CN114899312A - Graphene oxide memristor based on laminated structure and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of data storage, and particularly relates to a graphene oxide memristor based on a laminated structure and a preparation method thereof. The graphene oxide memristor based on the laminated structure comprises a conductive substrate layer, a first graphene oxide layer, a pyridinium thin film layer, a second graphene oxide layer and a metal electrode layer which are sequentially arranged. By means of the ingenious design of the laminated structure functional layer, the pyridinium film is used as the buffer layer to be inserted into the graphene oxide film layer, irregular migration of metal ions and disordered growth of conductive filaments are effectively inhibited, stable bidirectional tuning and quick response performance of the graphene oxide memristor are induced, preparation of high-performance artificial synapses is achieved, and the method has high application value in the fields of bionics and neuromorphism calculation.
Description
Technical Field
The invention belongs to the technical field of data storage, and particularly relates to a graphene oxide memristor based on a laminated structure and a preparation method thereof.
Background
The memristor has a great potential in the aspects of realizing high-capacity data storage, rapid transmission, rapid reading and writing and low power consumption due to the simple structure and excellent electrical performance. In addition, the electrical behavior of the memristor can simulate the weight change of biological synapses, so that the memristor has a wide application prospect in the fields of artificial synapses and neural computation. In addition, the memristor is expected to realize the construction of a computational integration computer, can break through the traditional von neumann computer architecture, and greatly improves the computational efficiency of the computer, so that the memristor is considered to be one of strong candidates of a new generation of data storage technology. Currently, many types of materials have been developed for the preparation of memristors, including metal oxides, two-dimensional materials, organic functional materials, perovskites, and the like. Among them, representative two-dimensional graphene oxide materials have attracted much attention due to their excellent physical and electronic properties.
In recent years, various graphene oxide memristors are developed successively and show good resistance change switch storage performance. However, several key problems still exist for further developing high-performance artificial synapses based on graphene oxide memristors and need to be solved. First, many graphene memristors exhibit only abrupt switching and unidirectional modulation, making bidirectional control of the memristor difficult to achieve, as the abrupt switching behavior of the memristor limits the possibility of modulating its multiple conductances. For memristors, good bidirectional modulation and multiple conductance modulation are key to simulating biological synaptic weight changes. Secondly, most of the graphene memristors at present are of an ion migration type, and active metals (such as silver and copper) are generally adopted as electrodes. Although the electrochemical-induced metal ion migration (such as silver ion and copper ion) in the device can simulate the diffusion process of calcium ion in biological neurons, the diffusion rate is high, the thermodynamic stability is low, and uncontrollable migration of metal ions and disordered growth of metal conductive filaments are often caused, so that the stability of the performance of the device is reduced, and even the degradation and the failure of the device are caused. These above problems present a great challenge to achieving high-performance artificial synapses based on graphene memristors. Therefore, an effective strategy for preparing the graphene memristor with stable bidirectional modulation and controllable ion migration is urgently needed.
Disclosure of Invention
The invention aims to solve the problems and provides a graphene oxide memristor based on a laminated structure and a preparation method thereof.
According to the technical scheme, the graphene oxide memristor based on the laminated structure comprises a conductive substrate layer;
the first graphene oxide layer is arranged on one side surface of the conductive substrate layer;
a pyridinium film layer disposed on a surface of the first graphene oxide layer opposite to the conductive substrate layer;
a second graphene oxide layer provided on a surface of the pyridinium thin film layer opposite to the first graphene oxide layer;
and the metal electrode layer is arranged on the surface of one side, opposite to the pyridinium thin film layer, of the second graphene oxide layer.
Furthermore, the conductive substrate layer is made of metal such as indium tin oxide, platinum, gold, copper, aluminum, or other conductive materials.
Further, the structural formula of the pyridinium in the pyridinium thin film layer is as follows:
Furthermore, the metal electrode layer is a metal electrode array, and the material of the metal electrode layer is active metal such as silver, copper and the like.
The invention provides a preparation method of the graphene oxide memristor based on the laminated structure, which comprises the following steps,
s1: coating a graphene oxide solution on the surface of the conductive substrate layer, and drying to form a first graphene oxide layer;
s2: coating a pyridinium solution on the surface of the first graphene oxide layer, and drying to form a pyridinium film layer;
s3: coating a graphene oxide solution on the surface of the pyridinium thin film layer, and drying to form a second graphene oxide layer;
s4: and sputtering a metal electrode on the surface of the second graphene oxide layer to obtain the graphene oxide memristor based on the laminated structure.
The preparation method is simple and high in repeatability, and the obtained graphene oxide memristor structure follows a laminated structure of a conductive substrate, three functional films and an electrode, wherein the three functional films are the graphene oxide/pyridinium oxide/graphene oxide laminated structure.
Further, the graphene oxide solution is prepared by dispersing graphene oxide in water. The specific operation can be as follows: and dispersing graphene oxide in deionized water, and carrying out ultrasonic treatment for 2-6 h.
Furthermore, the pyridine salt solution also comprises a film-forming aid, and the film-forming aid is a water-soluble polymer. The pyridine salt is added to assist the film formation by adding a film-forming assistant.
Preferably, the water-soluble polymer is selected from one or more of polyvinyl alcohol, polyethylene glycol and polyvinylpyrrolidone.
Further, the mass ratio of the pyridinium to the film-forming assistant in the pyridinium solution is 1: 1-3: 1.
Specifically, the preparation method of the pyridine salt solution comprises the following steps: respectively dissolving pyridinium and a film-forming aid in deionized water to prepare a solution, and uniformly mixing a pyridinium water solution and a film-forming aid water solution to prepare the pyridinium solution (a pyridinium-film-forming aid mixed solution, wherein the mass ratio of the pyridinium to the film-forming aid is 1: 1-3: 1).
Further, in the steps S1 and S3, the parameters of the graphene oxide solution coating are: spin-coating for 5-10 s at a rotation speed of 400-600 r/min, and then spin-coating for 15-25 s at a rotation speed of 2000-2500 r/min.
Further, in the step S2, the parameters of the pyridine salt solution coating are as follows: spin-coating for 5-10 s at a rotation speed of 400-600 r/min, and then spin-coating for 15-25 s at a rotation speed of 1000-1500 r/min.
Further, in the steps S1 to S3, the drying conditions are as follows: and (3) drying for 2-8 h under the condition of 60-90 ℃.
Further, in step S4, a magnetron sputtering apparatus is used to sputter a metal electrode layer, and the metal electrode layer is sputtered onto the upper surface of the second graphene oxide layer by a mask plate, and the pressure in the sputtering chamber is not higher than 10 -5 Pa, the sputtering rate is 1-4 nm/min.
The third aspect of the invention provides an application of the graphene oxide memristor based on the laminated structure in the fields of artificial synapses and neuromorphic computing.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the spin-coated graphene oxide shows a micron sheet structure in a film, the average size of the micron sheet is 10-30 microns, but the graphene oxide and the micron sheet are not well connected with each other, so that a large number of irregular grain boundary gaps exist; these irregular grain boundary gaps can lead to random diffusion of ion migration; in contrast, pyridinium exhibits a uniform nanocrystalline grain structure in the film; by inserting the pyridinium layer in the middle of the graphene film, the appearance of the functional film can be obviously improved and irregular crystal boundary gaps can be effectively reduced by means of electrostatic interaction between pyridinium positive ions and graphene oxide surface negative charges, so that random diffusion of metal ions and disordered growth of metal filaments are inhibited, and the performance stability of a device is improved; therefore, the problem that the performance of the graphene memristor is unstable is solved;
2. the pyridinium intermediate layer introduced into the laminated structure of the memristor can effectively serve as a buffer layer, so that the orderly formation of the conductive filaments is controlled in the operation period of a device; with the stable gradual increase of the conductive filament, the gradual tuning of the conductance of the graphene memristor is successfully induced, so that the memristor shows stable and reliable bidirectional modulation characteristics and can simulate the weight change of biological synapse; therefore, the method provides a reliable strategy for preparing the high-performance artificial synapse based on the graphene memristor, and is expected to be applied to further development of a bionic neuromorphic computing system.
Drawings
Fig. 1 is a raman spectrum of graphene oxide according to the present invention;
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) of graphene oxide according to the present invention;
FIG. 3 shows nuclear magnetic hydrogen spectrum of pyridinium salt of the present invention ( 1 HNMR)；
FIG. 4 is a Raman spectrum of a pyridinium salt of the present invention;
FIG. 5 is an X-ray photoelectron spectroscopy (XPS) of a pyridinium salt of the present invention;
fig. 6 is an Atomic Force Microscope (AFM) image of a single graphene oxide layer according to the present invention;
FIG. 7 is an Atomic Force Microscope (AFM) view of a single-layer pyridinium thin film layer of the present invention;
FIG. 8 is an Atomic Force Microscope (AFM) of graphene oxide/pyridinium salt/graphene oxide in a stacked configuration according to the invention;
fig. 9 is a schematic diagram of the molecular structures of graphene oxide (top left) and pyridinium (bottom left) and a schematic diagram of a stacked memristor (right) according to the present invention;
FIG. 10 is an electrical performance test chart of the single-layer graphene oxide memristor according to the present invention;
FIG. 11 is an electrical performance test chart of the single-layer pyridinium memristor of the present invention;
FIG. 12 is an electrical performance test chart of the laminated graphene oxide memristor according to the present invention;
FIG. 13 is an electrical performance test diagram of the laminated graphene oxide memristor under different voltage range scanning;
FIG. 14 is a stability curve test diagram of the laminated graphene oxide memristor according to the present invention;
FIG. 15 is an optical photograph of a laminated graphene oxide memristor of the present disclosure;
FIG. 16 is an electrical performance test chart of a laminated graphene oxide memristor before and after bending;
FIG. 17 is a stability curve test chart of the laminated graphene oxide memristor after 200 times of bending;
FIG. 18 is a pulse test chart of the laminated graphene oxide memristor conductance varying with a constant voltage pulse;
FIG. 19 is a pulse test chart of a laminated graphene oxide memristor simulating synaptic weight change according to the present invention.
Description of reference numerals: 1-a conductive substrate layer, 2-a first graphene oxide layer, 3-a pyridinium thin film layer, 4-a second graphene oxide layer and 5-a metal electrode layer.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Step one, weighing 50mg of graphene oxide, dispersing the graphene oxide in deionized water to prepare a 10mg/mL graphene oxide suspension solution, then carrying out ultrasonic treatment for 2h, and storing for later use;
and step two, dissolving polyvinyl alcohol particles (10mg) in deionized water, heating in a water bath at 80 ℃ by using a magnetic stirrer, and carrying out ultrasonic treatment for 20min after the polyvinyl alcohol particles are completely dissolved to prepare a 10mg/mL polyvinyl alcohol solution. Dissolving pyridinium powder (10mg, and iodide ion as anion) in deionized water to obtain 10mg/mL solution, and performing ultrasonic treatment for 20min after the pyridinium powder is completely dissolved. Uniformly mixing a pyridinium water solution and a polyvinyl alcohol water solution to prepare a pyridinium-polyvinyl alcohol mixed solution (the mass ratio of the pyridinium to the polyvinyl alcohol is 1:1), and filtering the mixed solution by a polytetrafluoroethylene membrane filter with the pore size of 0.22 mu m to prepare the pyridinium-polyvinyl alcohol mixed solution;
step three, preparing a first layer of film: dripping the prepared graphene oxide solution of 10mg/mL on an indium tin oxide conductive substrate, spin-coating by a spin coater, firstly, low-speed 500r/min and lasting for 6s, then high-speed 2000r/min and lasting for 20s, putting the spin-coated film into a vacuum drying oven, and vacuum-drying at 80 ℃ for 2 h;
step four, preparing a second membrane: dropwise adding the prepared pyridinium-polyvinyl alcohol mixed solution on the dried graphene oxide film, spin-coating by a spin coater, firstly performing low-speed drying at 500r/min for 6s, then performing high-speed drying at 1000r/min for 20s, putting the spin-coated film into a vacuum drying oven again, and performing vacuum drying at 80 ℃ for 2 h;
step five, preparing a third layer of film: dropwise adding the prepared 10mg/mL graphene oxide solution on two layers of spin-coated and dried films, spin-coating by a spin coater, firstly performing low-speed 500r/min and lasting for 6s, then performing high-speed 2000r/min and lasting for 20s, spin-coating a layer of graphene oxide film again to form a graphene oxide/pyridinium/graphene oxide laminated structure, putting the graphene oxide/pyridinium/graphene oxide laminated structure into a vacuum drying oven, and performing vacuum drying at 80 ℃ for 2 h;
sixthly, passing a mask plate with a circular pattern (the size of a circular electrode is 0.785 mm) on the surface of the three-layer graphene oxide/pyridinium/graphene oxide film by using a magnetron sputtering instrument 2 ) Sputtering a silver electrode array. The pressure in the sputtering cavity is 10 -6 Pa, the deposition rate of the silver electrode is 3nm/min, and the thickness is 100 nm. Finally obtaining the memristor with the vertical laminated structure, wherein the size of the device is 2 multiplied by 2cm 2 。
Test example
As shown in fig. 1 and 2, the graphene oxide has an accurate structure and very high purity, and meets the requirement of the purity of the material for preparing the memristor.
As shown in FIGS. 3-5, the pyridinium salt has an accurate structure and very high purity, and meets the requirement of the purity of the material for preparing the memristor.
As shown in fig. 6, an individual graphene oxide layer has a micron-scale sheet structure on a microscopic scale, but the continuity between the micron-scale sheets is poor, and a large number of grain boundary gaps exist, which can induce random migration and diffusion of ions in the functional film, so that the morphology of the functional film needs to be modified, thereby inducing controllable migration of ions.
As shown in fig. 7, the pyridinium thin film layer exhibits a uniform and continuous nanocrystalline structure on a microscopic scale, which indicates that the pyridinium can effectively avoid grain boundary gaps and irregular crystalline morphology, and thus can be used as an ideal material for improving the morphology of graphene oxide.
As shown in fig. 8, after the pyridinium is inserted between two layers of graphene oxide as the buffer layer, the morphology of the graphene oxide film is greatly improved, the continuity between the micron sheets is remarkably improved, the irregular grain boundary gap is greatly reduced, and the controllable migration of ions and the ordered growth of metal filaments are ensured.
As shown in fig. 9, the laminated graphene oxide memristor of the present invention includes conductive substrate layers 1 sequentially arranged, and the material of the conductive substrate layers is indium tin oxide; a first graphene oxide layer 2; the pyridine salt thin film layer 3 is made of a mixed layer of pyridine salt and polyvinyl alcohol; a second graphene oxide layer 4; and a metal electrode layer 5 made of silver and distributed in an array.
As shown in fig. 10 (the left side is scanned from top to bottom for the 1 st, 2 nd, 3 rd, 4 th, and 5 th times, and the right side is scanned from bottom to top for the 1 st, 2 nd, 3 rd, 4 th, and 5 th times), the electrical performance of the single-layer graphene oxide memristor is unstable, which is not beneficial to obtaining stable and reliable artificial synapses.
As shown in fig. 11 (the left side is the 1 st, 2 nd, 3 rd, 4 th, and 5 th scans from top to bottom, and the right side is the 1 st, 2 nd, 3 rd, 4 th, and 5 th scans from bottom to top), the electrical property of the single-layer pyridinium memristor is unstable, and the turn-on voltage is large, which is not favorable for practical application.
As shown in fig. 12 (the left side is scanned from top to bottom in the order of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10, and the right side is scanned from bottom to top in the order of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10), through the design of the stacked structure, the electrical property stability of the memristor based on the stacked graphene oxide/pyridinium oxide/graphene oxide is significantly improved, the device conductance shows the tuning characteristic of bidirectional nonlinear increase under the voltage scanning, and the weight change of the biological synapse can be simulated.
As shown in FIG. 13 (the voltages on the left side are-1.0V, -1.5V, -2.0V, -2.5V, -3.0V, -3.5V, -4.0V, -4.5V and-5.0V in sequence from top to bottom, and the voltages on the right side are-1.0V, -1.5V, -2.0V, -2.5V, -3.0V, -3.5V, -4.0V, -4.5V and-5.0V in sequence from bottom to top), the conductance of the device of the present invention still exhibits stable bidirectional nonlinear modulation characteristics under different voltage scans.
As shown in fig. 14, the conductance modulation of the device of the present invention can be maintained for a long time, showing good electrical stability.
As shown in fig. 15, the device of the present invention exhibits excellent flexibility and bendable characteristics, and can be well attached to a nail surface, facilitating implementation of a wearable smart electronic device.
As shown in fig. 16 (1 st, 2 nd, 3 rd, 4 th, 5 th, 6 th, 7 th, 8 th, 9 th and 10 th scans from top to bottom on the left side of each small graph, and 1 st, 2 nd, 3 th, 4 th, 5 th, 6 th, 7 th, 8 th, 9 th and 10 th scans from bottom to top on the right side of each small graph), the device of the present invention can still maintain stable nonlinear tuning characteristics after more than 200 repeated mechanical bends, demonstrating good device flexibility and performance reproducibility.
As shown in fig. 17, the conductance modulation of the device of the present invention can be maintained for a long time after 200 repeated mechanical bendings, showing good performance stability.
As shown in fig. 18, under the continuous constant voltage pulse stimulation, the conductance of the device of the present invention shows the characteristic of nonlinear increment, and shows good electric signal stimulation tuning characteristics.
As shown in FIG. 19, the rate of change of the conductance of the device of the invention gradually increases with the increase of the amplitude of the voltage pulse, and the nonlinear incremental characteristic of the conductance is more obvious, which indicates that the laminated graphene oxide memristor can simulate the weight change of biological synapse through the effective modulation of the conductance. Moreover, the response speed of the device is high, and the device can complete quick response under nanosecond-level voltage pulse stimulation.
In conclusion, the preparation method of the graphene oxide memristor based on the laminated structure is simple, has high repeatability, remarkably improves the performance stability of the device, and presents the characteristic of bidirectional conductance gradual tuning under different continuous voltage sweeps; in addition, the graphene oxide memristor has the characteristics of low working voltage, nanosecond-level quick response and low power consumption; therefore, the method has wide application prospect in the field of artificial synapse and neuromorphic calculation.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. A graphene oxide memristor based on a laminated structure is characterized by comprising
A conductive base layer;
the first graphene oxide layer is arranged on one side surface of the conductive substrate layer;
a pyridinium thin film layer disposed on a surface of the first graphene oxide layer opposite to the conductive substrate layer;
a second graphene oxide layer provided on a surface of the pyridinium thin film layer opposite to the first graphene oxide layer;
and the metal electrode layer is arranged on the surface of one side, opposite to the pyridinium thin film layer, of the second graphene oxide layer.
2. The graphene oxide memristor based on a stacked-layer structure of claim 1, wherein a structural formula of a pyridinium salt in the pyridinium salt thin film layer is as follows:
3. the graphene oxide memristor based on a stacked structure of claim 1, wherein the metal electrode layer is a metal electrode array.
4. The preparation method of the graphene oxide memristor based on the laminated structure is characterized by comprising the following steps,
s1: coating a graphene oxide solution on the surface of the conductive substrate layer, and drying to form a first graphene oxide layer;
s2: coating a pyridinium solution on the surface of the first graphene oxide layer, and drying to form a pyridinium film layer;
s3: coating a graphene oxide solution on the surface of the pyridinium thin film layer, and drying to form a second graphene oxide layer;
s4: and sputtering a metal electrode on the surface of the second graphene oxide layer to obtain the graphene oxide memristor based on the laminated structure.
5. The method of claim 4, wherein the pyridinium solution further comprises a film forming aid, wherein the film forming aid is a water soluble polymer.
6. The preparation method according to claim 5, wherein the mass ratio of the pyridinium to the film-forming aid in the pyridinium solution is 1:1 to 3: 1.
7. The method of claim 4, wherein in the steps S1 and S3, the parameters of the graphene oxide solution coating are as follows: spin-coating for 5-10 s at a rotation speed of 400-600 r/min, and then spin-coating for 15-25 s at a rotation speed of 2000-2500 r/min.
8. The method of claim 4, wherein in step S2, the pyridine salt solution is applied with the parameters: spin-coating for 5-10 s at a rotation speed of 400-600 r/min, and then spin-coating for 15-25 s at a rotation speed of 1000-1500 r/min.
9. The method of claim 4, wherein the drying conditions in steps S1-S3 are as follows: and (3) drying for 2-8 h under the condition of 60-90 ℃.
10. The application of the graphene oxide memristor based on the laminated structure in the fields of artificial synapses and neuromorphic computing is disclosed in any one of claims 1-3.
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