CN113683885A - Polydopamine film, application thereof, and method for preparing nonvolatile memristor and volatile memristor - Google Patents

Polydopamine film, application thereof, and method for preparing nonvolatile memristor and volatile memristor Download PDF

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CN113683885A
CN113683885A CN202010419989.5A CN202010419989A CN113683885A CN 113683885 A CN113683885 A CN 113683885A CN 202010419989 A CN202010419989 A CN 202010419989A CN 113683885 A CN113683885 A CN 113683885A
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film
gold
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polydopamine
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CN113683885B (en
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于贵
王华平
姜倩晴
蔡乐
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Institute of Chemistry CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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 without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011—Manufacture or treatment of multistable switching devices
    • 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 without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/20—Multistable switching devices, e.g. memristors
    • H10N70/24—Multistable switching devices, e.g. memristors based on migration or redistribution of ionic species, e.g. anions, vacancies
    • H10N70/245—Multistable switching devices, e.g. memristors based on migration or redistribution of ionic species, e.g. anions, vacancies the species being metal cations, e.g. programmable metallization cells
    • 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 without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/841—Electrodes
    • H10N70/8416—Electrodes adapted for supplying ionic species
    • 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 without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/881—Switching materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors

Abstract

The invention relates to the technical field of film materials, and particularly discloses a polydopamine film, application thereof, and a method for preparing a nonvolatile memristor and a volatile memristor. The uniform two-dimensional polydopamine film structure can realize the conversion from an amorphous structure to an ordered structure under the action of an electric field and is accompanied with the change from a high resistance state to a low resistance state. Based on the unique structural characteristic and the inherent abundant hydroxyl and amino groups on the surface of the large-area uniform two-dimensional polydopamine film, the polydopamine film can be applied to a nonvolatile memory and a volatile memory, and has high on-off ratio and good stability.

Description

Polydopamine film, application thereof, and method for preparing nonvolatile memristor and volatile memristor
Technical Field
The invention relates to the technical field of film materials, in particular to a polydopamine film, application thereof, and a method for preparing a nonvolatile memristor and a volatile memristor.
Background
In recent years, memristive devices (also referred to as resistive switching devices) have great application potential in the fields of nonvolatile memories, reconfigurable switches, biomimetic neuromorphic computing, radio frequency switches and the like due to the characteristics of low power consumption, high switching speed, high durability and the like.
In general, memristive devices employ a relatively simple metal/insulator/metal structure, operating primarily under two mechanisms. For example, in an electrochemical metallization memory system, low and high resistance states can be constructed using the formation and dissolution of a metal wire (e.g., Cu or Ag). In addition, in variable valence memory devices, movement of oxygen anions or migration of cations can cause a change in the resistance of the metal oxide material, thereby facilitating resistance switching of these devices.
To date, a variety of organic materials (e.g., complexes of ruthenium with azo aromatic ligands, pyrene with triazoles, two-dimensional imine polymers, etc.) and inorganic materials (e.g., TaOx, TiOx, HfOx, etc.) have been developed to construct memristive devices. Despite the great advances made in this area, the development of nanomaterials with controllable composition, thickness, size and conductivity for use in memristive devices remains of great significance.
With the research on the properties of the nano-materials and the wide application prospect thereof, the exploration of the nano-materials with new composition, structure, size, appearance and performance has important significance. Inspired by the strong adhesion property of marine mussels, Polydopamine (PDA) coatings are considered to be an effective method for modifying and functionalizing almost all material surfaces due to their similar catechol and amine functional groups.
Since its first discovery in 2007 (Science 2007,318(5849), 426-. Therefore, PDA has been applied to various fields including surface modification, biomedical device fabrication, electrochemistry, etc. (J.Am.chem.Soc.2013,135(1), 377-383; adv.Mater.2016,28(7), 1489-1494; Angew.chem.Int.Ed.2013,52(21), 5535-5538). However, the application of the PDA film in the field of memristors has been rarely reported.
At present, PDA film preparation has two modes of solid surface deposition and gas-liquid interface self-assembly. Compared with uneven deposition on the solid surface, the polymerization of dopamine on the air/water interface is a relatively uniform nucleation process, so that the large-area PDA film with controllable thickness and relatively ordered morphology can be prepared. However, the polymerization rate of dopamine on the air/water interface is too fast, so that the formed polydopamine film has the defects of poor continuity and too large thickness, and is not beneficial to the application of the film.
In order to enable the PDA to have wider application, a simple, convenient and effective method is developed to realize the controllable polymerization and preparation of the PDA, and the method has important significance for future research and application.
Disclosure of Invention
The invention aims to overcome the defects of poor continuity, poor smoothness and low thickness controllability of PDA (personal digital assistant) in the prior art, and provides a preparation method and application of a polydopamine film, and a method for preparing a nonvolatile memristor and a volatile memristor.
In order to achieve the above object, a first aspect of the present invention provides a polydopamine film, which is formed by a self-assembly method under a sealed condition, wherein polydopamine polymer chains are on a gas-liquid interface on the surface of a stationary dopamine solution; the thickness of the film is 1-20nm, and the roughness Ra is 0.2-0.5 nm.
The invention provides an application of a polydopamine film in a memristive device, wherein the memristive device comprises a nonvolatile memristor and a volatile memristor.
A third aspect of the invention provides a method of fabricating a non-volatile memristor, comprising: and transferring the polydopamine film to the surface of a silicon dioxide-silicon substrate, and then depositing a gold electrode on the polydopamine film to prepare the nonvolatile memristor.
A fourth aspect of the present invention provides a method of fabricating a volatile memristor, comprising: transferring the polydopamine film to the surface of a silicon dioxide-silicon substrate containing a gold bottom electrode, and then placing the polydopamine film in an oxygen-containing atmosphere for primary drying;
the obtained first dried product is contacted with a silver nitrate water solution, and then the first dried product is placed in an oxygen-containing atmosphere for continuous second drying;
and depositing a silver-gold top electrode on the obtained second dry product to prepare the volatile memristor.
The polydopamine film is formed by controlling the self-assembly on the gas-liquid interface to be in a closed state, the thickness of the polydopamine film is easy to control, the polydopamine film can have extremely small thickness, the minimum thickness reaches 1nm, the polydopamine film has good smoothness, and the roughness Ra of the polydopamine film is 0.2-0.5 nm.
Compared with the method for forming the polydopamine film on the solid-liquid interface and the gas-liquid interface in the prior art, the method has the following advantages that: 1) the uniformity and the continuity are better, and the performance of the device is more favorable; 2) the thickness of the polydopamine film can be controlled to be smaller, particularly, when the continuity of the polydopamine film is ensured, the integration of devices is facilitated, and the prepared devices can be smaller.
The polydopamine film has the characteristic of being converted from a high-resistance state to a low-resistance state under voltage, has high on-off ratio and good working stability when being used for a nonvolatile memristor, and the low-resistance state can be kept without obvious change for at least 12 days.
The polydopamine film has abundant hydroxyl and amino groups on the surface, can reduce silver ions into silver nanoparticles in situ, and can construct a volatile memristor due to migration of the silver nanoparticles, so that repeated storage of data can be realized.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a common photograph of a polydopamine film prepared before transfer; wherein (a) is the polydopamine film prepared in preparation example 1, and (b) is the polydopamine film prepared in preparation example 1 which is entirely transferred to the surface of deionized water.
FIG. 2 is an optical picture of a polydopamine film; wherein (a) is an optical microscope picture of the polydopamine film prepared in preparation example 1 after being transferred to a substrate; (b) is an optical microscope photograph of the polydopamine film prepared in comparative example 1 after being transferred to a substrate.
Fig. 3 is a raman spectrum of the polydopamine film prepared in preparation example 1.
Fig. 4 is an infrared spectrum of the polydopamine film prepared in preparation example 1.
Fig. 5 is an atomic force microscope image of the polydopamine film prepared in preparation example 1.
Fig. 6 is a transmission electron micrograph of the polydopamine film prepared in preparation example 1 after irradiation, in which (a) is a transmission electron micrograph of low resolution and (b) is a transmission electron micrograph of relatively high resolution.
FIG. 7 is a voltage-current plot of a non-volatile memristor prepared using example 1.
Fig. 8 is a stability test graph of the nonvolatile memristor prepared in application example 1.
Fig. 9 is a voltage-current plot of a volatile memristor prepared in application example 2.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a polydopamine film, which is formed by a self-assembly method under a closed condition that a polydopamine high-molecular chain is on a gas-liquid interface on the surface of a static dopamine solution; the thickness of the film is 1-20nm, and the roughness Ra is 0.2-0.5 nm.
The inventor of the invention finds that the polydopamine film formed by self-assembly on the gas-liquid interface on the surface of the closed and static dopamine solution has a more continuous and uniform structure and the minimum thickness can reach 1nm compared with the polydopamine film formed by the solid-liquid interface and the gas-liquid interface in the prior art.
Preferably, the thin film has a thickness of 1 to 10 nm.
In a preferred embodiment of the present invention, the method further comprises: and transferring the polydopamine film formed by the self-assembly of the surface of the dopamine solution, continuously standing the dopamine solution under a closed condition, and self-assembling the polydopamine film on the surface of the dopamine solution again to form the polydopamine film. By adopting the preferred scheme of the invention, the poly-dopamine film can be repeatedly prepared, and the poly-dopamine film can be repeatedly prepared as long as the dopamine solution exists in the container.
The sealing and standing conditions are particularly limited, and the dopamine solution is in a sealed state during standing, and is subjected to oxidative polymerization in the presence of air in a container. Because of the limited oxygen content and the inhibited evaporation of water, oxidative polymerization occurs more slowly, resulting in a more uniform film with less thickness and no significant breakage of large areas of the film. The sealing can be realized by closing and sealing the cover of the container in which the dopamine solution is arranged, or by arranging the container in which the dopamine solution is arranged in a sealed box body, or in other sealing modes. In the present invention, the standing refers to a case where stirring and disturbance are prohibited.
Preferably, the standing time is 0.5-48h, preferably 1-20 h.
Preferably, the standing is carried out without heating (i.e., at room temperature).
Preferably, the self-assembly is carried out in an oxygen-containing atmosphere, more preferably the self-assembly is carried out under air.
Preferably, the dopamine solution is obtained by dissolving dopamine hydrochloride in a Tris-HCl (i.e., Tris-HCl) buffer solution.
The concentration of the dopamine solution is particularly limited in the invention, because too low concentration of the dopamine solution leads to poor continuity of the obtained film, and too high concentration leads to too high film formation speed and poor uniformity. Preferably, the concentration of dopamine hydrochloride in the dopamine solution is 0.1-1 mg/mL.
The invention particularly limits the pH value of the Tris-HCl buffer solution, and the self-assembly reaction becomes slow or even non-reactive when the pH value is too low or too high; preferably, the concentration of Tris-HCl buffer solution is 5-50mM, and the pH value of the Tris-HCl buffer solution is 8-9.
The invention provides a specific implementation method for preparing a polydopamine film, which comprises the following steps:
(1) preparation of Tris-HCl buffer solution: adding Tris (hydroxymethyl) aminomethane into deionized water, and adjusting the pH value of the deionized water with dilute hydrochloric acid to obtain a Tris-HCl buffer solution;
(2) preparation of dopamine solution: dissolving dopamine hydrochloride in the Tris-HCl buffer solution to obtain a dopamine solution;
(3) preparing a polydopamine film: standing the dopamine solution at room temperature, and enabling the dopamine solution to be in a sealed state, and self-assembling the dopamine solution on a gas-liquid interface on the surface of the dopamine solution to form a macroscopic large-area continuous uniform film, namely the polydopamine film; transferring the generated polydopamine film to a substrate by adopting an LB film technology for later use;
(4) repeated preparation of polydopamine film: and then continuously standing the dopamine solution in the closed container, and self-assembling again on the surface of the dopamine solution to form a new polydopamine film.
In the present invention, the LB film technology is used to realize thin film transfer, and is not described herein again for the prior art. The substrate used in the above transfer process may be a common thin film substrate such as a silicon dioxide-silicon substrate, a quartz plate, a copper foil, or a transmissive micro-grid. The thickness of the substrate is not particularly limited, the silicon dioxide-silicon substrate comprises a silicon dioxide layer and a silicon layer positioned below the silicon dioxide layer, and the thickness of the silicon dioxide layer is preferably 250-400 nm; the thickness of the silicon layer is 250-500 nm. Preferably, the thickness of the quartz plate is 1-3 mm. Preferably, the copper foil may have a thickness of 25 μm.
The invention provides an application of a polydopamine film in a memristive device, wherein the memristive device comprises a nonvolatile memristor and a volatile memristor.
Preferably, the polydopamine film is a film as described above. The polydopamine film of the invention can also be used in other memory devices and can be used to fabricate smaller sized electronic devices.
A third aspect of the invention provides a method of fabricating a non-volatile memristor, comprising: and transferring the polydopamine film to the surface of a silicon dioxide-silicon substrate, and then depositing a gold electrode on the polydopamine film to prepare the nonvolatile memristor.
Preferably, the silicon dioxide-silicon substrate comprises a silicon layer I and a silicon dioxide layer I, wherein the silicon layer I is positioned below the silicon dioxide layer I, the thickness of the silicon dioxide layer I is 250-400nm, and the thickness of the silicon layer I is 250-500 μm.
Preferably, the gold electrode comprises a gold layer I, the thickness of the gold layer I is 10-100nm, and the size of the gold electrode is preferably 100 x 100 μm.
Preferably, the nonvolatile memristor is provided with a channel, the length of the channel is 10-100nm, and the width of the channel is 10-100 nm. The channels are well known in the art and will not be described further herein.
A fourth aspect of the present invention provides a method of fabricating a volatile memristor, comprising: transferring the polydopamine film to the surface of a silicon dioxide-silicon substrate containing a gold bottom electrode, and then placing the polydopamine film in an oxygen-containing atmosphere for primary drying;
the obtained first dried product is contacted with a silver nitrate water solution, and then the first dried product is placed in an oxygen-containing atmosphere for continuous second drying;
and depositing a silver-gold top electrode on the obtained second dry product to prepare the volatile memristor.
Preferably, the silicon dioxide-silicon substrate containing the gold bottom electrode comprises a gold layer II, a silicon layer II and a silicon dioxide layer II, wherein the thickness of the gold layer II is 10-100nm, the thickness of the silicon layer II is 250-500 μm, and the thickness of the silicon dioxide layer II is 250-400 nm. The silicon layer II is located below the silicon dioxide layer II, and the gold layer II is located below the silicon layer II.
Preferably, the silver-gold top electrode comprises a silver layer and a gold layer III, the thickness of the silver layer is 10-50nm, the thickness of the gold layer III is 10-50nm, and the size of the electrode is preferably 100 x 100 μm. The silver layer is positioned below the gold layer III.
Preferably, the bottom layer of the gold bottom electrode further comprises a titanium layer I to form a titanium-gold bottom electrode; the bottom layer of the silver-gold top electrode also contains a titanium layer II to form a titanium-silver-gold top electrode; the acting force between the electrode and the substrate or the channel is enhanced.
Preferably, the thickness of the titanium layer I is 1-10nm, and the thickness of the titanium layer II is 1-10 nm.
Preferably, the concentration of silver nitrate in the silver nitrate aqueous solution is 0.1-1 mmol/L.
Preferably, the contact time is 1-10 h.
The present invention will be described in detail below by way of examples. In the following preparation examples and application examples, the raw materials were all commercially available products unless otherwise specified. In the following preparation examples and application examples, the thickness of the polydopamine film was measured by a non-contact atomic force microscope (Bruker).
Preparation example 1
Preparing a polydopamine film:
(1) preparation of Tris-HCl buffer solution: adding the Tris into deionized water, and adjusting the pH value to 8.77 by using dilute hydrochloric acid to obtain a Tris-HCl buffer solution with the Tris concentration of 5 mM;
(2) preparation of dopamine solution: dissolving dopamine hydrochloride in the Tris-HCl buffer solution to obtain a dopamine solution with the concentration of 0.4 mg/mL;
(3) preparing a polydopamine film: under a closed condition, standing the dopamine solution at room temperature for 1.2h, self-assembling the dopamine solution on a gas-liquid interface on the surface of the dopamine solution to form a macroscopic large-area uniform film, namely a polydopamine film, and transferring the generated polydopamine film to a substrate for later use by adopting an LB (Langmuir-blogett) transfer method;
(4) repeated preparation of polydopamine film: and then continuously standing for 1.2h under a closed condition, and self-assembling again on the surface of the dopamine solution to form a new polydopamine film.
The thickness of the prepared polydopamine film is 1.85nm through testing.
The polydopamine film prepared was subjected to the following tests:
1) performing a general photography of the prepared polydopamine film, as shown in fig. 1 (a); transferring the prepared polydopamine film to the surface of deionized water for common shooting, as shown in fig. 1 (b); and transferring the prepared polydopamine film to 1 × 1cm2The silica-silicon substrate was subjected to optical microscope photography, as shown in fig. 2 (a).
And transferring the prepared polydopamine film to 1 × 1cm2Silicon dioxide substrate, raman spectroscopy was performed as shown in fig. 3.
As can be seen from FIG. 1, the present invention enables the preparation of a uniform and continuous large-area accumulation dopamine film with a diameter of up to 60 mm.
As can be seen from fig. 2, the polydopamine film prepared in preparation example 1 of the present invention shows good uniformity and continuity, compared to comparative example 1 described below, whereas the polydopamine film prepared in comparative example 1 is more dispersed and has poor continuity.
As can be seen from fig. 3, the raman spectrum shows sharp D peak, G peak and 2D envelope peak, which preliminarily proves the structure of the polydopamine film.
2) The polydopamine film was transferred to a copper sheet substrate and subjected to infrared spectroscopy, the results of which are shown in fig. 4.
FIG. 4 shows an IR spectrum of polydopamine film prepared at 3000-3700cm-1The expansion vibration peak of O-H, N-H is within 1600cm-1The stretching vibration peak of benzene ring is positioned at-1500 cm-1The peak of bending vibration at N-H. As can be seen from FIGS. 3 and 4, the preparation of this example was successful.
3) Transferring the prepared polydopamine film to 1 × 1cm2Atomic force microscopy tests were performed on the silicon dioxide substrate and the results are shown in fig. 5.
FIG. 5 is an atomic force microscope image showing that the prepared continuous polydopamine film has a thickness of only 1.85nm and has a very flat and uniform surface with a roughness Ra of only 0.25 nm.
4) The polydopamine film was transferred onto a micro-grid substrate, maintained for 40min under electron beam irradiation, and photographed by a transmission electron microscope, and transmission electron micrographs after irradiation are shown in fig. 6(a) and (b).
As can be seen from FIG. 6, the polydopamine film prepared by the invention generates obvious structural change after being irradiated by electron beams, and is converted into a more ordered structure, so that the polydopamine film can be used for preparing electronic devices.
Comparative example 1
This comparative example is illustrative of a polydopamine film formed at a solid-liquid interface in the prior art.
Preparing a polydopamine film:
(1) preparation of Tris-HCl buffer solution: adding the Tris into deionized water, and adjusting the pH value to 8.77 by using dilute hydrochloric acid to obtain a Tris-HCl buffer solution with the Tris concentration of 5 mM;
(2) preparation of dopamine solution: dissolving dopamine hydrochloride in the Tris-HCl buffer solution to obtain a dopamine solution with the concentration of 0.4 mg/mL;
(3) preparing a polydopamine film: mixing 1X 1cm2And (3) soaking the silicon dioxide-silicon substrate in the dopamine solution, stirring the solution at room temperature, taking out the substrate after 1.2h, depositing a polydopamine film on the surface, and drying in the air for later use.
The polydopamine film prepared in this comparative example was photographed by an optical microscope, as shown in fig. 2 (b). Tests show that the thickness of the polydopamine film prepared by the comparative example is far larger than that of the polydopamine film prepared by the example 1, and the roughness of the polydopamine film prepared by the comparative example is far larger than that of the polydopamine film prepared by the example 1.
Comparative example 2
The polydopamine film is prepared by adopting a method in the prior art on a gas-liquid interface under a non-closed condition. Tests show that the thickness of the polydopamine film prepared by the comparative example is far larger than that of the polydopamine film prepared by the example 1, and the roughness of the polydopamine film prepared by the comparative example is far larger than that of the polydopamine film prepared by the example 1.
Preparation examples 2 to 5
The polydopamine film of the present preparation was prepared according to the method of preparation example 1, except that the corresponding parameters in table 1 below were used instead of the parameters of preparation example 1, and the test results are shown in table 1.
TABLE 1
Figure BDA0002496501530000111
As can be seen from Table 1, the thickness of the film can be regulated and controlled by changing the standing time, and the polymerization speed is slow by adopting the method of the invention, so that the thickness of the polydopamine film is less than 10nm even after 6 hours of self-assembly. From example 1 and comparative examples 1-2, it can be seen that the polydopamine film prepared by the method of the present invention has a more controllable and smaller thickness and is flatter.
Application example 1
The application example is used for preparing the nonvolatile memristor.
The polydopamine film obtained in preparation example 1 is transferred to a silicon dioxide-silicon substrate (the thickness is 300nm and 400 microns respectively), and a gold electrode with the thickness of 30nm is deposited on the surface of the polydopamine film, so that the nonvolatile memristor is obtained. The nonvolatile memristor is provided with a channel, wherein the length of the channel is 20nm, and the width of the channel is 20 nm.
The nonvolatile memristors were tested for resistance versus voltage, as shown in FIG. 7. As can be seen from fig. 7, the polydopamine film of the present invention causes the non-volatile memristor to undergo an irreversible resistance transition after a voltage is applied. Due to the application of the forward voltage, the polydopamine film is converted into a more ordered structure, so that the resistance is reduced, and the changed resistance can not be changed along with the removal of the applied voltage or the application of the reverse voltage.
To test the stability of the nonvolatile memristor, the voltage-current curve was again tested after the nonvolatile memristor was left for 12 days, as shown in fig. 8. As can be seen from FIG. 8, after the nonvolatile memristor is placed for 12 days, the resistance does not change significantly, which indicates that the stability of the nonvolatile memristor is good.
Application example 2
The application example is used for preparing the volatile memristor.
Transferring the polydopamine film prepared in preparation example 1 to the surface of a silicon dioxide-silicon substrate (the thickness of the silicon dioxide-silicon substrate is 300nm and 400 microns respectively) with a titanium-gold bottom electrode, wherein the thickness of each titanium-gold layer is 2nm and 30nm respectively, and naturally airing in the air to obtain a first dried product; then, immersing the first dried product into 0.24mmol/L silver nitrate solution for 5 hours to enable the polydopamine film to adsorb and reduce silver ions, and naturally airing in the air to obtain a second dried product; and depositing a titanium-silver-gold top electrode on the surface of the second dried product, wherein the thickness of the three layers in the titanium-silver-gold top electrode is 2nm, 15nm and 15nm in sequence, so that the poly-dopamine film-based asymmetric vertical-structure volatile memristor is prepared.
The volatile memristors were tested for resistance versus voltage, as shown in FIG. 9. As can be seen from fig. 9, due to the reversibility of silver nanoparticle migration, the volatile memristor can realize a reversible change from a high resistance state to a low resistance state. The resistance of the volatile memristor does not change when a forward voltage is applied; however, the application of a negative voltage can cause the resistance of the volatile memristor to be changed from a high-resistance state to a low-resistance state; when the applied voltage is reduced to 0, the low resistance state returns to the high resistance state, so that repeated storage and erasure of data can be performed.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A polydopamine film is characterized in that the film is formed by a self-assembly method under a closed condition, wherein a polydopamine high-molecular chain is on a gas-liquid interface on the surface of a static dopamine solution; the thickness of the film is 1-20nm, and the roughness Ra is 0.2-0.5 nm.
2. The film of claim 1, wherein the method further comprises: after transferring the polydopamine film formed by the self-assembly of the surface of the dopamine solution, continuously standing the dopamine solution under a closed condition, and self-assembling the polydopamine film again on the surface of the dopamine solution to form the polydopamine film;
preferably, the standing time is 0.5-48h, more preferably 1-20 h;
preferably, the resting is carried out without heating;
preferably, the self-assembly is carried out in an oxygen-containing atmosphere, more preferably the self-assembly is carried out under air.
3. The membrane according to claim 1 or 2, wherein the dopamine solution is obtained by dissolving dopamine hydrochloride in Tris-HCl buffer solution;
preferably, the concentration of the dopamine hydrochloride in the dopamine solution is 0.1-1 mg/mL;
preferably, the concentration of Tris-HCl buffer solution is 5-50mM, and the pH value of the Tris-HCl buffer solution is 8-9.
4. The application of a polydopamine film in a memristive device, wherein the memristive device comprises a nonvolatile memristor and a volatile memristor.
5. Use according to claim 4, wherein the polydopamine film is a film according to any one of claims 1 to 3.
6. A method of fabricating a non-volatile memristor, comprising: transferring the polydopamine film of any one of claims 1-3 to the surface of a silica-silicon substrate, and then depositing a gold electrode on the polydopamine film to prepare a nonvolatile memristor.
7. The method as claimed in claim 6, wherein the silicon dioxide-silicon substrate comprises a silicon layer I and a silicon dioxide layer I, the thickness of the silicon dioxide layer I is 250-400nm, and the thickness of the silicon layer I is 250-500 μm;
preferably, the gold electrode comprises a gold layer I, and the thickness of the gold layer I is 10-100 nm;
preferably, the nonvolatile memristor is provided with a channel, the length of the channel is 10-100nm, and the width of the channel is 10-100 nm.
8. A method of fabricating a volatile memristor, comprising: transferring the polydopamine film according to any one of claims 1 to 3 onto the surface of a silicon dioxide-silicon substrate containing a gold bottom electrode, and then placing the polydopamine film in an oxygen-containing atmosphere for primary drying;
the obtained first dried product is contacted with a silver nitrate water solution, and then the first dried product is placed in an oxygen-containing atmosphere for continuous second drying;
and depositing a silver-gold top electrode on the obtained second dry product to prepare the volatile memristor.
9. The method as claimed in claim 8, wherein the silicon dioxide-silicon substrate with the gold bottom electrode comprises a gold layer II, a silicon layer II and a silicon dioxide layer II, wherein the thickness of the gold layer II is 10-100nm, the thickness of the silicon layer II is 250-500 μm, and the thickness of the silicon dioxide layer II is 250-400 nm;
preferably, the silver-gold top electrode comprises a silver layer and a gold layer III, the thickness of the silver layer is 10-50nm, and the thickness of the gold layer III is 10-50 nm;
preferably, the bottom layer of the gold bottom electrode further comprises a titanium layer I to form a titanium-gold bottom electrode; the bottom layer of the silver-gold top electrode also contains a titanium layer II to form a titanium-silver-gold top electrode;
preferably, the thickness of the titanium layer I is 1-10nm, and the thickness of the titanium layer II is 1-10 nm.
10. The method according to claim 8 or 9, wherein the concentration of silver nitrate in the aqueous silver nitrate solution is 0.1-1 mmol/L;
preferably, the contact time is 1-10 h.
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