CN110317309A - Memristor and preparation method thereof based on two-dimensional polymer film - Google Patents

Memristor and preparation method thereof based on two-dimensional polymer film Download PDF

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CN110317309A
CN110317309A CN201810278806.5A CN201810278806A CN110317309A CN 110317309 A CN110317309 A CN 110317309A CN 201810278806 A CN201810278806 A CN 201810278806A CN 110317309 A CN110317309 A CN 110317309A
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polymer film
dimensional polymer
fragrance
aldehyde
memristor
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CN110317309B (en
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雷圣宾
刘洁
杨方旭
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Tianjin University
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Tianjin University
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/06Amines
    • C08G12/08Amines aromatic
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/20Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08J2361/22Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds

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Abstract

The invention discloses a kind of memristor and preparation method thereof based on two-dimensional polymer film, preparation method, the following steps are included: being added dropwise the more aldehyde mixed solutions of fragrance on the liquid level of aromatic multi-amine mixed solution, the aromatics organic solvent B volatilization placed at 20~25 DEG C of room temperature into the more aldehyde mixed solutions of fragrance finishes, and two-dimensional polymer film is obtained on liquid level.The present invention prepares covalently organic two-dimentional polymer thin film using the more aldehyde of fragrance and aromatic multi-amine as reaction monomers for the first time, provides the growth conditions for preparing covalently organic two-dimensional polymer.The preparation method simple economy, the instrument of high-end precision is not needed, the uniform two-dimensional polymer film of large area can be obtained without providing high-energy, and the adjusting to two-dimensional polymer film thickness is reached by the adjusting to amount of monomer, be suitble to the demand of actual production.

Description

Memristor and preparation method thereof based on two-dimensional polymer film
Technical field
The invention belongs to organic two-dimensional material technical fields, relate in particular to a kind of recalling based on two-dimensional polymer film Hinder device and preparation method thereof.
Background technique
The lateral dimension of two-dimensional material is greater than 100nm or even several microns of even greater laminated structures, but thickness is only single Atom or several atomic thickness (usually less than 5 nanometers) are a kind of high score of the inside with region repetitive unit, periodic structure Sub- material.In two-dimensional material, electronics is limited in two dimensions, to obtain unprecedented physics, electronics and chemistry Property.The two-dimensional material being originally found is the graphene being stripped out from graphite.Graphene is as a kind of monoatomic layer thickness Two-dimensional material, be by sp2The hexagonal honeycomb shape lattice of the carbon atom composition of hydridization is constituted, the big π formed based on this structure Conjugated system is with excellent electron-transport, optics, machinery and heating conduction.The discovery of these excellent properties of graphene, Researchers are evoked from atom or the interest of molecular level design and rational and synthesizing new two-dimension polymer.
Further exploration after study, it was found that the covalent organic grid material (2D COFs) of two dimension.This material by Organic structure ele is with the New Two Dimensional material made of covalent linkage, with periodic structure and single structure element thickness. The monomer that the material is made of C, H, O, N these " light elements " is formed highly stable by covalent bond stronger between atom Porosity nano material.Therefore can be reached by the adjusting to monomer type and position to two-dimensional polymer function The regulation of energy.Similar with graphene, traditional two-dimensional polymer is to remove covalent organic frame using the method for " from top to bottom " Material (COF) obtains.Due to the organic size of grid framework material (COFs) of two dimension itself, greatly limit monatomic The area of thickness degree two dimension monocrystal material, so that two-dimensional material be made to be difficult to meet the requirement of nano electron device.And another " from bottom to top " method is also often used in the preparation of two-dimensional material.This method is first by monomer deposition appropriate Then substrate material surface gives certain environmental stimuli, prepare two-dimensional polymer by surface reaction.It is this to be made on interface The two dimension that the method for standby two-dimensional material can make full use of the catalytic activity of substrate and the effect of Van der Waals extension to prepare single layer is poly- Object is closed, and is possible to obtain the monolayer material of large area.But this method generally requires some exacting terms, such as high Temperature, ultra-high vacuum environment etc. can just promote the generation of reaction.In addition to this, there is hardly possiblies to turn for the two-dimensional material that this method obtains The problem of shifting.Whether the two-dimensional material of method preparation " from top to bottom " or " from bottom to top ", in size and properties All it is difficult meet the needs of practical application.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of memristors based on two-dimensional polymer film Device, the preparation method of the two-dimensional polymer film are based on interface method, ultra-thin can closely prepare in atmospheric environment at room temperature Two-dimensional polymer film passes through concentration and the mole (ratio of fragrance more aldehyde and aromatic multi-amine of change monomer during the preparation process Example) method the two-dimensional polymer film of different-thickness can be obtained.The two-dimensional polymer that preparation method obtains through the invention Film, which can according to need, to be transferred in any required substrate, and the electronic device (memristor) for constructing different structure is conducive to.
The purpose of the present invention is what is be achieved by following technical proposals.
A kind of preparation method of two-dimensional polymer film, comprising the following steps:
The more aldehyde mixed solutions of fragrance are added dropwise on the liquid level of aromatic multi-amine mixed solution, are placed at 20~25 DEG C of room temperature It is finished to the aromatics organic solvent B volatilization in the more aldehyde mixed solutions of the fragrance, two-dimensional polymer film is obtained on liquid level, Wherein,
The more aldehyde of fragrance in the more aldehyde mixed solutions of fragrance and the aromatic multi-amine in the aromatic multi-amine mixed solution The ratio (0.0015~0.005) of the amount of substance: 0.01389;
The configuration method of the aromatic multi-amine mixed solution are as follows: aromatic multi-amine is evenly distributed in organic solvent A, is obtained Deionized water is added in the solution A and uniformly mixes, obtains the aromatic multi-amine mixed solution of light brown for solution A, wherein The concentration of aromatic multi-amine is 0.185~4.63mmol/mL in the solution A, and the organic solvent A is aprotic and mutual with water Molten organic reagent;
The configuration method of the more aldehyde mixed solutions of fragrance are as follows: the more aldehyde of fragrance are evenly distributed on aromatics organic solvent B In, solution B is obtained, organic acid is added in the solution B, obtains the more aldehyde mixed solutions of fragrance, wherein the aromatics are organic The ratio of the amount number of the substance of the volume parts of solvent B and the more aldehyde of fragrance is (0.5~1): (0.0008~0.01), described The volume of organic acid is the 0.7~1.5% of the volume of the solution B;
The organic acid is acetic acid, trifluoroacetic acid or trifluoromethanesulfonic acid;
Aromatics organic solvent B is chlorobenzene, dichloro-benzenes or toluene.
In the above-mentioned technical solutions, the organic solvent A is n,N-Dimethylformamide, n,N-dimethylacetamide or two Methyl sulfoxide.
In the above-mentioned technical solutions, aromatics organic solvent B of the placement into the more aldehyde mixed solutions of the fragrance is waved Distributing the complete time is at least 24 hours.
In the above-mentioned technical solutions, in the aromatic multi-amine mixed solution, the volume parts of the deionized water and institute The ratio for stating the amount number of the substance of aromatic multi-amine is 1:(0.005~0.03).
In the above-mentioned technical solutions, the unit of the volume parts is mL, and the unit of a mass fraction is Mg, the unit of the amount number of a substance are mmol.
In the above-mentioned technical solutions, the more aldehyde of fragrance include two or 2 or more aldehyde radicals.
In the above-mentioned technical solutions, the aromatic multi-amine includes two or 2 or more amidos.
In the above-mentioned technical solutions, the deionized water is ultrapure water, and resistivity is 18.2M Ω ﹒ cm.
The two-dimensional polymer film that above-mentioned preparation method obtains.
In the above-mentioned technical solutions, the two-dimensional polymer film with a thickness of 2~80nm.
The memristor that above-mentioned two-dimensional polymer film is obtained as active layer.
In the above-mentioned technical solutions, the memristor is from top to bottom successively are as follows: active electrode, two-dimensional polymer film and lazy Property electrode, the active electrode be aluminium layer, layers of copper or silver layer;The inert electrode is ITO conductive glass layer, layer gold or platinum layer.
In the above-mentioned technical solutions, the active electrode with a thickness of 10~200nm.
The preparation method of above-mentioned memristor, comprising the following steps:
A) the two-dimensional polymer film is transferred to the upper surface of inert electrode, in a vacuum drying oven in 15~40 DEG C 2~10h of lower vacuum drying;
B) active electrode is deposited on the two-dimensional polymer film.
In the step b), when the active electrode is silver layer, method that the silver layer is deposited are as follows: use copper mesh as Mask plate is attached to the upper surface of the two-dimensional polymer film, withRate deposition thickness be 20~100nm silver Layer, the copper mesh is removed after deposition, completes vapor deposition silver layer.
In the above-mentioned technical solutions, the mesh number of the copper mesh is 200~300 mesh.
Application of the above-mentioned two-dimensional polymer film as active layer in memristor.
Compared with the prior art, two-dimensional polymer film of the invention has the beneficial effect that
1, it is thin to prepare covalently organic two dimension polymerization using the more aldehyde of fragrance and aromatic multi-amine as reaction monomers for the first time by the present invention Film provides the growth conditions for preparing covalently organic two-dimensional polymer.The preparation method simple economy does not need high-end precision Instrument can be obtained the uniform two-dimensional polymer film of large area without providing high-energy, and pass through the adjusting to amount of monomer Reach the adjusting to two-dimensional polymer film thickness, is suitble to the demand of actual production.
2, the present invention proposes to prepare covalently organic two-dimensional polymer film at water-air interface using solution epitaxy, together When the characteristics of being connected by two kinds of monomer covalents, uniform cavernous structure can not only be provided, while also making the material a variety of Stable presence in organic solvent and water.Pass through the film that the methods of spin coating, droplet casting obtain compared to one-dimensional Polymers, which removes Have outside uniform cavernous structure, also there is good solvent resistance, expanded the application places of material.
3, the present invention proposes that preparing covalently organic two-dimensional polymer film at water-air interface using solution epitaxy is presented Unformed state out, the characteristics of making the two-dimensional polymer film show flexible self-supporting.
4, the present invention is provided for the first time using two-dimensional polymer film as the memristor of functional layer, by the porous knot of the material Structure prepares the memristor based on conductive filament principle using active electrode.What it is due to two-dimensional polymer film of the present invention is in gas-liquid It is prepared on interface, so very convenient be transferred in any substrate, other materials are by inorganic vapor deposition, spin coating etc. Method is transferred in substrate, our method has convenient and easy-operating advantage by comparison, and can be transferred to institute In any substrate needed.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of memristor of the invention;
Fig. 2 be two-dimensional polymer film of the invention 10 μ m, 10 μ m atomic force microscope characterize pattern, 2 (a) in two-dimensional polymer film with a thickness of 20nm, in 2 (b) two-dimensional polymer film with a thickness of 50nm, two dimension is poly- in 2 (c) Close object film with a thickness of 70nm;
Fig. 3 is the curve of unlatching and the erasing of memristor of the invention (using the two-dimensional polymer film of 20nm thickness);
Fig. 4 is the statistics of the cyclical stability of memristor of the invention (using the two-dimensional polymer film of 20nm thickness);
Fig. 5 is the statistics of the high low resistance state of different components (using the two-dimensional polymer film of 20nm thickness);
Fig. 6 is to be read the memristor obtained retention time of the present invention (to polymerize using the thick two dimension of 20nm with 0.1V voltage Object film);
Fig. 7 is the curve of unlatching and the erasing of memristor of the invention (using the two-dimensional polymer film of 50nm thickness);
Fig. 8 is the statistics of the cyclical stability of memristor of the invention (using the two-dimensional polymer film of 5 0nm thickness);
Fig. 9 is the statistics of the high low resistance state of different components (using the two-dimensional polymer film of 50nm thickness);
Figure 10 is to be read the memristor obtained retention time of the present invention (to polymerize using the thick two dimension of 50nm with 0.1V voltage Object film);
Figure 11 is the curve of unlatching and the erasing of memristor of the invention (using the two-dimensional polymer film of 70nm thickness);
Figure 12 is the statistics of the cyclical stability of memristor of the invention (using the two-dimensional polymer film of 70nm thickness);
Figure 13 is the statistics of the high low resistance state of different components (using the two-dimensional polymer film of 70nm thickness);
Figure 14 is to be read the memristor obtained retention time of the present invention (to polymerize using the thick two dimension of 70nm with 0.1V voltage Object film);
Figure 15 is nitrogen adsorption/desorption curve of two-dimensional polymer film;
Figure 16 is the graph of pore diameter distribution of two-dimensional polymer film;
Figure 17 is the Fourier transform infrared map of two-dimensional polymer film of the invention;
Figure 18 is the high resolution transmission electron microscopy picture for the two-dimensional polymer film that embodiment 2 is prepared;
Figure 19 is the image of the selective electron diffraction for the two-dimensional polymer film that embodiment 2 is prepared.
Specific embodiment
In a specific embodiment of the invention, related instrument is as follows:
Atomic force microscope model: German Bruker Dimension Icon ScanAsyst, when atomic force microscope is tested Using tapping mode, what probe was selected is Brooker VSEP-2A type needle point.
Optical microscopy model: karr Zeiss Axio Scope A1 pol
Electrical testing probe station property: South Korea Ecopia EPS-1000
Semiconductor property tester: Shanghai carries moral EPS-300, when testing device performance using semiconductor property tester, ITO ground connection, applies voltage, step-length 0.02V on Ag electrode.In device property figure, 1 refers to applying voltage from 0V-1.5V The curve of scanning process, 2 refer to applying the curve that voltage is scanned from 1.5-0V, and 3 refer to that apply voltage scans from 0-3.3V The curve of appearance, 4 refer to applying the curve that voltage occurs from 3.3-0V scanning.
BET test: JB-2020 type specific-surface area detection instrument, when BET is tested, 200 DEG C of activation, 77K test.
The purchase source of involved drug are as follows:
Agents useful for same is all purchased from Chinese medicines group, and purity is that analysis is pure.
In the following embodiments, the unit of a volume parts is mL, and the unit of a mass fraction is mg, a substance Amount number unit be mmol.Deionized water is ultrapure water, and resistivity is 18.2M Ω ﹒ cm.
In the inventive solutions, reaction vessel can be surface plate, weighing bottle, culture dish, glass flume or glass Glass cylinder etc., according to the difference of reaction vessel area, the area of the two-dimensional polymer film obtained can be 1um2-1m2.It is following Examples 1 to 3 be all made of diameter be 7cm weighing bottle as reaction vessel, therefore, the two-dimensional polymer of following embodiment 1-3 The shape of film is 7 centimetres of diameter of circle, the shape of embodiment 4-6 be cut into 1*1 centimetres two-dimensional polymer it is thin Film.
Technical solution of the present invention is further illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of two-dimensional polymer film, comprising the following steps:
Aromatic multi-amine mixed solution is configured in the weighing bottle that diameter is 7cm, and the more aldehyde mixed solutions of fragrance are added dropwise in virtue On the liquid level of fragrant polyamines mixed solution, the lid of weighing bottle is covered, a 0.5cm wide is pressed from both sides between lid and the bottle body of weighing bottle Filter paper item (folder filter paper item for reserve come some gaps, allow aromatics organic solvent B volatilize), in 20~25 DEG C of room temperature transfer The aromatics organic solvent B volatilization set into the more aldehyde mixed solutions of fragrance finishes (standing time is 24 hours), on liquid level To the two-dimensional polymer film with a thickness of 20nm, wherein
The amount of the substance of the more aldehyde of fragrance in the more aldehyde mixed solutions of fragrance and the aromatic multi-amine in aromatic multi-amine mixed solution Ratio 0.00167:0.01389;
The configuration method of aromatic multi-amine mixed solution are as follows: aromatic multi-amine is evenly distributed in organic solvent A, obtains solution Deionized water is added in solution A and uniformly mixes, obtains the aromatic multi-amine mixed solution of light brown, wherein deionized water by A Volume parts and aromatic multi-amine substance amount number ratio be 1:0.01389.The concentration of aromatic multi-amine is in solution A 1.2mmol/mL, organic solvent A are aprotic and organic reagent miscible with water, organic solvent A N, N- dimethyl formyl Amine.
The configuration method of the more aldehyde mixed solutions of fragrance are as follows: the more aldehyde of fragrance are evenly distributed in aromatics organic solvent B, are obtained To solution B, organic acid is added in solution B, obtains the more aldehyde mixed solutions of fragrance, wherein the parts by volume of aromatics organic solvent B Several ratios with the amount number of the substance of the more aldehyde of fragrance are 1:0.00167, and the volume of organic acid is the 1% of the volume of solution B;
Organic acid is acetic acid;
Aromatics organic solvent B is chlorobenzene.
The more aldehyde of fragrance are equal benzene trioxin.
Aromatic multi-amine is p-phenylenediamine.
Embodiment 2
A kind of preparation method of two-dimensional polymer film, comprising the following steps:
Aromatic multi-amine mixed solution is configured in the weighing bottle that diameter is 7cm, and the more aldehyde mixed solutions of fragrance are added dropwise in virtue On the liquid level of fragrant polyamines mixed solution, the lid of weighing bottle is covered, a 0.5cm wide is pressed from both sides between lid and the bottle body of weighing bottle Filter paper item, the aromatics organic solvent B volatilization placed at 20~25 DEG C of room temperature into the more aldehyde mixed solutions of fragrance, which finishes, (puts Setting the time is 36 hours), the two-dimensional polymer film with a thickness of 50nm is obtained on liquid level, wherein
The amount of the substance of the more aldehyde of fragrance in the more aldehyde mixed solutions of fragrance and the aromatic multi-amine in aromatic multi-amine mixed solution Ratio 0.00333:0.01389;
The configuration method of aromatic multi-amine mixed solution are as follows: aromatic multi-amine is evenly distributed in organic solvent A, obtains solution Deionized water is added in solution A and uniformly mixes, obtains the aromatic multi-amine mixed solution of light brown, wherein deionized water by A Volume parts and aromatic multi-amine substance amount number ratio be 1:0.01389.The concentration of aromatic multi-amine is in solution A 1.2mmol/mL, organic solvent A are aprotic and organic reagent miscible with water, organic solvent A N, N- dimethyl formyl Amine.
The configuration method of the more aldehyde mixed solutions of fragrance are as follows: the more aldehyde of fragrance are evenly distributed in aromatics organic solvent B, are obtained To solution B, organic acid is added in solution B, obtains the more aldehyde mixed solutions of fragrance, wherein the parts by volume of aromatics organic solvent B Several ratios with the amount number of the substance of the more aldehyde of fragrance are 1:0.00333, and the volume of organic acid is the 1% of the volume of solution B;
Organic acid is acetic acid;
Aromatics organic solvent B is chlorobenzene.
The more aldehyde of fragrance are equal benzene trioxin.
Aromatic multi-amine is p-phenylenediamine.
Embodiment 3
A kind of preparation method of two-dimensional polymer film, comprising the following steps:
Aromatic multi-amine mixed solution is configured in the weighing bottle that diameter is 7cm, and the more aldehyde mixed solutions of fragrance are added dropwise in virtue On the liquid level of fragrant polyamines mixed solution, the lid of weighing bottle is covered, a 0.5cm wide is pressed from both sides between lid and the bottle body of weighing bottle Filter paper item, the aromatics organic solvent B volatilization placed at 20~25 DEG C of room temperature into the more aldehyde mixed solutions of fragrance, which finishes, (puts Setting the time is 48 hours), the two-dimensional polymer film with a thickness of 70nm is obtained on liquid level, wherein
The amount of the substance of the more aldehyde of fragrance in the more aldehyde mixed solutions of fragrance and the aromatic multi-amine in aromatic multi-amine mixed solution Ratio 0.005:0.01389;
The configuration method of aromatic multi-amine mixed solution are as follows: aromatic multi-amine is evenly distributed in organic solvent A, obtains solution Deionized water is added in solution A and uniformly mixes, obtains the aromatic multi-amine mixed solution of light brown, wherein deionized water by A Volume parts and aromatic multi-amine substance amount number ratio be 1:0.01389.The concentration of aromatic multi-amine is in solution A 1.2mmol/mL, organic solvent A are aprotic and organic reagent miscible with water, organic solvent A N, N- dimethyl formyl Amine.
The configuration method of the more aldehyde mixed solutions of fragrance are as follows: the more aldehyde of fragrance are evenly distributed in aromatics organic solvent B, are obtained To solution B, organic acid is added in solution B, obtains the more aldehyde mixed solutions of fragrance, wherein the parts by volume of aromatics organic solvent B Several ratios with the amount number of the substance of the more aldehyde of fragrance are 1:0.005, and the volume of organic acid is the 1% of the volume of solution B;
Organic acid is acetic acid;
Aromatics organic solvent B is chlorobenzene.
The more aldehyde of fragrance are equal benzene trioxin.
Aromatic multi-amine is p-phenylenediamine.
Fig. 2 is that the atomic force microscope for the two-dimensional polymer film that Examples 1 to 3 is prepared characterizes pattern, wherein 2 (a) the two-dimensional polymer film being prepared for embodiment 1, with a thickness of 20nm;2 (b) gather for the two dimension that embodiment 2 is prepared Object film is closed, with a thickness of 50nm;2 (c) the two-dimensional polymer films being prepared for embodiment 3, with a thickness of 70nm;It can by figure Know, the two-dimensional polymer film that the present invention is prepared has good homogeneity, and roughness is respectively 0.2nm in 10um (embodiment 1), 0.7nm (embodiment 2) and 1.8nm (embodiment 3), roughness is lower.
Two-dimensional polymer film (2DP) DMF, the methylene chloride, three chloromethanes that obtained Examples 1 to 3 is prepared After alkane and acetone impregnate cleaning in 5 hours respectively, discovery 2DP material, which is appointed, to be so stabilized.
Embodiment 4
The two-dimensional polymer film that embodiment 1 is prepared is obtained into memristor as active layer, memristor is from top to bottom Successively are as follows: active electrode, two-dimensional polymer film and inert electrode, as shown in Figure 1.Active electrode is silver layer, with a thickness of 50nm; Inert electrode is ITO conductive glass layer.The preparation method of memristor, comprising the following steps:
A) two-dimensional polymer film is transferred to the upper surface of inert electrode, vacuum is dry at 30 DEG C in a vacuum drying oven Dry 8h;
B) active electrode is deposited on two-dimensional polymer film.The method that silver layer is deposited are as follows: use 100/400 copper mesh as Mask plate is attached to the upper surface (mesh number of copper mesh is 200 mesh) of two-dimensional polymer film, withRate deposition thickness be The silver layer of 50nm removes copper mesh after deposition, completes vapor deposition silver layer.
Fig. 3 is the curve of unlatching and erasing that embodiment 4 obtains memristor (using the two-dimensional polymer film of 20nm thickness); When testing device, ITO (ITO conductive glass layer) ground connection applies voltage, step-length 0.02V on Ag electrode (silver layer).Scheming In 3,1 refers to the curve from 0V-1.5V scanning process, and 2 refer to the curve scanned from 1.5-0V, and curve 1 and 2 is in test Limitation electric current be 10-3;3 refer to the curve that 0-3.3V scanning occurs, and 4 refer to scanning the curve occurred from 3.3-0V, bent The limitation electric current of line 3 and 4 is 10-2.The step of curve 1 and 2 is the writing process of memristor, is equivalent to information storage, 3 He of curve 4 be the process of memristor erasing.From the figure 3, it may be seen that can be carried out by the memristor that embodiment 1 obtains two-dimensional polymer film preparation Complete write-in and erase process.
Fig. 4 is the statistics of the cyclical stability for the memristor that embodiment 4 obtains, and is carried out to the same device (memristor) Unlatching and erasing operation repeatedly, it is found that the two-dimensional polymer film of the thickness can carry out 100 times as the device of active layer Normal operating.
Fig. 5 is the statistics of the high low resistance state for the memristor that embodiment 4 obtains;To the two dimension polymerization thick with a batch of 20nm The memristor of object film preparation carries out unlatching and erasing operation, and counts the value of high low resistance state of 200 devices in -0.1V, As shown in Figure 5, find the memristor on-off ratio of the two-dimensional polymer film preparation of 20nm thickness 102Magnitude.
Fig. 6 is the retention time of the memristor obtained with 0.1V voltage reading Example 4;Write operation is being carried out to device Afterwards, device is read out with 0.1V voltage, obtains device in the retention time of low resistance state;Erasing behaviour is being carried out to same device After work, device is read out with 0.1V voltage, obtains device in the retention time of high-impedance state.By obtain two retention times Drawing of Curve found in same figure, read access time of the device under the thickness under 0.1V voltage be 8*103s。
Embodiment 5
The two-dimensional polymer film that embodiment 2 is prepared is obtained into memristor as active layer, memristor is from top to bottom Successively are as follows: active electrode, two-dimensional polymer film and inert electrode, active electrode is silver layer, with a thickness of 50nm;Inert electrode is ITO conductive glass layer.The preparation method of memristor, comprising the following steps:
A) two-dimensional polymer film is transferred to the upper surface of inert electrode, vacuum is dry at 30 DEG C in a vacuum drying oven Dry 8h;
B) active electrode is deposited on two-dimensional polymer film.The method that silver layer is deposited are as follows: use 100/400 copper mesh as Mask plate is attached to the upper surface (mesh number of copper mesh is 200 mesh) of two-dimensional polymer film, withRate deposition thickness be The silver layer of 50nm removes copper mesh after deposition, completes vapor deposition silver layer.
Fig. 7 is the curve of unlatching and erasing that embodiment 5 obtains memristor;When testing device, ITO ground connection, in Ag electricity It is extremely upper to apply voltage, step-length 0.02V.In Fig. 7,1 refers to the curve from 0V-1.5V scanning process, and 2 refer to from 1.5- The curve of 0V scanning, limitation electric current of the curve 1 and 2 in test is 10-3;3 refer to the curve that 0-3.3V scanning occurs, and 4 refer to Be the curve occurred from 3.3-0V scanning, the limitation electric current of curve 3 and 4 is 10-2.Curve 1 and 2 is the write-in of memristor Journey, is equivalent to the step of information stores, and curve 3 and 4 is the process of memristor erasing.As seen from the figure, 50nm thick two dimension polymerization The memristor of object film preparation can be completely written and erase process.
Fig. 8 is the statistics of the cyclical stability for the memristor that embodiment 5 obtains, to by 50nm thickness two-dimensional polymer film system Standby memristor carries out cyclical stability test.The same device is being opened and erasing operation repeatedly, is finding the thickness Two-dimensional polymer film can carry out 180 subnormal operations as the device of active layer.
Fig. 9 is the statistics of the high low resistance state for the memristor that embodiment 5 obtains (using the two-dimensional polymer film of 50nm thickness); Unlatching and erasing operation are carried out to the memristor of the two-dimensional polymer film preparation with a batch of 50nm thickness, and count 200 The value of high low resistance state of the device in -0.1V, as shown in figure 9, the memristor switch of the two-dimensional polymer preparation of discovery 50nm thickness Than 104Magnitude.
Figure 10 is that the retention time of memristor is obtained with 0.1V voltage reading Example 5 (using the thick two dimension polymerization of 50nm Object film);As seen from the figure, after carrying out write operation to device, device is read out with 0.1V voltage, obtains device low The retention time of resistance state;After carrying out erasing operation to same device, device is read out with 0.1V voltage, device is obtained and exists The retention time of high-impedance state.By to the Drawing of Curve of two retention times found in same figure, the device under the thickness Read access time of the part under 0.1V voltage is 1*104s。
Embodiment 6
The two-dimensional polymer film that embodiment 3 is prepared is obtained into memristor as active layer, memristor is from top to bottom Successively are as follows: active electrode, two-dimensional polymer film and inert electrode, active electrode is silver layer, with a thickness of 50nm;Inert electrode is ITO conductive glass layer.The preparation method of memristor, comprising the following steps:
A) two-dimensional polymer film is transferred to the upper surface of inert electrode, vacuum is dry at 30 DEG C in a vacuum drying oven Dry 8h;
B) active electrode is deposited on two-dimensional polymer film.The method that silver layer is deposited are as follows: use 100/400 copper mesh as Mask plate is attached to the upper surface (mesh number of copper mesh is 200 mesh) of two-dimensional polymer film, withRate deposition thickness be The silver layer of 50nm removes copper mesh after deposition, completes vapor deposition silver layer.
Figure 11 is that embodiment 6 obtains the curve of unlatching and erasing of memristor (two-dimensional polymer using 70nm thickness is thin Film);When testing device, ITO ground connection applies voltage, step-length 0.02V on Ag electrode.In Figure 11,1 is referred to from 0V- The curve of 1.5V scanning process, 2 refer to the curve scanned from 1.5-0V, and limitation electric current of the curve 1 and 2 in test is 10-3; 3 refer to the curve that 0-3.3V scanning occurs, and 4 refer to scanning the curve occurred, the limitation electric current of curve 3 and 4 from 3.3-0V It is 10-2.The step of curve 1 and 2 is the writing process of memristor, is equivalent to information storage, curve 3 and 4 are memristor erasings Process.As seen from the figure, the device that prepared by the two-dimensional polymer of 70nm thickness can be completely written and erase process.
Figure 12 is that embodiment 6 obtains the statistics of cyclical stability of memristor (two-dimensional polymer using 70nm thickness is thin Film);Cyclical stability test is carried out to the memristor of 70nm thickness two-dimensional polymer film preparation.It is carried out instead to the same device Multiple unlatching and erasing operation, it is found that the two-dimensional polymer of the thickness can carry out 200 subnormal behaviour as the device of active layer Make.
(two-dimensional polymer using 70nm thickness is thin for the statistics of the high low resistance state for the memristor that Figure 13 obtains for embodiment 6 Film);Unlatching and erasing operation are carried out to the memristor with a batch of 70nm thickness two-dimensional polymer film preparation, and count 200 The value of high low resistance state of a device in -0.1V is depicted as Figure 13, finds the memristor of the two-dimensional polymer film preparation of 70nm thickness Device on-off ratio is 105Magnitude.
Figure 14 is that the retention time of memristor is obtained with 0.1V voltage reading Example 6 (using the thick two dimension polymerization of 70nm Object film), after carrying out write operation to device, device is read out with 0.1V voltage, obtains device in the guarantor of low resistance state Hold the time;After carrying out erasing operation to same device, device is read out with 0.1V voltage, obtains device in high-impedance state Retention time.By to the Drawing of Curve of two retention times find that the device under the thickness is in 0.1V in same figure Read access time under voltage is 3.5*104s。
Figure 15 is the nitrogen adsorption/desorption curve for the two-dimensional polymer film that embodiment 2 is prepared.It can by figure Know, which belongs to I types of absorbent curve, but desorption curve illustrates some nitrogen there is no being overlapped with adsorption curve It is fixed on 2DPBTA+PDAIn, thus with the presence of micropore in testimonial material.The specific surface area for calculating material is 74.4m2/ G, pore volume are 8.82 × 10-2cm3/g.2DP is obtained by non-localized Density functional theory computation with the data of Figure 15BTA+PDA The aperture of (two-dimensional polymer film) is 1.41nm, as shown in figure 16.(Figure 15 and 16 instrument models: JB-2020 type compares table Area tester)
Figure 17 is to obtain the Fourier transform infrared map of two-dimensional polymer film, 3392cm by embodiment 2-1It is N-H key Stretching vibration, 2292cm-1It is-NH on unreacted aromatic multi-amine monomer2Stretching vibration, 1694cm-1It is that fragrance is aldehyde BTA points more It is the stretching vibration of the C=O of reaction, 1621cm on son-1It is the C=that the more aldehyde of fragrance and aromatic multi-amine generate after schiff base reaction The stretching vibration of N, 1260cm-1It is the C-N key stretching vibration of phenyl ring and nitrogen-atoms.The wherein appearance of 1621 characteristic peaks, shows Schiff base reaction has occurred in the more aldehyde of fragrance and aromatic multi-amine really under the catalysis of organic acid, and the 2DP of generation is existed by two monomers It is polymerized under schiff bases reflection (answering).(instrument model: Brooker VERTEX80/80v.)
As shown in Figure 18, which belongs to the material of undefined structure.It appears from figure 19 that the image is presented Out the phenomenon that diffraction ring, illustrates that material belongs to unformed state, demonstrate the result of Figure 18.(instrument: Hitachi HT7800)
In the inventive solutions, n,N-Dimethylformamide is modified to n,N-dimethylacetamide or dimethyl Sulfoxide, or acetic acid is modified to trifluoroacetic acid or trifluoromethanesulfonic acid, or chlorobenzene is modified to dichloro-benzenes or toluene, technical effect It is consistent with above-described embodiment.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal Fall into protection scope of the present invention.

Claims (10)

1. a kind of memristor that two-dimensional polymer film is obtained as active layer, which is characterized in that the two-dimensional polymer film Preparation method the following steps are included:
The more aldehyde mixed solutions of fragrance are added dropwise on the liquid level of aromatic multi-amine mixed solution, are placed at 20~25 DEG C of room temperature to institute The aromatics organic solvent B volatilization stated in the more aldehyde mixed solutions of fragrance finishes, and two-dimensional polymer film is obtained on liquid level, In,
The substance of fragrance more aldehyde and the aromatic multi-amine in the aromatic multi-amine mixed solution in the more aldehyde mixed solutions of fragrance Amount ratio (0.0015~0.005): 0.01389;
The configuration method of the aromatic multi-amine mixed solution are as follows: aromatic multi-amine is evenly distributed in organic solvent A, obtains solution Deionized water is added in the solution A and uniformly mixes, obtains the aromatic multi-amine mixed solution of light brown, wherein described by A The concentration of aromatic multi-amine is 0.185~4.63mmol/mL in solution A, and the organic solvent A is aprotic and miscible with water Organic reagent;
The configuration method of the more aldehyde mixed solutions of fragrance are as follows: the more aldehyde of fragrance are evenly distributed in aromatics organic solvent B, are obtained To solution B, organic acid is added in the solution B, obtains the more aldehyde mixed solutions of fragrance, wherein the aromatics organic solvent B Volume parts and the more aldehyde of fragrance substance amount number ratio be (0.5~1): (0.0008~0.01), it is described organic The volume of acid is the 0.7~1.5% of the volume of the solution B;
The organic acid is acetic acid, trifluoroacetic acid or trifluoromethanesulfonic acid;
Aromatics organic solvent B is chlorobenzene, dichloro-benzenes or toluene.
2. memristor according to claim 1, which is characterized in that the memristor is from top to bottom successively are as follows: active electrode, Two-dimensional polymer film and inert electrode, the active electrode are aluminium layer, layers of copper or silver layer;The inert electrode is ITO conductive Glassy layer, layer gold or platinum layer.
3. memristor according to claim 2, which is characterized in that the aromatics organic solvent B is volatilized the time finished It is at least 24 hours.
4. memristor according to claim 3, which is characterized in that in the aromatic multi-amine mixed solution, it is described go from The ratio of the amount number of the substance of the volume parts of sub- water and the aromatic multi-amine is 1:(0.005~0.03);One volume The unit of number is mL, and the unit of a mass fraction is mg, and the unit of the amount number of a substance is mmol.
5. memristor according to claim 4, which is characterized in that the more aldehyde of fragrance include two or 2 or more aldehyde Base;The aromatic multi-amine includes two or 2 or more amidos;The deionized water is ultrapure water, and resistivity is 18.2M Ω ﹒ cm。
6. memristor according to claim 5, which is characterized in that the organic solvent A be n,N-Dimethylformamide, N, N- dimethyl acetamide or dimethyl sulfoxide.
7. memristor according to claim 6, which is characterized in that the active electrode with a thickness of 10~200nm;It is described Two-dimensional polymer film with a thickness of 2~80nm.
8. the preparation method of memristor as described in any one of claim 1~7, which comprises the following steps:
A) the two-dimensional polymer film is transferred to the upper surface of inert electrode, it is true at 15~40 DEG C in a vacuum drying oven Dry 2~the 10h of sky;
B) active electrode is deposited on the two-dimensional polymer film.
9. the preparation method of memristor according to claim 8, which is characterized in that in the step b), when the work Property electrode when being silver layer, method that the silver layer is deposited are as follows: copper mesh is used to be attached to the two-dimensional polymer film as mask plate Upper surface, withRate deposition thickness be 20~100nm silver layer, remove the copper mesh after deposition, complete Silver layer is deposited.
10. the preparation method of memristor according to claim 9, which is characterized in that the mesh number of the copper mesh be 200~ 300 mesh.
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