CN110317310B - Two-dimensional polymer film and preparation method thereof - Google Patents
Two-dimensional polymer film and preparation method thereof Download PDFInfo
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- CN110317310B CN110317310B CN201810278812.0A CN201810278812A CN110317310B CN 110317310 B CN110317310 B CN 110317310B CN 201810278812 A CN201810278812 A CN 201810278812A CN 110317310 B CN110317310 B CN 110317310B
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- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
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Abstract
The invention discloses a two-dimensional polymer film and a preparation method thereof, wherein the preparation method comprises the following steps: and (3) dropwise adding the aromatic polyaldehyde mixed solution on the liquid surface of the aromatic polyamine mixed solution, and placing the solution at room temperature of 20-25 ℃ until the aromatic organic solvent B in the aromatic polyaldehyde mixed solution is completely volatilized, thereby obtaining the two-dimensional polymer film on the liquid surface. The invention takes the aromatic polyaldehyde and the aromatic polyamine as the reaction monomer to prepare the covalent organic two-dimensional polymer film for the first time, and provides the growth condition for preparing the covalent organic two-dimensional polymer. The preparation method is simple and economical, a high-end precise instrument is not needed, a large-area uniform two-dimensional polymer film can be obtained without providing high energy, the thickness of the two-dimensional polymer film can be adjusted by adjusting the monomer amount, and the preparation method is suitable for the requirement of actual production.
Description
Technical Field
The invention belongs to the technical field of organic two-dimensional materials, and particularly relates to a two-dimensional polymer film and a preparation method thereof.
Background
Two-dimensional materials have sheet-like structures with lateral dimensions greater than 100nm, even several micrometers or even greater, but are only a single atom or a few atoms thick (typically less than 5 nm), and are a polymeric material with regio-repetitive, periodic structures inside. In two-dimensional materials, electrons are confined in two dimensions, thereby achieving unprecedented physical, electronic, and chemical properties. The two-dimensional material originally found was graphene exfoliated from graphite. Graphene is a two-dimensional material with the thickness of a monoatomic layer and is formed by sp2The hexagonal honeycomb lattice composed of hybridized carbon atoms has excellent electron transmission, optical, mechanical and heat conducting performances due to a large pi conjugated system formed on the basis of the structure. The discovery of these excellent properties of graphene has prompted researchers to follow atomic or atomic propertiesInterest in molecular level rational design and synthesis of novel two-dimensional macromolecules.
Further exploration by researchers has led to the discovery of two-dimensional covalent organic lattice materials (2D COFs). The material is a novel two-dimensional material which is formed by organic structural units which are linked by covalent bonds and has a periodic structure and a single structural unit thickness. The material is a monomer consisting of C, H, O, N light elements, and forms a very stable porous nano material through stronger covalent bonds among atoms. Therefore, the regulation and control of the two-dimensional polymer function can be achieved by regulating the types and positions of the monomer functional groups. Similar to graphene, conventional two-dimensional polymers are obtained by peeling off a covalent organic framework material (COF) in a "top-down" manner. Due to the size of two-dimensional organic grid framework materials (COFs), the area of a two-dimensional single crystal material with the thickness of a monoatomic layer is greatly limited, so that the two-dimensional material is difficult to meet the requirements of nano electronic devices. Yet another "bottom-up" approach is often used in the preparation of two-dimensional materials. The method is that monomer is first deposited on the surface of proper base material, and then certain external stimulus is given to prepare two-dimensional polymer through surface reaction. The method for preparing the two-dimensional material on the interface can prepare the single-layer two-dimensional polymer by fully utilizing the catalytic activity of the substrate and the van der Waals epitaxial effect, and can obtain the single-layer material with large area. However, this method often requires severe conditions, such as high temperature, ultra-high vacuum environment, etc., to promote the reaction. In addition, the two-dimensional material obtained by this method has a problem of being difficult to transfer. The two-dimensional material prepared by the method of either the top-down method or the bottom-up method hardly meets the requirements of practical application in terms of size and properties.
Disclosure of Invention
In view of the defects of the prior art, the present invention aims to provide a method for preparing a two-dimensional polymer film, wherein the method for preparing the two-dimensional polymer film is based on an interface method, an ultra-thin two-dimensional polymer film can be prepared in an atmospheric environment at a temperature close to room temperature, and two-dimensional polymer films with different thicknesses can be obtained by changing the concentration and the molar quantity (the ratio of aromatic polyaldehyde to aromatic polyamine) of a monomer in the preparation process. The two-dimensional polymer film obtained by the preparation method can be transferred to any required substrate according to the needs, and is beneficial to constructing electronic devices with different structures.
The purpose of the invention is realized by the following technical scheme.
A method for preparing a two-dimensional polymer film, comprising the steps of:
dripping the aromatic polyaldehyde mixed solution on the liquid surface of the aromatic polyamine mixed solution, placing the solution at the room temperature of 20-25 ℃ until the aromatic organic solvent B in the aromatic polyaldehyde mixed solution is completely volatilized, and obtaining a two-dimensional polymer film on the liquid surface, wherein,
the ratio of the amount of the aromatic polyaldehyde in the aromatic polyaldehyde mixed solution to the amount of the aromatic polyamine in the aromatic polyamine mixed solution (0.0015 to 0.005): 0.01389;
the preparation method of the aromatic polyamine mixed solution comprises the following steps: uniformly distributing aromatic polyamine in an organic solvent A to obtain a solution A, adding deionized water into the solution A, and uniformly mixing to obtain a light brown aromatic polyamine mixed solution, wherein the concentration of the aromatic polyamine in the solution A is 0.185-4.63 mmol/mL, and the organic solvent A is an aprotic organic reagent mutually soluble with water;
the preparation method of the aromatic polyaldehyde mixed solution comprises the following steps: uniformly distributing aromatic polyaldehyde in an aromatic organic solvent B to obtain a solution B, and adding an organic acid into the solution B to obtain an aromatic polyaldehyde mixed solution, wherein the ratio of the volume parts of the aromatic organic solvent B to the mass parts of the aromatic polyaldehyde is (0.5-1): (0.0008 to 0.01) and the volume of the organic acid is 0.7 to 1.5% of the volume of the solution B;
the organic acid is acetic acid, trifluoroacetic acid or trifluoromethanesulfonic acid;
the aromatic organic solvent B is chlorobenzene, dichlorobenzene or toluene.
In the technical scheme, the organic solvent A is N, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide.
In the above technical scheme, the time for the aromatic organic solvent B placed in the aromatic polyaldehyde mixed solution to complete volatilization is at least 24 hours.
In the above technical solution, in the aromatic polyamine mixed solution, a ratio of parts by volume of the deionized water to parts by weight of the aromatic polyamine is 1: (0.005-0.03).
In the above technical solution, one unit of the volume parts is mL, one unit of the mass parts is mg, and one unit of the mass parts is mmol.
In the above technical scheme, the aromatic polyaldehyde comprises two or more than 2 aldehyde groups.
In the above technical solution, the aromatic polyamine includes two or more than 2 amine groups.
In the above technical solution, the deionized water was ultrapure water, and the resistivity was 18.2 M.OMEGA.cm.
The two-dimensional polymer film obtained by the preparation method.
In the technical scheme, the thickness of the two-dimensional polymer film is 2-80 nm.
The two-dimensional polymer film is used as an active layer to obtain the memristor.
In the above technical scheme, the memristor sequentially comprises from top to bottom: the electrode comprises an active electrode, a two-dimensional polymer film and an inert electrode, wherein the active electrode is an aluminum layer, a copper layer or a silver layer; the inert electrode is an ITO conductive glass layer, a gold layer or a platinum layer.
In the technical scheme, the thickness of the active electrode is 10-200 nm.
The preparation method of the memristor comprises the following steps:
a) transferring the two-dimensional polymer film to the upper surface of an inert electrode, and carrying out vacuum drying in a vacuum drying oven at 15-40 ℃ for 2-10 h;
b) and evaporating the active electrode on the two-dimensional polymer film.
In the step b), when the active electrode is a silver layer, evaporating the active electrodeThe method for preparing the silver layer comprises the following steps: a copper net is used as a mask plate to be attached to the upper surface of the two-dimensional polymer film so as to
And depositing a silver layer with the thickness of 20-100 nm at the speed, and taking down the copper mesh after the deposition is finished to finish the evaporation of the silver layer.
In the technical scheme, the mesh number of the copper mesh is 200-300 meshes.
The two-dimensional polymer film is used as an active layer in the application of a memristor.
Compared with the prior art, the two-dimensional polymer film has the beneficial effects that:
1. the invention takes the aromatic polyaldehyde and the aromatic polyamine as the reaction monomer to prepare the covalent organic two-dimensional polymer film for the first time, and provides the growth condition for preparing the covalent organic two-dimensional polymer. The preparation method is simple and economical, a high-end precise instrument is not needed, a large-area uniform two-dimensional polymer film can be obtained without providing high energy, the thickness of the two-dimensional polymer film can be adjusted by adjusting the monomer amount, and the preparation method is suitable for the requirement of actual production.
2. The invention provides a method for preparing a covalent organic two-dimensional polymer film on a water-air interface by using a solution epitaxy method, and simultaneously, by means of the characteristic of covalent connection of two monomers, the uniform porous structure can be provided, and the material can stably exist in various organic solvents and water. Compared with a film obtained by a one-dimensional polymer through methods such as spin coating, drop casting and the like, the material has a uniform porous structure, and also has good solvent resistance, so that the application range of the material is expanded.
3. The invention provides a method for preparing a covalent organic two-dimensional polymer film on a water-air interface by using a solution epitaxy method, wherein the covalent organic two-dimensional polymer film presents an amorphous state, so that the two-dimensional polymer film presents the characteristic of flexible self-support.
4. The invention provides a memristor taking a two-dimensional polymer film as a functional layer for the first time, and the memristor based on the principle of conductive wires is prepared by adopting an active electrode by virtue of a porous structure of the material. The two-dimensional polymer film is prepared on a gas-liquid interface, so that the two-dimensional polymer film is very convenient to transfer to any substrate, other materials are transferred to the substrate by methods such as inorganic evaporation, spin coating and the like, and compared with the method, the method has the advantages of convenience and easiness in operation, and the two-dimensional polymer film can be transferred to any required substrate.
Drawings
FIG. 1 is a schematic diagram of a memristor of the present disclosure;
FIG. 2 is an atomic force microscope characterization of the two-dimensional polymer film of the present invention in the range of 10 μm × 10 μm, wherein the thickness of the two-dimensional polymer film in 2(a) is 20nm, the thickness of the two-dimensional polymer film in 2(b) is 50nm, and the thickness of the two-dimensional polymer film in 2(c) is 70 nm;
FIG. 3 is a plot of turn-on and erase for a memristor of the present invention (using a 20nm thick two-dimensional polymer film);
FIG. 4 is a statistic of the cycling stability of memristors of the present invention (using a 20nm thick two-dimensional polymer film);
FIG. 5 is a graph showing statistics of high and low resistance states of different devices (using a 20nm thick two-dimensional polymer film);
FIG. 6 is a graph of retention time (using a 20nm thick two-dimensional polymer film) obtained by reading a memristor of the present invention with a voltage of 0.1V;
FIG. 7 is a plot of turn-on and erase for a memristor of the present invention (using a 50nm thick two-dimensional polymer film);
FIG. 8 is a statistic of the cycling stability of memristors of the present invention (using a 50nm thick two-dimensional polymer film);
FIG. 9 is a statistical analysis of the high and low resistance states of different devices (using a 50nm thick two-dimensional polymer film);
FIG. 10 is a graph of the retention time (using a 50nm thick two-dimensional polymer film) obtained by reading a memristor of the present invention with a voltage of 0.1V;
FIG. 11 is a plot of turn-on and erase for a memristor of the present invention (using a 70nm thick two-dimensional polymer film);
FIG. 12 is a statistic of the cycling stability of memristors of the present disclosure (using a 70nm thick two-dimensional polymer film);
FIG. 13 is a graph showing statistics of high and low resistance states of different devices (using a 70nm thick two-dimensional polymer film);
FIG. 14 is a graph of retention time (using a 70nm thick two-dimensional polymer film) obtained by reading a memristor of the present invention with a voltage of 0.1V;
FIG. 15 is a plot of nitrogen adsorption/desorption for a two-dimensional polymer film;
FIG. 16 is a pore size distribution plot for a two-dimensional polymer film;
FIG. 17 is a Fourier transform infrared spectrum of a two-dimensional polymer film of the present invention;
FIG. 18 is a high resolution TEM image of a two-dimensional polymer film prepared in example 2;
fig. 19 is an image of selected area electron diffraction of the two-dimensional polymer film prepared in example 2.
Detailed Description
In a particular embodiment of the invention, the apparatus concerned is as follows:
atomic force microscope model: in Bruker Dimension Icon ScanAsyst Germany, tapping mode is adopted during atomic microscope test, and Bruker Dimension Icon ScanAsyst Germany, and Bruker VSEP-2A type tip is selected as a probe.
Model of optical microscope: carl. Caiss Axio Scope A1pol
Electrical test probe station properties: korean Ecopia EPS-1000
Semiconductor property tester: in Shanghai Carrier EPS-300, when a semiconductor property tester is used for testing the performance of a device, ITO is grounded, and voltage is applied to an Ag electrode with the step size of 0.02V. In the device property diagram, 1 refers to a curve of the applied voltage during the scan from 0V to 1.5V, 2 refers to a curve of the applied voltage during the scan from 1.5V to 0V, 3 refers to a curve of the applied voltage occurring from 0V to 3.3V, and 4 refers to a curve of the applied voltage occurring from 3.3V to 0V.
BET test: JB-2020 specific surface area tester, BET test, 200 deg.C activation, 77K test.
The purchase sources of the related medicines are:
all the reagents are purchased from the national medicine group, and the purity is analytically pure.
In the examples described below, one part by volume is in mL, one part by mass is in mg, and one part by mass is in mmol. Deionized water was ultrapure water, and the resistivity was 18.2 M.OMEGA.. cm.
In the technical scheme of the invention, the reaction container can be a surface dish, a weighing bottle, a culture dish, a glass water tank or a glass jar and the like, and the area of the obtained two-dimensional polymer film can be 1um according to the difference of the areas of the reaction containers2-1m2. In each of examples 1 to 3, a weighing bottle having a diameter of 7cm was used as a reaction vessel, and thus, the two-dimensional polymer films of examples 1 to 3 were all circular in shape having a diameter of 7cm, and the two-dimensional polymer films of examples 4 to 6 were all two-dimensional polymer films cut to 1 × 1 cm.
The technical scheme of the invention is further explained by combining specific examples.
Example 1
A method for preparing a two-dimensional polymer film, comprising the steps of:
preparing aromatic polyamine mixed solution in a weighing bottle with the diameter of 7cm, dripping the aromatic polyaldehyde mixed solution on the liquid surface of the aromatic polyamine mixed solution, covering the cover of the weighing bottle, clamping a filter paper strip with the width of 0.5cm between the cover and the bottle body of the weighing bottle (the filter paper strip is clamped for reserving a plurality of gaps to volatilize the aromatic organic solvent B), placing the mixture at the room temperature of 20-25 ℃ until the volatilization of the aromatic organic solvent B in the aromatic polyaldehyde mixed solution is finished (the placing time is 24 hours), and obtaining a two-dimensional polymer film with the thickness of 20nm on the liquid surface, wherein,
the ratio of the amount of the aromatic polyaldehyde in the aromatic polyaldehyde mixed solution to the amount of the aromatic polyamine in the aromatic polyamine mixed solution is 0.00167: 0.01389;
the preparation method of the aromatic polyamine mixed solution comprises the following steps: uniformly distributing aromatic polyamine in an organic solvent A to obtain a solution A, adding deionized water into the solution A and uniformly mixing to obtain a light brown aromatic polyamine mixed solution, wherein the ratio of the volume parts of the deionized water to the mass parts of the aromatic polyamine is 1: 0.01389. the concentration of the aromatic polyamine in the solution A is 1.2mmol/mL, the organic solvent A is an aprotic organic reagent which is mutually soluble with water, and the organic solvent A is N, N-dimethylformamide.
The preparation method of the aromatic polyaldehyde mixed solution comprises the following steps: uniformly distributing aromatic polyaldehyde in an aromatic organic solvent B to obtain a solution B, and adding an organic acid into the solution B to obtain an aromatic polyaldehyde mixed solution, wherein the ratio of the volume parts of the aromatic organic solvent B to the mass parts of the aromatic polyaldehyde is 1: 0.00167, the volume of organic acid is 1% of the volume of solution B;
the organic acid is acetic acid;
the aromatic organic solvent B is chlorobenzene.
The aromatic polyaldehyde is trimesic aldehyde.
The aromatic polyamine is p-phenylenediamine.
Example 2
A method for preparing a two-dimensional polymer film, comprising the steps of:
preparing an aromatic polyamine mixed solution in a weighing bottle with the diameter of 7cm, dripping the aromatic polyaldehyde mixed solution on the liquid surface of the aromatic polyamine mixed solution, covering a cover of the weighing bottle, clamping a filter paper strip with the width of 0.5cm between the cover and a bottle body of the weighing bottle, placing the bottle at the room temperature of 20-25 ℃ until the volatilization of the aromatic organic solvent B in the aromatic polyaldehyde mixed solution is finished (the placing time is 36 hours), and obtaining a two-dimensional polymer film with the thickness of 50nm on the liquid surface, wherein,
ratio 0.00333 of the amount of aromatic polyaldehyde in the aromatic polyaldehyde mixed solution to the amount of aromatic polyamine in the aromatic polyamine mixed solution: 0.01389;
the preparation method of the aromatic polyamine mixed solution comprises the following steps: uniformly distributing aromatic polyamine in an organic solvent A to obtain a solution A, adding deionized water into the solution A and uniformly mixing to obtain a light brown aromatic polyamine mixed solution, wherein the ratio of the volume parts of the deionized water to the mass parts of the aromatic polyamine is 1: 0.01389. the concentration of the aromatic polyamine in the solution A is 1.2mmol/mL, the organic solvent A is an aprotic organic reagent which is mutually soluble with water, and the organic solvent A is N, N-dimethylformamide.
The preparation method of the aromatic polyaldehyde mixed solution comprises the following steps: uniformly distributing aromatic polyaldehyde in an aromatic organic solvent B to obtain a solution B, and adding an organic acid into the solution B to obtain an aromatic polyaldehyde mixed solution, wherein the ratio of the volume parts of the aromatic organic solvent B to the mass parts of the aromatic polyaldehyde is 1: 0.00333, the volume of the organic acid is 1% of the volume of the solution B;
the organic acid is acetic acid;
the aromatic organic solvent B is chlorobenzene.
The aromatic polyaldehyde is trimesic aldehyde.
The aromatic polyamine is p-phenylenediamine.
Example 3
A method for preparing a two-dimensional polymer film, comprising the steps of:
preparing an aromatic polyamine mixed solution in a weighing bottle with the diameter of 7cm, dripping the aromatic polyaldehyde mixed solution on the liquid surface of the aromatic polyamine mixed solution, covering a cover of the weighing bottle, clamping a filter paper strip with the width of 0.5cm between the cover and a bottle body of the weighing bottle, placing the bottle at the room temperature of 20-25 ℃ until the volatilization of the aromatic organic solvent B in the aromatic polyaldehyde mixed solution is finished (the placing time is 48 hours), and obtaining a two-dimensional polymer film with the thickness of 70nm on the liquid surface, wherein,
the ratio of the amount of the aromatic polyaldehyde in the aromatic polyaldehyde mixed solution to the amount of the aromatic polyamine in the aromatic polyamine mixed solution is 0.005: 0.01389;
the preparation method of the aromatic polyamine mixed solution comprises the following steps: uniformly distributing aromatic polyamine in an organic solvent A to obtain a solution A, adding deionized water into the solution A and uniformly mixing to obtain a light brown aromatic polyamine mixed solution, wherein the ratio of the volume parts of the deionized water to the mass parts of the aromatic polyamine is 1: 0.01389. the concentration of the aromatic polyamine in the solution A is 1.2mmol/mL, the organic solvent A is an aprotic organic reagent which is mutually soluble with water, and the organic solvent A is N, N-dimethylformamide.
The preparation method of the aromatic polyaldehyde mixed solution comprises the following steps: uniformly distributing aromatic polyaldehyde in an aromatic organic solvent B to obtain a solution B, and adding an organic acid into the solution B to obtain an aromatic polyaldehyde mixed solution, wherein the ratio of the volume parts of the aromatic organic solvent B to the mass parts of the aromatic polyaldehyde is 1: 0.005, the volume of the organic acid is 1% of the volume of the solution B;
the organic acid is acetic acid;
the aromatic organic solvent B is chlorobenzene.
The aromatic polyaldehyde is trimesic aldehyde.
The aromatic polyamine is p-phenylenediamine.
FIG. 2 is an atomic force microscope characterization feature of the two-dimensional polymer thin films prepared in examples 1-3, wherein 2(a) is the two-dimensional polymer thin film prepared in example 1, and the thickness is 20 nm; 2(b) is the two-dimensional polymer film prepared in example 2, 50nm thick; 2(c) is the two-dimensional polymer film prepared in example 3, having a thickness of 70 nm; as can be seen from the figure, the two-dimensional polymer film prepared by the invention has good uniformity, and the roughness in 10um is respectively 0.2nm (example 1), 0.7nm (example 2) and 1.8nm (example 3), and the roughness is lower.
After the two-dimensional polymer films (2DP) obtained in examples 1 to 3 were washed by immersing them in DMF, dichloromethane, chloroform, and acetone for 5 hours, the 2DP material was found to be present stably.
Example 4
The two-dimensional polymer film prepared in the embodiment 1 is used as an active layer to obtain a memristor, and the memristor sequentially comprises the following components from top to bottom: an active electrode, a two-dimensional polymer film, and an inert electrode, as shown in fig. 1. The active electrode is a silver layer with the thickness of 50 nm; the inert electrode is an ITO conductive glass layer. The preparation method of the memristor comprises the following steps:
a) transferring the two-dimensional polymer film to the upper surface of an inert electrode, and carrying out vacuum drying for 8 hours in a vacuum drying oven at 30 ℃;
b) and evaporating the active electrode on the two-dimensional polymer film. The method for evaporating the silver layer comprises the following steps: using 100/400 copper mesh as mask plate, and sticking it on the upper surface of two-dimensional polymer film (mesh number of copper mesh is 200 meshes) to obtain
And depositing a silver layer with the thickness of 50nm at the speed of (1), and taking down the copper mesh after the deposition is finished to finish the evaporation of the silver layer.
FIG. 3 is a plot of turn-on and erase for memristors obtained from example 4 (using a 20nm thick two-dimensional polymer film); when a device is tested, the ITO (ITO conductive glass layer) is grounded, and voltage is applied to the Ag electrode (silver layer) with the step length of 0.02V. In FIG. 3, 1 refers to the curve of the scanning process from 0V to 1.5V, 2 refers to the curve of the scanning from 1.5 to 0V, and the limited current of the curves 1 and 2 at the time of test is 10-3(ii) a 3 refers to the curve that occurs from a 0-3.3V sweep, 4 refers to the curve that occurs from a 3.3-0V sweep, and the limiting current for curves 3 and 4 is 10-2. Curves 1 and 2 are the memristor write process, equivalent to the information storage step, and curves 3 and 4 are the memristor erase process. As can be seen from fig. 3, the memristor prepared from the two-dimensional polymer thin film obtained in example 1 can perform complete writing and erasing processes.
Fig. 4 is a statistic of the cycling stability of the memristor obtained in example 4, and when the same device (memristor) is repeatedly turned on and erased, it is found that the device with the two-dimensional polymer thin film with the thickness as the active layer can perform 100 times of normal operations.
FIG. 5 is statistics of high and low resistance states of memristors from example 4; starting and erasing operations are carried out on the memristors prepared from the two-dimensional polymer thin film with the thickness of 20nm in the same batch, the high-low resistance state values of 200 devices at-0.1V are counted, and as can be seen from fig. 5, the switching ratio of the memristor prepared from the two-dimensional polymer thin film with the thickness of 20nm is found to be 102Magnitude.
FIG. 6 is a graph of retention time of memristors from example 4 read with a voltage of 0.1V; after the writing operation is carried out on the device, the voltage of 0.1V is used for reading the device, and the retention time of the device in a low resistance state is obtained; after erasing the same device, the device is read with 0.1V voltage to obtain the retention time of the device in the high-resistance state. The two retention time curves obtained are plotted in the same graph, and the reading time of the device at the thickness under the voltage of 0.1V is 8 x 103s。
Example 5
The two-dimensional polymer film prepared in the embodiment 2 is used as an active layer to obtain a memristor, and the memristor sequentially comprises the following components from top to bottom: the device comprises an active electrode, a two-dimensional polymer film and an inert electrode, wherein the active electrode is a silver layer and has the thickness of 50 nm; the inert electrode is an ITO conductive glass layer. The preparation method of the memristor comprises the following steps:
a) transferring the two-dimensional polymer film to the upper surface of an inert electrode, and carrying out vacuum drying for 8 hours in a vacuum drying oven at 30 ℃;
b) and evaporating the active electrode on the two-dimensional polymer film. The method for evaporating the silver layer comprises the following steps: using 100/400 copper mesh as mask plate, and sticking it on the upper surface of two-dimensional polymer film (mesh number of copper mesh is 200 meshes) to obtain
And depositing a silver layer with the thickness of 50nm at the speed of (1), and taking down the copper mesh after the deposition is finished to finish the evaporation of the silver layer.
FIG. 7 is a plot of turn-on and erase of memristors from example 5; when testing the device, the ITO is grounded, and a voltage is applied to the Ag electrode with a step size of 0.02V. In FIG. 7, 1 refers to the curve of the scanning process from 0V to 1.5V, 2 refers to the curve of the scanning from 1.5 to 0V, and the limiting current of the curves 1 and 2 at the time of test is 10-3(ii) a 3 refers to the curve that occurs from a 0-3.3V sweep, 4 refers to the curve that occurs from a 3.3-0V sweep, and the limiting current for curves 3 and 4 is 10-2. Curves 1 and 2 are the writing process of the memristor, which is equivalent to the step of information storage, and curves 3 and 4 are the erasing process of the memristor. As can be seen, the memristor prepared by the two-dimensional polymer film with the thickness of 50nm can carry out complete writing and erasing processes.
Fig. 8 is statistics of the cycling stability of the memristor obtained in example 5, and the cycling stability test was performed on the memristor prepared from a 50nm thick two-dimensional polymer thin film. After repeated opening and erasing operations of the same device, the device with the two-dimensional polymer film with the thickness as the active layer can perform 180 times of normal operations.
FIG. 9 shows the high and low resistance states of the memristor obtained in example 5Statistics (using a 50nm thick two-dimensional polymer film); starting and erasing operations are carried out on memristors prepared by 50nm thick two-dimensional polymer films in the same batch, and the high-low resistance state values of 200 devices at-0.1V are counted, as shown in FIG. 9, the on-off ratio of the memristors prepared by the 50nm thick two-dimensional polymer is found to be 104Magnitude.
FIG. 10 is a graph of the retention time of memristors obtained from example 5 read with a voltage of 0.1V (using a 50nm thick two-dimensional polymer film); as can be seen from the figure, after the device is written, the device is read by using the voltage of 0.1V, and the retention time of the device in the low resistance state is obtained; after the same device is erased, the device is read by using 0.1V voltage, and the retention time of the device in a high-resistance state is obtained. The two retention time curves obtained are plotted in the same graph, and the reading time of the device at the thickness under the voltage of 0.1V is 1 x 104s。
Example 6
The two-dimensional polymer film prepared in the embodiment 3 is used as an active layer to obtain a memristor, and the memristor sequentially comprises the following components from top to bottom: the device comprises an active electrode, a two-dimensional polymer film and an inert electrode, wherein the active electrode is a silver layer and has the thickness of 50 nm; the inert electrode is an ITO conductive glass layer. The preparation method of the memristor comprises the following steps:
a) transferring the two-dimensional polymer film to the upper surface of an inert electrode, and carrying out vacuum drying for 8 hours in a vacuum drying oven at 30 ℃;
b) and evaporating the active electrode on the two-dimensional polymer film. The method for evaporating the silver layer comprises the following steps: using 100/400 copper mesh as mask plate, and sticking it on the upper surface of two-dimensional polymer film (mesh number of copper mesh is 200 meshes) to obtain
And depositing a silver layer with the thickness of 50nm at the speed of (1), and taking down the copper mesh after the deposition is finished to finish the evaporation of the silver layer.
FIG. 11 is a plot of turn-on and erase for memristors from example 6 (using a 70nm thick two-dimensional polymer film); when testing the device, the ITO is grounded, and a voltage is applied to the Ag electrode with a step size of 0.02V. In FIG. 11, 1 refers toThe curve of the scanning process from 0V to 1.5V, 2 refers to the curve scanned from 1.5 to 0V, and the limiting current of the curves 1 and 2 is 10 when testing-3(ii) a 3 refers to the curve that occurs from a 0-3.3V sweep, 4 refers to the curve that occurs from a 3.3-0V sweep, and the limiting current for curves 3 and 4 is 10-2. Curves 1 and 2 are the memristor write process, equivalent to the information storage step, and curves 3 and 4 are the memristor erase process. It can be seen that a device made of a two-dimensional polymer 70nm thick can perform the complete writing and erasing process.
FIG. 12 is a statistic of the cycling stability of memristors obtained in example 6 (using a 70nm thick two-dimensional polymer film); and (3) carrying out a cycling stability test on the memristor prepared by the 70nm thick two-dimensional polymer film. In the repeated opening and erasing operations of the same device, the device with the two-dimensional polymer as the active layer with the thickness can perform 200 times of normal operations.
FIG. 13 is a statistic of the high and low resistance states of the memristor obtained in example 6 (using a 70nm thick two-dimensional polymer film); starting and erasing operations are carried out on memristors prepared by 70nm thick two-dimensional polymer films in the same batch, the high-low resistance state values of 200 devices at-0.1V are counted, a graph 13 is drawn, and the switching ratio of the memristors prepared by the 70nm thick two-dimensional polymer films is found to be 105Magnitude.
FIG. 14 is a graph of the retention time of the memristor from example 6 read with a voltage of 0.1V (using a 70nm thick two-dimensional polymer film), after a write operation is performed on the device, the retention time of the device in the low resistance state is obtained by reading the device with a voltage of 0.1V; after the same device is erased, the device is read by using 0.1V voltage, and the retention time of the device in a high-resistance state is obtained. The two retention times obtained were plotted in the same graph, and the device at this thickness had a read time of 3.5 x 10 at 0.1V4s。
Fig. 15 is a graph showing nitrogen adsorption/desorption of the two-dimensional polymer film prepared in example 2. As can be seen, this curve is a type I absorption curve, but the desorption curve does not coincide with the adsorption curve, indicating that a portion of the nitrogen is fixed at 2DPBTA+PDAThus proving the presence of micropores in the material. The specific surface area of the material was calculated to be 74.4m2Per g, pore volume 8.82X 10-2cm3(ii) in terms of/g. 2DP is calculated by the data of fig. 15 through the theory of non-localized density functionBTA+PDAThe pore diameter of the (two-dimensional polymer film) was 1.41nm, as shown in FIG. 16. (type of apparatus used in FIGS. 15 and 16: JB-2020 type specific surface area tester)
FIG. 17 is a Fourier transform infrared spectrum of a two-dimensional polymer film obtained in example 2, 3392cm-1Is N-H bond stretching vibration, 2292cm-1is-NH on unreacted aromatic polyamine monomer2Stretching vibration of 1694cm-1Is the stretching vibration of C ═ O reacted on the molecule of aromatic polyaldehyde BTA, 1621cm-1Is the C-N stretching vibration generated by the reaction of aromatic polyaldehyde and aromatic polyamine with Schiff base, 1260cm-1Is the C-N bond stretching vibration of the benzene ring and the nitrogen atom. The existence of 1621 characteristic peak indicates that aromatic polyaldehyde and aromatic polyamine are actually subjected to Schiff base reaction under the catalysis of organic acid, and the generated 2DP is polymerized by two monomers under the reaction of Schiff base. (apparatus model: Brookvertex 80/80 v.)
As can be seen from fig. 18, the two-dimensional polymer film is a material having an amorphous structure. As can be seen from fig. 19, the image shows a diffraction ring phenomenon, which indicates that the material is in an amorphous state, and the result of fig. 18 is verified. (apparatus used: Hitachi HT7800)
In the technical scheme of the invention, the technical effect is consistent with the above embodiment by changing N, N-dimethylformamide into N, N-dimethylacetamide or dimethyl sulfoxide, or changing acetic acid into trifluoroacetic acid or trifluoromethanesulfonic acid, or changing chlorobenzene into dichlorobenzene or toluene.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (8)
1. A method for preparing a two-dimensional polymer film, comprising the steps of:
dripping the aromatic polyaldehyde mixed solution on the liquid surface of the aromatic polyamine mixed solution, placing the solution at the room temperature of 20-25 ℃ until the aromatic organic solvent B in the aromatic polyaldehyde mixed solution is completely volatilized, and obtaining a two-dimensional polymer film on the liquid surface, wherein,
the ratio of the amount of the aromatic polyaldehyde in the aromatic polyaldehyde mixed solution to the amount of the aromatic polyamine in the aromatic polyamine mixed solution (0.0015 to 0.005): 0.01389;
the preparation method of the aromatic polyamine mixed solution comprises the following steps: uniformly distributing aromatic polyamine in an organic solvent A to obtain a solution A, adding deionized water into the solution A, and uniformly mixing to obtain a light brown aromatic polyamine mixed solution, wherein the concentration of the aromatic polyamine in the solution A is 0.185-4.63 mmol/mL, and the organic solvent A is an aprotic organic reagent mutually soluble with water;
the preparation method of the aromatic polyaldehyde mixed solution comprises the following steps: uniformly distributing aromatic polyaldehyde in an aromatic organic solvent B to obtain a solution B, and adding an organic acid into the solution B to obtain an aromatic polyaldehyde mixed solution, wherein the ratio of the volume parts of the aromatic organic solvent B to the mass parts of the aromatic polyaldehyde is (0.5-1): (0.0008 to 0.01), the volume of the organic acid being 0.7 to 1.5% of the volume of the solution B;
the organic acid is acetic acid, trifluoroacetic acid or trifluoromethanesulfonic acid;
the aromatic organic solvent B is chlorobenzene, dichlorobenzene or toluene, the aromatic polyaldehyde is trimesic aldehyde, and the aromatic polyamine is p-phenylenediamine.
2. The method according to claim 1, wherein the organic solvent A is N, N-dimethylformamide, N-dimethylacetamide, or dimethylsulfoxide.
3. The method according to claim 2, wherein the time taken for the aromatic organic solvent B in the aromatic polyaldehyde mixture solution to evaporate is at least 24 hours.
4. The method according to claim 3, wherein the ratio of parts by volume of the deionized water to parts by weight of the aromatic polyamine substance in the aromatic polyamine mixed solution is 1: (0.005-0.03).
5. The method of claim 4, wherein the volume fraction is in mL and the quantity fraction is in mmol.
6. The preparation method according to claim 5, wherein the deionized water is ultrapure water, and the resistivity is 18.2 Μ Ω.
7. A two-dimensional polymer film obtained by the production method according to any one of claims 1 to 6.
8. The two-dimensional polymer film according to claim 7, wherein the thickness of the two-dimensional polymer film is 2 to 80 nm.
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