral titanium dioxide film between two Pt nanowires, and although the structure is simple, the switching speed is relatively low. Although the research on the memristor has been greatly advanced in recent years, it is also observed that the research on the memristor just starts as a basic circuit element, which is mainly expressed in the following aspects:
(1) in recent years, new memristor materials and memristor systems are reported continuously, but at present, physically realized memristor models are few and relatively single, and a uniform universal model is not available for describing memristor behaviors.
In recent years, physical memristors are proposed for some applications or simulation of some functions, such as high-density nonvolatile memory, Crossbar Latch (cross lattice logic gate) technology, and simulated nerve synapses. Most of the memristors adopt a switch model and a working mechanism similar to those of the HP memristors, the manufacturing process is complex, the cost is high, and the HP memristors do not have generality and universality in researching memristor characteristics, memristor circuit theory, electronic circuit design and the like.
(2) The reported preparation of the physical memristor has high requirements and harsh conditions on raw material selection and preparation process methods, and the preparation of related physical memristor elements is difficult to complete in laboratories or scientific research units with common conditions.
In terms of physical realization of the memristor, in the prior art, the preparation method of the memristor has the main disadvantages and shortcomings that:
(1) the preparation process is complex, the preparation period is long, and the prepared memristor is weak in memristive performance and only suitable for low-frequency signals.
The reason is that the resistance change layer is mostly deposited on the surface of the lower electrode by ceramic materials, the internal structure of the materials is compact, and the number of lattice defects and holes is small.
(2) The prepared memristor is hard and brittle in quality, is easy to break or damage due to collision, bending and the like, and is not a flexible memristor.
In addition, the method also has the problems and disadvantages of relatively strict process conditions and low product rate.
Disclosure of Invention
In order to solve the problems, the invention provides the flexible memristor with the self-repairing capability and the preparation method thereof, the design is reasonable, the defects of the prior art are overcome, and the flexible memristor has a good effect.
In order to achieve the aim 1, the invention adopts the following technical scheme:
the flexible memristor with the self-repairing capability comprises a positive electrode, a negative electrode and an electrolyte solution, wherein a metal thin plate is used as the positive electrode of the memristor, manganese dioxide deposited on Carbon Fiber Paper (CFP) is used as the negative electrode of the memristor, and ZnSO is used for4-MnSO4The weak acidic solution is used as electrolyte solution, and is formed by oxidation/reduction reaction generated on the manganese dioxide film by diffusion of ions in the solution, and the electrolyte solution has the capability of spontaneously generating electrochemical reactionThe structure realizes the change of memristor resistance.
Preferably, the metal used for the positive electrode includes any one of gold Au, silver Ag, copper Cu, platinum Pt, aluminum Al, and zinc Zn.
Preferably, ZnSO4-MnSO4Molar ratio of components of electrolyte solution ZnSO4:MnSO4Y, wherein 0<X≤1，0<Y.ltoreq.1, as one of the preferences, ZnSO4The concentration of the solution can be 2mol/L, MnSO4The concentration of the solution can be selected to be 0.2 mol/L.
Preferably, ZnSO4-MnSO4The electrolyte solution is a weakly acidic solution having a pH of 5.
Preferably, the sealable container is selected from flexible materials such as aluminium plastic film.
In order to achieve the aim 2, the invention adopts the following technical scheme:
a preparation method of a flexible memristor with self-repairing capability comprises the following steps:
step 1: ZnSO is added4And MnSO4Mixing the solutions to obtain weakly acidic solution with a molar ratio of X to Y of 0<X≤1，0<Y is less than or equal to 1, and stirring is carried out for 5-10 minutes to obtain ZnSO4-MnSO4Mixing the solution;
step 2: cutting the metal electrode and the carbon fiber paper into sheets with fixed thickness;
and step 3: cleaning the metal electrode by acetone, absolute ethyl alcohol and deionized water in sequence, and drying for later use after cleaning;
and 4, step 4: the top of the sealable container is the position of a negative electrode of the memristor, the carbon fiber paper is placed at the top of the sealable container, the bottom of the sealable container is the positive electrode of the memristor, and the metal electrode sheet is placed at the bottom of the sealable container to serve as the positive electrode of the memristor;
and 5: ZnSO is added4-MnSO4Filling the mixed solution between two electrodes to prepare a memristor, placing the memristor under a voltage of 1.8V for 8 hours, and under the action of an external power supply, adding Mn in a manganese sulfate solution2+Oxidized to form uniform manganese dioxide, and deposited on the surface of Carbon Fiber Paper (CFP) to form a negative electrode of the memristor;
step 6: applying-1V voltage to two ends of the memristor, and observing and testing the memristor performance of the memristor;
manganese dioxide deposited on carbon fiber paper is Mn in manganese sulfate solution under the action of external power supply2+The memristor is formed by oxidation, if the manganese dioxide thin film is cracked due to bending and the like, the memristor can be self-repaired in the using process, and the size of the manganese dioxide nano-particles after deposition is generally 10nm-50 um. The nano-crystal and porous characteristics of manganese dioxide also provide rich contact interfaces between the electrode and electrolyte, increase the redox reaction space of ions, ensure that the redox reaction on the electrode is carried out more stably, maintain good cycle stability, show good memristive performance and facilitate process control.
When Mn is present in the electrolyte2+When the ion concentration increases to a certain level, Mn dissolved in the electrolyte2+The ions can generate oxidation reaction with the manganese dioxide cathode to generate manganese oxide (MnO)x) The dissolution loss of manganese dioxide is balanced, thereby demonstrating the extremely long cycle life of the memristor. In the process of repeatedly applying positive and negative bias voltages to the memristor, the manganese dioxide negative electrode undergoes a continuous ion insertion process, and good memristive characteristics can be displayed through a voltage-current characteristic curve of the manganese dioxide negative electrode.
The manganese dioxide negative electrode of the memristor can be renewed in the process of electrifying the memristor for use, and if the manganese dioxide film is cracked due to bending and the like, the memristor can realize self-repairing.
Preferably, the sealable container is barrel-shaped or of another type;
preferably, on the basis of ensuring the performance of the memristor, the thicknesses of the metal electrode and the carbon fiber paper are selected within the wide range of 10nm-1mm, so that the process difficulty is reduced, and the yield is improved;
preferably, the memristor can realize flexible packaging and is made into a wearable flexible memristor.
The beneficial and technical effects brought by the invention are as follows:
in the invention, the two electrodes are in interface contact with the electrolyte, so that the required switching current is smaller and the reaction is more stable. The manganese dioxide negative electrode is prepared by taking carbon fiber paper as a cathode current collector and electrodepositing manganese dioxide in situ to prepare the manganese dioxide negative electrode without the adhesive, and the method ensures that the manganese dioxide is tightly contacted with the carbon fiber paper, thereby not using any polymer adhesive or conductive additive, not only increasing the efficiency of ion reaction, but also shortening the preparation process and improving the preparation efficiency. The nanocrystalline and porous structure of manganese dioxide provides a rich electrode contact interface and reduces the diffusion path of ions. The weak acid solution is used as the liquid electrolyte, so that the electrochemical performance of the memristor is greatly improved, the solution is used as the electrolyte, the ion concentration in the solution can be flexibly adjusted to research the performance of the memristor under different conditions, and the memristor performance is verified from multiple aspects.
The preparation method of the memristor is easy to physically realize, simple in preparation process, stable in quality, high in cyclicity, high in ionic conductivity and low in cost, and the prepared liquid memristor can better show the memristor performance, so that a reference is provided for researching a novel memristor.
Drawings
FIG. 1 is a schematic diagram of a flexible memristor with self-repair capability according to the present invention;
Detailed Description
To facilitate understanding and practice of the invention by those of ordinary skill in the art, embodiments of the invention are further described below with reference to the accompanying drawings and specific examples:
as shown in FIG. 1, a flexible memristor with self-repairing capability adopts a metal thin plate as a memristor anode, manganese dioxide deposited on Carbon Fiber Paper (CFP) as a memristor cathode, and ZnSO4-MnSO4The weak acid solution is used as an electrolyte solution, and a structure capable of spontaneously generating electrochemical reaction is formed by oxidation/reduction reaction of ions in the solution on the manganese dioxide film, so that the resistance of the memristor is changed.
Specifically, the metal used for the positive electrode includes any one of gold Au, silver Ag, copper Cu, platinum Pt, aluminum Al, and zinc Zn.
Specifically, ZnSO4-MnSO4Molar ratio of components of electrolyte solution ZnSO4:MnSO4Y, wherein 0<X≤1，0<Y≤1。ZnSO4-MnSO4The electrolyte solution is a weakly acidic solution having a pH of 5.
The present invention will be described in further detail with reference to the following examples:
1. examples 1 to 6, all using ZnSO4-MnSO4The solution is used as an electrolyte, the non-metal negative electrode adopts manganese dioxide deposited on carbon fibers, and the metal positive electrode adopts any one of gold Au, silver Ag, copper Cu, platinum Pt, aluminum Al and zinc Zn, so that the influence of different electrodes on the memristive performance of the liquid memristor is researched.
The molar ratio of the raw materials for preparing the solution and the formula is as follows: ZnSO4:MnSO4＝1:0.1。
2. Examples 7-14, all of which used Zn as the positive metal electrode and electrodeposited manganese dioxide as the negative non-metal electrode, by changing ZnSO4-MnSO4The influence of different electrolyte ratios (different ion concentrations) on the memristive performance of the liquid memristor is researched by the molar ratio of the mixed solution.
The molar ratio of the raw materials for preparing the solution and the formula is as follows: ZnSO4:MnSO4＝X:Y(0≤X≤1，0≤Y≤1)。
The specific embodiment is as follows:
example 1:
step 1: adding a certain amount of ZnSO4And MnSO4Mixing the solutions to prepare a weak acid solution with a molar ratio of 1:0.1, and stirring for 5-10 minutes to obtain a mixed solution.
Step 2: and cutting the metal zinc Zn electrode and the carbon fiber paper into sheets with fixed thickness.
And step 3: and (3) cleaning the metal zinc Zn electrode by acetone, absolute ethyl alcohol and deionized water in sequence, and drying for later use after cleaning.
And 4, step 4: the top of the sealable container is the position of a negative electrode of the memristor, the carbon fiber paper is placed at the top of the sealable container, the bottom of the sealable container is the positive electrode of the memristor, and the metal electrode sheet is placed at the bottom of the sealable container to serve as the positive electrode of the memristor;
and 5: ZnSO is added4-MnSO4The mixed solution was charged between the two electrodes, the memristor was placed at 1.8V for 8 hours, and a manganese dioxide negative electrode was electrodeposited on the carbon fiber paper.
Step 6: and applying-1V voltage to two ends of the memristor, and observing and testing the memristor performance of the memristor.
Example 2
Example 2 the same procedure and method as in example 1 was followed, with the only difference that the metallic zinc Zn electrode in example 1 was replaced by a gold Au electrode.
Example 3
Example 3 the same procedure and method as in example 1 was followed, with the only difference that the metallic zinc Zn electrode in example 1 was replaced by a silver Ag electrode.
Example 4
Example 4 the same procedure and method as in example 1 was followed, with the only difference that the metallic zinc Zn electrode in example 1 was replaced by a copper Cu electrode.
Example 5
Example 5 the same procedure and method as in example 1 was followed, with the only difference that the metallic zinc Zn electrode in example 1 was replaced by a platinum Pt electrode.
Example 6
Example 6 the same procedure and method as in example 1 was followed, with the only difference that the metallic zinc Zn electrode in example 1 was replaced by an aluminum Al electrode.
Example 7
Example 7 the same preparation method and procedure as in example 1 were carried out, with the only difference that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO4:MnSO4＝1:0.2。
Example 8
Example 8 the same procedure and procedure were followed as in example 1,the only difference is that the molar ratio of the formulation composition of the electrolyte solution is adjusted to ZnSO4:MnSO4＝1:0.3。
Example 9
Example 9 the same preparation method and procedure as in example 1 were carried out, with the only difference that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO4:MnSO4＝1:0.4。
Example 10
Example 10 the same preparation method and procedure as in example 1 were carried out, with the only difference that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO4:MnSO4＝1:0.5。
Example 11
Example 11 the same preparation method and procedure as in example 1 were carried out, with the only difference that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO4:MnSO4＝1:0.6。
Example 12
Example 12 the same preparation method and procedure as in example 1 were carried out, with the only difference that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO4:MnSO4＝1:0.7。
Example 13
Example 13 the same preparation method and procedure as in example 1 were carried out, with the only difference that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO4:MnSO4＝1:0.8。
Example 14
Example 14 the same preparation method and procedure as in example 1 were carried out, with the only difference that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO4:MnSO4＝1:0.9。
Example 15
Example 15 the same preparation method and procedure as in example 7 were carried out, with the only difference that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO4:MnSO4＝1:1。
Example 16
Example 16 the same procedure and procedure were followed as in example 1, except thatIs different in that the molar ratio of the formulation composition of the electrolyte solution is adjusted to ZnSO4:MnSO4＝0.1:1。
Example 17
Example 17 the same preparation method and procedure as in example 1 were carried out, with the only difference that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO4:MnSO4＝0.2:1。
Example 18
Example 18 the same preparation method and procedure as in example 1 were carried out, with the only difference that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO4:MnSO4＝0.3:1。
Example 19
Example 19 the same preparation method and procedure as in example 1 were carried out, with the only difference that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO4:MnSO4＝0.4:1。
Example 20
Example 20 the same preparation method and procedure as in example 1 were carried out, with the only difference that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO4:MnSO4＝0.5:1。
Example 21
Example 21 the same preparation method and procedure as in example 1 were carried out, with the only difference that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO4:MnSO4＝0.6:1。
Example 22
Example 22 the same preparation method and procedure as in example 1 were carried out, with the only difference that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO4:MnSO4＝0.7:1。
Example 23
Example 23 the same preparation method and procedure as in example 1 were carried out, with the only difference that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO4:MnSO4＝0.8:1。
Example 24
Example 24 the same procedure and procedure were followed as in example 1, except thatIs different in that the molar ratio of the formulation composition of the electrolyte solution is adjusted to ZnSO4:MnSO4＝0.9:1。
And (3) detection and inspection of the product:
I-V characteristic tests of the finally prepared memristors of the above examples 1-24 show that
I-V characteristic curves of the memristors are all in 8 shapes; and by changing the pressurization size and the pressurization time, the I-V characteristics of the memristor show nonvolatile property, namely memorability, which is peculiar to the memristor.
It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art may make modifications, alterations, additions or substitutions within the spirit and scope of the present invention.
Claims (9)
1. The flexible memristor with self-repairing capability is characterized by comprising a positive electrode, a negative electrode and an electrolyte solution, wherein a metal thin plate is used as the positive electrode, and manganese dioxide (MnO) is deposited on Carbon Fiber Paper (CFP)2) As a negative electrode, ZnSO4-MnSO4The weak acid solution is used as an electrolyte solution, and a structure capable of spontaneously generating electrochemical reaction is formed by oxidation/reduction reaction of ions in the solution on the manganese dioxide film, so that the resistance of the memristor is changed.
2. The flexible memristor with the self-repairing capability of claim 1, wherein the metal adopted by the positive electrode comprises any one of gold Au, silver Ag, copper Cu, platinum Pt, aluminum Al and zinc Zn.
3. The flexible memristor with self-repairing capability according to claim 1, wherein ZnSO4-MnSO4Molar ratio of components of electrolyte solution ZnSO4:MnSO4Y, wherein 0<X≤1，0<Y≤1。
4. According to claimThe flexible memristor with self-repairing capability of claim 3 is characterized in that ZnSO4-MnSO4The electrolyte solution is a weakly acidic solution having a pH of 5.
5. The flexible memristor with self-repairing capability of claim 1, wherein the sealable container is made of flexible aluminum plastic film.
6. A preparation method of the flexible memristor with the self-repairing capability, which is characterized by comprising the following steps:
step 1: ZnSO is added4And MnSO4Mixing the solutions to obtain weakly acidic solution with a molar ratio of X to Y of 0<X≤1，0<Y is less than or equal to 1, and stirring is carried out for 5-10 minutes to obtain ZnSO4-MnSO4Mixing the solution;
step 2: cutting the metal electrode and the carbon fiber paper into sheets with fixed thickness;
and step 3: cleaning the metal electrode by acetone, absolute ethyl alcohol and deionized water in sequence, and drying for later use after cleaning;
and 4, step 4: the top of the sealable container is the position of a negative electrode of the memristor, the carbon fiber paper is placed at the top of the sealable container, the bottom of the sealable container is the positive electrode of the memristor, and the metal electrode sheet is placed at the bottom of the sealable container to serve as the positive electrode of the memristor;
and 5: ZnSO is added4-MnSO4Filling the mixed solution between the two electrodes, placing the memristor under a voltage of 1.8V for 8 hours, and electrodepositing a manganese dioxide negative electrode on the carbon fiber paper;
step 6: and applying-1V voltage to two ends of the memristor, and observing and testing the memristor performance of the memristor.
7. The method for preparing the flexible memristor with the self-repairing capability according to claim 6, wherein the thickness of the thin sheet in the step 2 is 10nm-1 mm.
8. The preparation method of the flexible memristor with the self-repairing capability of claim 6, wherein the memristor can be flexibly packaged to be made into a wearable flexible memristor.
9. The preparation method of the flexible memristor with the self-repairing capability, as claimed in claim 6, is characterized in that the manganese dioxide negative electrode of the memristor can be renewed during the electrifying use of the memristor, and if the manganese dioxide thin film is cracked due to bending and the like, the memristor can realize self-repairing.
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