CN112687794B - Flexible memristor with self-repairing capability and preparation method - Google Patents
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
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Abstract
The invention provides a flexible memristor with self-repairing capability and a preparation method thereof, wherein a metal sheet is used as a positive electrode of the memristor, manganese dioxide is deposited on Carbon Fiber Paper (CFP) as a negative electrode of the memristor, and ZnSO is used 4 ‑MnSO 4 The weak acid solution is used as electrolyte solution, and oxidation/reduction reaction which occurs on the manganese dioxide film by virtue of diffusion of ions in the solution forms a structure capable of spontaneously generating electrochemical reaction, so that the change of the memristor resistance is realized. The memristive performance is realized by adopting the liquid electrolyte as the medium layer and the film layer in which oxidation/reduction reaction is carried out between the liquid electrolyte and the negative electrode, so that the reaction efficiency is increased by utilizing interface reaction, the ion concentration can be regulated according to different requirements, and further the adjustment of the memristive performance is realized. The invention provides the preparation method of the liquid flexible memristor, which is easy to physically realize, simple in preparation process, stable in quality, high in circularity, low in cost and high in production efficiency.
Description
Technical Field
The invention relates to the application fields of micro-nano electronic devices and nonlinear circuits, in particular to a flexible memristor with self-repairing capability and a preparation method thereof.
Background
Memristors (memristors) are the fourth passive circuit element after the secondary resistance, capacitance and inductance enter the mainstream electronics field, and are one passive circuit element related to magnetic flux and charge. As early as 1971, international nonlinear circuits and cellular neural network theory predecessor, leon Chua, theoretically predicted the existence of memristors based on the logical integrity of circuit theory. In 2008, the hewlett packard laboratory has constructed memristor prototype devices for the first time experimentally, confirming that Leon Chua's theory about memristors has attracted strong attention worldwide. Memristors have novel nonlinear electrical properties, and have the characteristics of high density, small size, low power consumption, non-volatility and the like, and are considered as one of ideal schemes for developing a next-generation novel non-volatile storage technology. Therefore, the method becomes a research hot spot in the fields of information, materials and the like. In addition, the memristor has high similarity between the resistance behavior and the organism nerve plasticity, so that the memristor has potential in the aspects of developing nerve synapse bionic devices, nerve morphology computers and the like.
The existing memristor has a structure that a laboratory researcher of Hewlett-packard corporation clamps a nano-scale double-layer titanium dioxide semiconductor film between two nanowires made of Pt in a published paper of J.Nature published in 5 of 2008, and has a sandwich structure. 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 a high resistance value is defined as "0", a low resistance value is defined as "1". Such a resistor may perform the function of storing data. The acknowledged memristor manufacturing model is composed of a nano-level anoxic titanium dioxide film and a neutral titanium dioxide film which are sandwiched between two Pt nanowires, and the memristor manufacturing model has a simple structure but relatively low switching speed. Despite the recent great progress in memristor research, we also see that, as a basic circuit element, memristor research has just started, and mainly appears in the following aspects:
(1) In recent years, new memristive materials and memristive systems are continuously reported, but the memristor models which are physically realized at present are few and relatively single, and no unified universal model is used for describing the memristor behaviors.
The physical memristors reported in recent years are mostly proposed for some kind of application or simulation of some function, such as high-density nonvolatile memory, crossbar Latch (cross lattice logic gate) technology, and simulation of nerve synapses. Most of the memristors adopt a similar switch model and working mechanism as the HP memristors, have complex manufacturing process and high cost, and have no generality and universality for researching the characteristics of the memristors, the memristor circuit theory, the 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 the related physical memristor element is difficult to be completed by a laboratory or scientific research unit under the general conditions.
In the prior art, the preparation method of the memristor has the following main defects:
(1) The preparation process is complex, the preparation period is long, and the prepared memristor has weak memristance and is 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 material is compact, and the number of lattice defects and holes is small.
(2) The manufactured memristor is hard and brittle, is easy to crack or damage due to collision, bending and the like, and is not a flexible memristor.
In addition, the problems and the disadvantages of relatively harsh process conditions and low product rate exist.
Disclosure of Invention
In order to solve the problems, the invention provides the flexible memristor with self-repairing capability and the preparation method thereof, which have reasonable design, overcome the defects of the prior art and have good effects.
In order to achieve the purpose 1, the invention adopts the following technical scheme:
a flexible memristor with self-repairing capability comprises an anode, a cathode and electrolyte solution, wherein a metal sheet is used as the anode of the memristor, manganese dioxide is deposited on Carbon Fiber Paper (CFP) as the cathode of the memristor, and ZnSO is used as the cathode of the memristor 4 -MnSO 4 The weak acid solution is used as electrolyte solution, and oxidation/reduction reaction which occurs on the manganese dioxide film by virtue of diffusion of ions in the solution forms a structure capable of spontaneously generating electrochemical reaction, so that the change of the memristor resistance is realized.
Preferably, the metal used for the positive electrode includes any one of gold Au, silver Ag, copper Cu, platinum Pt, aluminum Al, zinc Zn.
Preferably, znSO 4 -MnSO 4 Electrolyte solution composition molar ratio ZnSO 4 :MnSO 4 X: Y, wherein 0<X≤1，0<Y.ltoreq.1, as one of the preferred, znSO 4 The concentration of the solution can be selected to be 2mol/L, mnSO 4 The concentration of the solution can be selected to be 0.2mol/L.
Preferably, znSO 4 -MnSO 4 The electrolyte solution is a weak acid solution with a pH value of 5.
Preferably, the sealable container is of a flexible material such as an aluminium plastic film.
In order to achieve the purpose 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 added to 4 And MnSO 4 Mixing the solutions to prepare a weakly acidic solution with a molar ratio of X to Y, wherein 0<X≤1，0<Y is less than or equal to 1, and the ZnSO is obtained after stirring for 5 to 10 minutes 4 -MnSO 4 Mixing the solutions;
step 2: cutting the metal electrode and the carbon fiber paper into slices with fixed thickness;
step 3: sequentially cleaning the metal electrode by acetone, absolute ethyl alcohol and deionized water, and drying for later use after cleaning;
step 4: the top of the sealable container is the anode position of the memristor, carbon fiber paper is arranged at the top of the sealable container, the bottom of the sealable container is the anode of the memristor, and a metal electrode sheet is arranged at the bottom of the sealable container and is used as the anode of the memristor;
step 5: znSO is added to 4 -MnSO 4 The mixed solution is filled between two electrodes to prepare a memristor, the memristor is placed under the voltage of 1.8V for 8 hours, and Mn in the manganese sulfate solution is added under the action of an external power supply 2+ Oxidized to form uniform manganese dioxide, and deposited on the surface of Carbon Fiber Paper (CFP) to form a memristor negative electrode;
step 6: applying-1V voltage to two ends of the memristor, and observing and testing memristor performance;
manganese dioxide deposited on the carbon fiber paper is Mn in manganese sulfate solution under the action of an external power supply 2+ Is oxidized to form, if the manganese dioxide film is broken due to bending and the like, the memristor can be self-repaired in the use process, and the size of the deposited manganese dioxide nano particles is generally 10nm-50um. The nano crystal and porous characteristic of manganese dioxide also provide rich contact interface between the electrode and electrolyte, increase the redox reaction space of ions, make the redox reaction on the electrode more stably proceed, maintain good cycling stability, exhibit good memristance, and facilitateIn process control.
Mn in the electrolyte 2+ When the ion concentration is increased to a certain level, mn is dissolved in the electrolyte 2+ The ions can be oxidized with the manganese dioxide cathode to produce manganese oxide (MnO) x ) The dissolution loss of manganese dioxide is balanced, thus 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 is subjected to a continuous ion insertion process, and good memristor characteristics can be shown through a volt-ampere characteristic curve of the manganese dioxide negative electrode.
The manganese dioxide negative electrode of the memristor can be updated in the power-on use process of the memristor, and if the manganese dioxide film breaks due to bending and other reasons, the memristor can be self-repaired.
Preferably, the sealable container is in the form of a tub or other 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 a wide range of 10nm-1mm, so that the process difficulty is reduced, and the yield is improved;
preferably, the memristor can be flexibly packaged, and is manufactured into a wearable flexible memristor.
The invention has the beneficial technical effects that:
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. In the manganese dioxide negative electrode, carbon fiber paper is used as a cathode current collector, and the manganese dioxide negative electrode without the binder is prepared by in-situ electrodeposition of manganese dioxide. 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 adopted as the liquid electrolyte, so that the electrochemical performance of the memristor is greatly improved, and the ionic concentration in the solution can be flexibly regulated to study the performance of the memristor under different conditions by adopting the solution as the electrolyte, so that 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 circularity, high in ionic conductivity and low in cost, and the prepared liquid memristor can better exhibit 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-repairing capability in accordance with the present disclosure;
Detailed Description
In order to facilitate an understanding and practice of the invention by those of ordinary skill in the art, a detailed description of the invention is provided below with reference to the drawings and examples:
as shown in FIG. 1, a flexible memristor with self-repairing capability is provided, wherein a metal sheet is used as a positive electrode of the memristor, manganese dioxide is deposited on Carbon Fiber Paper (CFP) as a negative electrode of the memristor, and ZnSO is used for preparing the memristor 4 -MnSO 4 The weak acid solution is used as electrolyte solution, and oxidation/reduction reaction which occurs on the manganese dioxide film by virtue of diffusion of ions in the solution forms a structure capable of spontaneously generating electrochemical reaction, so that the change of the memristor resistance is realized.
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, znSO 4 -MnSO 4 Electrolyte solution composition molar ratio ZnSO 4 :MnSO 4 X: Y, wherein 0<X≤1，0<Y≤1。ZnSO 4 -MnSO 4 The electrolyte solution is a weak acid solution with a pH value of 5.
The invention is further described in detail below with reference to examples:
1. examples 1 to 6 all employ ZnSO 4 -MnSO 4 The solution is used as electrolyte, the non-metal negative electrode adopts manganese dioxide deposited on carbon fiber, the metal positive electrode adopts any one of gold Au, silver Ag, copper Cu, platinum Pt, aluminum Al and zinc Zn for grindingThe influence of different electrodes on the memristance performance of the liquid memristor is studied.
The raw materials and the formula of the preparation solution have the following molar ratio: znSO (ZnSO) 4 :MnSO 4 ＝1:0.1。
2. Examples 7 to 14, all of which used Zn as the metal positive electrode and manganese dioxide after electrodeposition as the non-metal negative electrode, were prepared by changing ZnSO 4 -MnSO 4 The molar ratio of the mixed solution is used for researching the influence of different electrolyte ratios (different ion concentrations) on the memristance performance of the liquid memristor.
The raw materials and the formula of the preparation solution have the following molar ratio: znSO (ZnSO) 4 :MnSO 4 ＝X:Y(0≤X≤1，0≤Y≤1)。
Specific examples are as follows:
example 1:
step 1: to a certain amount of ZnSO 4 And MnSO 4 The solution is mixed to prepare weak acid solution with the molar ratio of 1:0.1, and the mixed solution is obtained after stirring for 5-10 minutes.
Step 2: the metallic zinc Zn electrode and the carbon fiber paper are cut into slices with fixed thickness.
Step 3: and cleaning the metal zinc Zn electrode by acetone, absolute ethyl alcohol and deionized water in sequence, and drying for standby after cleaning.
Step 4: the top of the sealable container is the anode position of the memristor, carbon fiber paper is arranged at the top of the sealable container, the bottom of the sealable container is the anode of the memristor, and a metal electrode sheet is arranged at the bottom of the sealable container and is used as the anode of the memristor;
step 5: znSO is added to 4 -MnSO 4 The mixed solution was charged between the two electrodes, the memristor was placed at a voltage of 1.8V for 8 hours, and a manganese dioxide negative electrode was electrodeposited on carbon fiber paper.
Step 6: and applying a voltage of-1 to 1V to two ends of the memristor, and observing and testing the memristor performance.
Example 2
Example 2 the same procedure and method as in example 1 was followed, except that the metallic zinc Zn electrode in example 1 was replaced with a gold Au electrode.
Example 3
Example 3 the same procedure and method as in example 1 was followed, except that the metallic zinc Zn electrode in example 1 was replaced with a silver Ag electrode.
Example 4
Example 4 the same procedure and method as in example 1 was followed, except that the metallic zinc Zn electrode in example 1 was replaced with a copper Cu electrode.
Example 5
Example 5 the same procedure and method was used as in example 1, except that the metallic zinc Zn electrode in example 1 was replaced with a platinum Pt electrode.
Example 6
Example 6 the same procedure and method as in example 1 was followed, except that the metallic zinc Zn electrode in example 1 was replaced with an aluminum Al electrode.
Example 7
Example 7 the same preparation and procedure as in example 1, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝1:0.2。
Example 8
Example 8 the same preparation and procedure as in example 1, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝1:0.3。
Example 9
Example 9 the same preparation and procedure as in example 1, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝1:0.4。
Example 10
Example 10 the same preparation and procedure as in example 1, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝1:0.5。
Example 11
Example 11 and example 1 preparation methods andthe steps are the same, the only difference being that the molar ratio of the formulation composition of the electrolyte solution is adjusted to ZnSO 4 :MnSO 4 ＝1:0.6。
Example 12
Example 12 the same preparation and procedure as in example 1, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝1:0.7。
Example 13
Example 13 the same preparation and procedure as in example 1, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝1:0.8。
Example 14
Example 14 the same preparation and procedure as in example 1, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝1:0.9。
Example 15
Example 15 the same preparation and procedure as in example 7, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝1:1。
Example 16
Example 16 the same preparation and procedure as in example 1, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝0.1:1。
Example 17
Example 17 the same preparation and procedure as in example 1, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝0.2:1。
Example 18
Example 18 the same preparation and procedure as in example 1, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝0.3:1。
Example 19
The preparation methods and procedures of example 19 and example 1The steps are the same, the only difference is that the mole ratio of the formulation composition of the electrolyte solution is adjusted to ZnSO 4 :MnSO 4 ＝0.4:1。
Example 20
Example 20 the same preparation and procedure as in example 1, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝0.5:1。
Example 21
Example 21 the same preparation and procedure as in example 1, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝0.6:1。
Example 22
Example 22 the same preparation and procedure as in example 1, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝0.7:1。
Example 23
Example 23 the same preparation and procedure as in example 1, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝0.8:1。
Example 24
Example 24 the same preparation and procedure as in example 1, the only difference being that the molar ratio of the formulation composition of the electrolyte solution was adjusted to ZnSO 4 :MnSO 4 ＝0.9:1。
Detecting and checking products:
the memristors finally prepared in examples 1-24 were subjected to I-V characteristic test, and the results show that the ratio of the characteristics is
The I-V characteristic curves of the memristors all show an 8 shape; and by varying the magnitude and duration of the pressurization, the I-V characteristics thereof exhibit non-volatility, i.e., memory, characteristic of memristors.
It should be understood that the above description is not intended to limit the invention to the particular embodiments disclosed, but to limit the invention to the particular embodiments disclosed, and that the invention is not limited to the particular embodiments disclosed, but is intended to cover modifications, adaptations, additions and alternatives falling within the spirit and scope of the invention.
Claims (8)
1. A preparation method of a flexible memristor with self-repairing capability is characterized in that the flexible memristor comprises an anode, a cathode and electrolyte solution, a metal sheet is used as the anode, and manganese dioxide (MnO) is deposited on Carbon Fiber Paper (CFP) 2 ) As a negative electrode, znSO 4 -MnSO 4 The weak acid solution is used as electrolyte solution, and oxidation/reduction reaction which occurs on the manganese dioxide film by virtue of diffusion of ions in the solution forms a structure capable of spontaneously generating electrochemical reaction, so that the change of the resistance of the memristor is realized;
the preparation method comprises the following steps:
step 1: znSO is added to 4 And MnSO 4 Mixing the solutions to prepare a weakly acidic solution with a molar ratio of X to Y, wherein 0<X≤1，0<Y is less than or equal to 1, and the ZnSO is obtained after stirring for 5 to 10 minutes 4 -MnSO 4 Mixing the solutions;
step 2: cutting the metal electrode and the carbon fiber paper into slices with fixed thickness;
step 3: sequentially cleaning the metal electrode by acetone, absolute ethyl alcohol and deionized water, and drying for later use after cleaning;
step 4: the top of the sealable container is the anode position of the memristor, carbon fiber paper is arranged at the top of the sealable container, the bottom of the sealable container is the anode of the memristor, and a metal electrode sheet is arranged at the bottom of the sealable container and is used as the anode of the memristor;
step 5: znSO is added to 4 -MnSO 4 Filling the mixed solution between two electrodes, placing the memristor at a voltage of 1.8V for 8 hours, and electrodepositing a manganese dioxide negative electrode on carbon fiber paper;
step 6: and applying a voltage of-1 to 1V to two ends of the memristor, and observing and testing the memristor performance.
2. The method for manufacturing the flexible memristor with self-repairing capability according to 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 method for manufacturing the flexible memristor with self-repairing capability as claimed in claim 1, wherein the ZnSO is 4 -MnSO 4 Electrolyte solution composition molar ratio ZnSO 4 :MnSO 4 X: Y, wherein 0<X≤1，0<Y≤1。
4. The method for manufacturing the flexible memristor with self-repairing capability as claimed in claim 3, wherein the ZnSO is 4 -MnSO 4 The electrolyte solution is a weak acid solution with a pH value of 5.
5. The method for manufacturing the flexible memristor with self-repairing capability of claim 1, wherein the sealable container is made of a flexible material aluminum plastic film.
6. The method for manufacturing the flexible memristor with self-repairing capability according to claim 1, wherein the thickness of the thin sheet in the step 2 is 10nm-1mm.
7. The method for manufacturing the flexible memristor with self-repairing capability according to claim 1, wherein the memristor can be flexibly packaged to manufacture the wearable flexible memristor.
8. The method for manufacturing the flexible memristor with self-repairing capability according to claim 1, wherein the manganese dioxide negative electrode of the memristor can be updated in the power-on use process of the memristor, and if the manganese dioxide film breaks due to bending, the memristor can realize self-repairing.
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