CN115376757A - Oxidation-resistant copper nanowire transparent electrode and preparation method and application thereof - Google Patents
Oxidation-resistant copper nanowire transparent electrode and preparation method and application thereof Download PDFInfo
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 38
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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Abstract
The invention provides an antioxidant copper nanowire transparent electrode and a preparation method and application thereof, and belongs to the technical field of magnetic sensing. The preparation method of the oxidation-resistant copper nanowire transparent electrode comprises the steps of cleaning and purifying a copper nanowire stock solution, spraying the copper nanowire stock solution at high pressure to form a film, carrying out acid washing and argon plasma treatment, and finally depositing an aluminum oxide protective layer on a copper nanowire conductive network by an Atomic Layer Deposition (ALD) technology to form a heterostructure taking the copper nanowire as a core and the aluminum oxide as a shell, so that the oxidation-resistant copper nanowire transparent electrode is obtained. The aluminum oxide deposited by the atomic layer is compact, good in isolation effect and strong in oxidation resistance; the thickness of the introduced alumina shell is uniform and nano-level, and almost has no influence on the light transmittance and the sheet resistance of the transparent electrode; the argon plasma treatment can play a role in welding the copper nanowire conductive network, greatly reduces the contact resistance and improves the conductivity.
Description
Technical Field
The invention belongs to the technical field of magnetic sensing, and relates to an antioxidant copper nanowire transparent electrode and a preparation method and application thereof.
Background
The metal nanowires are widely concerned in the field of flexible display electronics due to excellent optical properties, electrical properties, mechanical properties and thermal properties. Among the metal nanowires, the copper nanowires have very obvious advantages in production cost and have great economic research value. However, the newly synthesized copper nanowire is attached with a coating agent and a metal oxide on the surface, so that the conduction of the copper nanowire network is influenced; the copper added with the copper has more active metal property, when the copper reaches the nano level, the specific surface area is enlarged, the effective contact area with oxygen and water vapor is enlarged, the oxidation corrosion is aggravated, the sheet resistance of the copper nanowire conductive network which is not subjected to protection treatment at normal temperature is sharply increased in a short time, the defects are also very obvious, and the development and the application of the copper nanowire conductive network are limited to a great extent.
In the prior art, chinese patent publication No. CN108707997a discloses a method for preparing a reduced graphene oxide coated copper nanowire composite material, wherein reduced graphene oxide is used to coat a copper nanowire, so that oxidation resistance is improved in a short period, but the process is too complicated, the conductivity of the reduced graphene oxide is good, and if the copper nanowire is coated for a long period, electrochemical reaction occurs, and corrosion of the copper nanowire is accelerated. Chinese patent publication No. CN106536094a discloses silver-coated copper nanowires and a method for preparing the same by using piperazine (C) 4 H 10 N 2 ) And/or hexamethylenediamine (C) 6 H 16 N 2 ) The chemical method of (1) synthesizing copper nano-wire, then coating the copper nano-wire with silver by using chemical plating method, thereby preventing oxidation of the copper nano-wire, the method greatly improves oxidation resistance, but the chemical plating method is difficult to control the thickness of silver plating layer, and is easy to generate large silver particles, which greatly affects optical performance after film forming, and expensive cost also limits large-scale popularization. As can be seen, the prior art copper nanowire anti-oxidation treatment methodBut the defects of uneven oxidation resistant coating layer on the surface of the copper nanowire, serious reduction of light transmittance, weak oxidation resistance or excessively complex operation and the like always exist.
Therefore, a copper nanowire transparent electrode having high transparency, low sheet resistance and strong oxidation resistance, and a preparation method and an application thereof are urgently needed to be researched.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing an oxidation-resistant copper nanowire transparent electrode, in which an ALD technology is used to deposit an alumina protective layer on a copper nanowire conductive network to prepare a copper nanowire transparent electrode with high oxidation resistance, so that the copper nanowire transparent electrode has high transparency, low sheet resistance and high oxidation resistance, thereby solving the problems in the prior art in whole or in part.
In order to achieve the purpose, the invention provides a preparation method of an oxidation-resistant copper nanowire transparent electrode, which comprises the following steps:
s1: taking a copper nanowire stock solution prepared by a liquid phase method, cleaning by adopting a non-polar organic solvent, carrying out centrifugal separation, and dissolving the obtained copper nanowire in absolute ethyl alcohol to obtain a copper nanowire dispersion solution;
s2: diluting the copper nanowire dispersion liquid obtained in the step S1 with deionized water, and carrying out ultrasonic treatment;
s3: adding an organic acid solution into the solution obtained in the step S2, and simultaneously carrying out ultrasonic treatment to remove the coating agent on the surface of the copper nanowire;
s4: filtering and purifying the solution obtained in the step S3 by using a filter membrane, and then re-dissolving the copper nanowires in absolute ethyl alcohol;
s5: repeating the diluting in the step S2 and the filtering, purifying and re-dissolving processes of the filter membrane in the step S4 to obtain copper nanowire spraying liquid for later use;
s6: carrying out high-pressure spraying on the spraying liquid obtained in the step S5 on a flexible substrate to form a film, and simultaneously heating and evaporating a solvent at the bottom of the flexible substrate by using a heating table to obtain a copper nanowire film;
s7: adding the copper nanowire film obtained in the step S6 into the organic acid solution for soaking treatment, then rinsing with absolute ethyl alcohol, and then drying in vacuum to obtain a copper nanowire transparent electrode preliminarily;
s8: performing argon plasma treatment on the copper nanowire transparent electrode obtained in the step S7, and then performing vacuum storage to obtain a copper nanowire transparent electrode with stronger conductivity;
s9: and depositing an aluminum oxide protective layer on the surface of the copper nanowire transparent electrode obtained in the step S8 by adopting an atomic layer deposition technology to obtain the antioxidant copper nanowire transparent electrode.
Preferably, the nonpolar organic solvent in step S1 is at least one of petroleum ether, n-hexane, toluene, and benzene; in the copper nanowire dispersion liquid obtained in the step S1, the weight percentage of the copper nanowires is 0.010-0.150 wt%.
Preferably, in the diluted copper nanowire dispersion liquid in the step S2, the weight percentage of the copper nanowires is 0.002 to 0.030wt%, and the ultrasonic time in the step S2 is 0.5 to 60min.
Preferably, in steps S3 and S7, the organic acid solution is an aqueous solution of an organic acid, the organic acid is at least one selected from acetic acid, citric acid, tartaric acid, benzoic acid, ascorbic acid, malic acid and salicylic acid, and the concentration of the organic acid solution is 0.1 to 10wt%; in the step S3, the volume of the added organic acid solution is 10-100 mL, and the ultrasonic time is 0.5-60 min; in the step S7, the time of acid soaking treatment is 0.5-10 min.
Preferably, the pore diameter of the filter membrane used in the step S4 is 220 nm-8 μm; in the copper nanowire dispersion liquid obtained by re-dissolving in the step S4, the weight percentage of the copper nanowires is 0.010-0.150 wt%; in the copper nanowire spraying solution obtained in the step S5, the weight percentage of the copper nanowires is 0.010-0.150 wt%.
Preferably, before the step S6, the method further includes performing pretreatment on the flexible substrate, where the pretreatment specifically includes: firstly, absolute ethyl alcohol is used for cleaning the flexible substrate, and then the flexible substrate is dried and then is subjected to activation treatment of oxygen plasma, wherein the power is 300-500W, the oxygen gas flow is 10-300 SCCM, and the treatment time is 3-300 min.
Preferably, in step S6, the flexible substrate is made of one of polyethylene terephthalate (PET), polydimethylsiloxane, polymethyl methacrylate, polyurethane and polytetrafluoroethylene; the step S6 specifically includes: the flexible substrate is placed on a heating table to be preheated for 1-20 min, then the temperature of the heating table is controlled to be 50-120 ℃, and then high-pressure spraying is carried out to form a film.
Preferably, in the step S8, the power of the argon plasma treatment is 300-500W, the argon flow is 10-300 SCCM, and the treatment time is 1-20 min; the vacuum storage pressure is-12 to-15 psi.
Preferably, in step S9, the number of cycles of atomic layer deposition is 50 to 500, and the thickness of the alumina protective layer is 5 to 50nm.
The invention also provides the oxidation-resistant copper nanowire transparent electrode prepared by the preparation method.
The invention also provides an application of the copper nanowire transparent electrode in the field of transparent flexible electrodes.
The invention adopts the technical scheme that the method has the advantages that:
the preparation method of the oxidation-resistant copper nanowire transparent electrode comprises the steps of cleaning and purifying a copper nanowire stock solution, spraying the copper nanowire stock solution at high pressure to form a film, carrying out acid washing and argon plasma treatment, and finally depositing an aluminum oxide protective layer on a copper nanowire conductive network by an Atomic Layer Deposition (ALD) technology to form a heterostructure taking the copper nanowire as an inner core and the aluminum oxide as an outer shell, so as to obtain the oxidation-resistant copper nanowire transparent electrode. The invention adopts a coating process of high-pressure spraying, and simultaneously, the solvent is removed by heating and evaporating the bottom to obtain a copper nanowire network with uniform dispersion; the alumina deposited by the atomic layer is compact, has good isolation effect and longer duration of oxidation resistance; the thickness of the introduced alumina shell is uniform and nano-level, and almost has no influence on the light transmittance and the sheet resistance of the transparent electrode; the argon plasma treatment can play a role in welding the copper nanowire conductive network, greatly reduces the contact resistance and improves the conductivity. The copper nanowire transparent electrode prepared by the method has strong oxidation resistance, and also has excellent electrical property, optical property and bending resistance, so that the copper nanowire transparent electrode has great potential in the field of flexible display electronics.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows the sheet resistance change rate (R/R) of the copper nanowire transparent electrodes of examples 1 and 2 of the present invention stored at room temperature 0 ) A graph of change over time;
fig. 2 is an SEM image of the copper nanowire transparent electrode in example 1 of the present invention after being stored at room temperature for 14 days;
fig. 3 is an SEM image of the copper nanowire transparent electrode in example 2 of the present invention after being stored at room temperature for 14 days;
FIG. 4 shows the sheet resistance change rate (R/R) of the copper nanowire transparent electrodes in examples 3 and 4 of the present invention when the electrodes are stored at 85 ℃ and 85% relative humidity 0 ) A graph of change over time;
FIG. 5 is an SEM image of the copper nanowire transparent electrode in example 3 of the present invention after being stored at 85 ℃ and 85% relative humidity for 15 days;
fig. 6 is an SEM image of the copper nanowire transparent electrode in example 4 of the present invention, which was stored at 85 ℃ and 85% relative humidity for 80 min.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a preparation method of an antioxidant copper nanowire transparent electrode, which comprises the following steps:
s1: taking a copper nanowire stock solution prepared by a liquid phase method, cleaning by adopting a non-polar organic solvent, carrying out centrifugal separation, and dissolving the obtained copper nanowire in absolute ethyl alcohol to obtain a copper nanowire dispersion solution;
s2: diluting the copper nanowire dispersion liquid obtained in the step S1 with deionized water, and carrying out ultrasonic treatment;
s3: adding an organic acid solution into the solution obtained in the step S2, and simultaneously carrying out ultrasonic treatment to remove the coating agent on the surface of the copper nanowire;
s4: filtering and purifying the solution obtained in the step S3 by using a filter membrane, and then re-dissolving the copper nanowires in absolute ethyl alcohol;
s5: repeating the diluting in the step S2 and the filtering, purifying and re-dissolving processes of the filter membrane in the step S4 to obtain copper nanowire spraying liquid for later use;
s6: carrying out high-pressure spraying on the spraying liquid obtained in the step S5 on a flexible substrate to form a film, and simultaneously heating and evaporating a solvent at the bottom of the flexible substrate by using a heating table to obtain a copper nanowire film;
s7: adding the copper nanowire film obtained in the step S6 into the organic acid solution for soaking treatment, then rinsing with absolute ethyl alcohol, and then drying in vacuum to obtain a copper nanowire transparent electrode preliminarily;
s8: performing argon plasma treatment on the copper nanowire transparent electrode obtained in the step S7, and then performing vacuum storage to obtain a copper nanowire transparent electrode with higher conductivity;
s9: and depositing an aluminum oxide protective layer on the surface of the copper nanowire transparent electrode obtained in the step S8 by adopting an atomic layer deposition technology to obtain the antioxidant copper nanowire transparent electrode.
In the above steps S3 and S7, the coating agent is removed by acid washing or acid treatment with an organic acid solution, and the principle of removing the coating agent by acid washing is as follows: cu on the surface of the copper nanowire in the process of synthesizing the copper nanowire 2+ (mainly from CuO) and coatingOf the agent-NH 2 Complexing to form a complex, wherein the complex cannot be completely removed by conventional cleaning; citric acid is introduced to generate chemical reaction of CuO +2H + ＝H 2 O+Cu 2+ The metal oxide is stripped from the surface of the copper nanowire, and the coating agent is stripped along with the metal oxide. The coating agent on the surface of the copper nanowire can be completely peeled off after 2 times of acid washing.
In the step S6, a coating process of high pressure spraying is adopted, and simultaneously heat treatment is performed to evaporate and remove the solvent, so as to obtain the copper nanowire network with uniform dispersion.
In the step S8, the argon plasma treatment is adopted, so that the welding effect can be achieved, the contact resistance between the copper nanowires is greatly reduced, and the conductivity of the transparent electrode is improved. The principle of argon plasma welding is as follows: argon plasma airflow improves the surface energy of the copper nanowire, so that copper atoms are diffused on the surface; in addition, the surface plasma resonance effect exists at the junction of the contact points of the copper nanowires, so that the absorption of electrons to light energy is greatly increased, the temperature of the junction is increased, and local nano welding is realized, wherein the temperature of the nano welding is far lower than the melting point of the material.
In the step S9, the aluminum oxide protective layer is deposited on the copper nanowire conductive network by adopting the atomic layer deposition technology, a heterostructure taking the copper nanowires as a core and the aluminum oxide as a shell is formed, the compact aluminum oxide shell has a barrier effect on oxygen and water vapor, the condition of oxidation corrosion of the copper nanowires is destroyed, the isolation effect is good, the duration time of the oxidation resistance is longer, and the oxidation resistance stability of the copper nanowire transparent electrode is greatly improved. In addition, the thickness of the introduced alumina shell is uniform in nanometer level, and the transparency and the sheet resistance of the transparent electrode are hardly influenced.
Preferably, the nonpolar solvent in the step S1 is one or more of petroleum ether, n-hexane, toluene and benzene; for the copper nanowire dispersion liquid obtained in the step S1, the weight percentage of the copper nanowire is 0.010-0.150 wt%;
preferably, for the copper nanowire dispersion liquid obtained in step S2, the weight percentage of the copper nanowires is 0.002 to 0.030wt%, and the ultrasonic time in step S2 is 0.5 to 60min.
Preferably, in steps S3 and S7, the organic acid solution is an aqueous solution of an organic acid, and is prepared by selecting one or more of acetic acid, citric acid, tartaric acid, benzoic acid, ascorbic acid, malic acid, and salicylic acid, and the concentration of the organic acid solution is 0.1 to 10wt%; in the step S3, the volume of the added acid solution is 10-100 mL, and the ultrasonic time is 0.5-60 min; in the step S7, the time of acid soaking treatment is 0.5-10 min.
Preferably, the filter pore size used in step S4 is 220nm to 8 μm; for the copper nanowire dispersion liquid obtained in the step S4, the weight percentage of the copper nanowire is 0.010-0.150 wt%; in the copper nanowire spraying solution obtained in the step S5, the weight percentage of the copper nanowires is 0.010-0.150 wt%.
Preferably, in step S6, the flexible substrate needs to be pretreated, and the pretreatment specifically includes: firstly, absolute ethyl alcohol is used for cleaning the flexible substrate, and then activation treatment of oxygen plasma is carried out after drying, the power is 300-500W, the oxygen gas flow is 10-300 SCCM, and the treatment time is 3-300 min.
Preferably, the material of the flexible substrate in step S6 is one of polyethylene terephthalate (PET), polydimethylsiloxane, polymethyl methacrylate, polyurethane and polytetrafluoroethylene; the step S6 specifically includes: the flexible substrate is placed on a heating table to be preheated for 1-20 min, then the temperature of the heating table is controlled to be 50-120 ℃, and then high-pressure spraying is carried out to form a film.
Preferably, in the step S8, the power of the argon plasma treatment is 300-500W, the argon flow is 10-300 SCCM, and the treatment time is 1-20 min; the vacuum storage pressure is-12 to-15 psi.
Preferably, in step S9, the number of cycles of atomic layer deposition is 50 to 500, and the thickness of the aluminum oxide layer is 5 to 50nm.
The preparation method of the oxidation-resistant copper nanowire transparent electrode comprises the steps of cleaning and purifying a copper nanowire stock solution, spraying the copper nanowire stock solution at high pressure to form a film, carrying out acid washing and argon plasma treatment, and finally depositing an aluminum oxide protective layer on a copper nanowire conductive network by an Atomic Layer Deposition (ALD) technology to form a heterostructure taking the copper nanowire as a core and the aluminum oxide as a shell, so that the oxidation-resistant copper nanowire transparent electrode is obtained. The invention adopts a coating process of high-pressure spraying, simultaneously carries out heating treatment, evaporates and removes a solvent, and obtains a copper nanowire network with uniform dispersion; the alumina deposited by the atomic layer is compact, the isolation effect is good, and the duration of the oxidation resistance is longer; the thickness of the introduced alumina shell is uniform and nano-level, and almost has no influence on the light transmittance and the sheet resistance of the transparent electrode; the argon plasma treatment can play a role in welding the copper nanowire conductive network, greatly reduces the contact resistance and improves the conductivity.
The invention also provides the oxidation-resistant copper nanowire transparent electrode prepared by the preparation method, which has strong oxidation resistance, and also has excellent electrical property, optical property and bending resistance, so that the oxidation-resistant copper nanowire transparent electrode has great potential in the field of flexible display electronics.
The invention also provides an application of the copper nanowire transparent electrode in the field of transparent flexible electrodes.
Example 1
An oxidation-resistant copper nanowire transparent electrode is prepared by the following steps:
s1: taking a copper nanowire stock solution prepared by a liquid phase method, cleaning by adopting normal hexane and carrying out centrifugal separation, and dissolving the obtained copper nanowire in absolute ethyl alcohol to obtain a copper nanowire dispersion solution, wherein the weight percentage of the copper nanowire is 0.010wt%;
s2: taking 10.000g of the copper nanowire dispersion liquid obtained in the step S1, adding 40.000g of deionized water for dilution, wherein the weight percentage of the copper nanowires is 0.002wt%, and carrying out ultrasonic treatment for 3min;
s3: adding 10mL of citric acid solution (the citric acid solution is prepared by taking 1.000g of citric acid, 9.000g of deionized water and 40.000g of absolute ethyl alcohol to obtain 2.000wt% of citric acid solution) into the solution obtained in the step S2 for acid washing, and carrying out ultrasonic treatment for 3min at the same time to remove the coating agent on the surface of the copper nanowire;
s4: filtering and purifying the solution obtained in the step S3 by using a filter membrane with a pore size of 5 microns, and then dissolving the obtained copper nanowires in absolute ethyl alcohol again;
s5: repeating the dilution in the step S2 and the filter membrane suction filtration purification and re-dissolution processes in the step S4 to obtain a spraying liquid for later use, wherein the weight percentage of the copper nanowires in the spraying liquid is 0.100wt%;
s6: carrying out high-pressure spraying on the PET to form a film by using the spraying liquid obtained in the step S5, simultaneously heating (placing the flexible substrate PET on a heating table at 80 ℃) to process, and heating and evaporating to remove the solvent to obtain a copper nanowire film; wherein, before high-pressure spraying, the PET is firstly subjected to oxygen plasma activation treatment, the power is 300W, the oxygen gas flow is 100SCCM, and the treatment time is 5min;
s7: adding an acid solution into the copper nanowire film obtained in the step S6, soaking for 1min (the acid solution used in the step is the same as the step S3), then rinsing with absolute ethyl alcohol, and then drying in vacuum to obtain a copper nanowire transparent electrode preliminarily;
s8: performing argon plasma treatment on the copper nanowire transparent electrode obtained in the step S7, wherein the power is 300W, the oxygen gas flow is 100SCCM, the treatment time is 5min, obtaining the copper nanowire transparent electrode with good conductivity, and then performing vacuum storage, wherein the storage pressure is-13 psi for later use;
s9: depositing aluminum oxide on the surface of the copper nanowire transparent electrode obtained in the step S8 by using an Atomic Layer Deposition (ALD) technology, wherein the cycle deposition frequency is 50 times, and the deposition thickness is about 5nm, so that the oxidation-resistant copper nanowire transparent electrode is obtained.
The copper nanowire transparent electrode obtained in this example was stored at room temperature, and the sheet resistance was measured periodically.
Example 2
The difference from example 1 is that step S9 was not performed in the preparation method, an Atomic Layer Deposition (ALD) step was not performed, and the copper nanowire had no alumina protective layer.
The copper nanowire transparent electrode obtained in this example was stored at room temperature, and the sheet resistance was measured periodically.
Example 3
The difference from example 1 is that the copper nanowire transparent electrode obtained in this example was stored under a condition of double 85 (85 ℃, 85% relative humidity) and the sheet resistance thereof was measured periodically.
Example 4
The difference from example 2 is that the copper nanowire transparent electrode obtained in this example was stored under a condition of double 85 (85 ℃, 85% relative humidity) and the sheet resistance thereof was measured periodically.
FIG. 1 shows the sheet resistance change rate (R/R) of two copper nanowire transparent electrodes in examples 1 and 2 of the present invention when stored at room temperature 0 ) Graph of change over time. Comparative analysis shows that the oxidation resistance of the copper nanowire transparent electrode is very strong when the copper nanowire transparent electrode is isolated and protected by the aluminum oxide layer, the sheet resistance is almost kept unchanged after 14 days, and the sheet resistance of the copper nanowire transparent electrode without the protective layer is rapidly increased in a short time.
Fig. 2 is an SEM image of the copper nanowire transparent electrode in example 1 of the present invention after being stored at room temperature for 14 days, and it can be seen from the SEM image that the surface of the copper nanowire is bright and has no sign of oxidation when the copper nanowire is insulated and protected by the alumina layer.
Fig. 3 is an SEM image of the copper nanowire transparent electrode in example 2 of the present invention after being stored at room temperature for 14 days, from which it can be seen that rough oxide particles are grown on the surface of the copper nanowires.
FIG. 4 shows the sheet resistance change rate (R/R) of two copper nanowire transparent electrodes of examples 3 and 4 of the present invention when they are stored at 85 ℃ and 85% relative humidity 0 ) According to the change chart along with time, comparative analysis shows that the oxidation resistance of the copper nanowire transparent electrode is very strong when the copper nanowire transparent electrode is isolated and protected by the aluminum oxide layer, the sheet resistance is almost kept unchanged after 15 days under the double 85 treatment condition, and the sheet resistance of the copper nanowire transparent electrode without the protection layer is increased at the highest speed after 80min under the double 85 treatment condition and exceeds the range.
Fig. 5 is an SEM image of the copper nanowire transparent electrode in example 3 of the present invention after being stored for 15 days at 85 ℃ and 85% relative humidity, and it can be seen from the SEM image that the surface of the copper nanowire is bright and has no sign of oxidation even under the double 85 condition when the copper nanowire is insulated and protected by the alumina layer.
Fig. 6 is an SEM image of the copper nanowire transparent electrode in example 4 of the present invention after being stored for 80min at 85 ℃ and 85% relative humidity, and it can be seen from the SEM image that the surface oxidation degree of the copper nanowire is very severe, and a large amount of coarse oxide particles are grown.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (11)
1. A preparation method of an oxidation-resistant copper nanowire transparent electrode is characterized by comprising the following steps:
s1: taking a copper nanowire stock solution prepared by a liquid phase method, cleaning by adopting a non-polar organic solvent, carrying out centrifugal separation, and dissolving the obtained copper nanowire in absolute ethyl alcohol to obtain a copper nanowire dispersion solution;
s2: diluting the copper nanowire dispersion liquid obtained in the step S1 with deionized water, and carrying out ultrasonic treatment;
s3: adding an organic acid solution into the solution obtained in the step S2, and simultaneously carrying out ultrasonic treatment to remove the coating agent on the surface of the copper nanowire;
s4: filtering and purifying the solution obtained in the step S3 by using a filter membrane, and then re-dissolving the copper nanowires in absolute ethyl alcohol;
s5: repeating the dilution in the step S2 and the filtration, purification and redissolution processes of the filter membrane in the step S4 to obtain copper nanowire spraying liquid for later use;
s6: carrying out high-pressure spraying on the spraying liquid obtained in the step S5 on a flexible substrate to form a film, and simultaneously heating and evaporating a solvent at the bottom of the flexible substrate by using a heating table to obtain a copper nanowire film;
s7: adding the copper nanowire film obtained in the step S6 into the organic acid solution for soaking treatment, then rinsing with absolute ethyl alcohol, and then drying in vacuum to obtain a copper nanowire transparent electrode preliminarily;
s8: performing argon plasma treatment on the copper nanowire transparent electrode obtained in the step S7, and then performing vacuum storage to obtain a copper nanowire transparent electrode with stronger conductivity;
s9: and (5) depositing an aluminum oxide protective layer on the surface of the copper nanowire transparent electrode obtained in the step (S8) by adopting an atomic layer deposition technology to obtain the antioxidant copper nanowire transparent electrode.
2. The method for preparing the oxidation-resistant copper nanowire transparent electrode according to claim 1, wherein the non-polar organic solvent in step S1 is at least one of petroleum ether, n-hexane, toluene and benzene; in the copper nanowire dispersion liquid obtained in the step S1, the weight percentage of the copper nanowires is 0.010-0.150 wt%.
3. The method for preparing the oxidation-resistant copper nanowire transparent electrode according to claim 1, wherein the weight percentage of the copper nanowires in the diluted copper nanowire dispersion liquid in the step S2 is 0.002-0.030 wt%, and the ultrasonic time in the step S2 is 0.5-60 min.
4. The method for preparing the oxidation-resistant copper nanowire transparent electrode according to claim 1, wherein in steps S3 and S7, the organic acid solution is an aqueous solution of an organic acid, the organic acid is at least one selected from acetic acid, citric acid, tartaric acid, benzoic acid, ascorbic acid, malic acid and salicylic acid, and the concentration of the organic acid solution is 0.1 to 10wt%; in the step S3, the volume of the added organic acid solution is 10-100 mL, and the ultrasonic time is 0.5-60 min; in the step S7, the time of acid soaking treatment is 0.5-10 min.
5. The method for preparing the oxidation-resistant copper nanowire transparent electrode as claimed in claim 1, wherein the pore size of the filter membrane adopted in the step S4 is 220nm to 8 μm; in the copper nanowire dispersion liquid obtained by re-dissolving in the step S4, the weight percentage of the copper nanowire is 0.010-0.150 wt%; in the copper nanowire spraying solution obtained in the step S5, the weight percentage of the copper nanowires is 0.010-0.150 wt%.
6. The method for preparing the oxidation-resistant copper nanowire transparent electrode according to claim 1, further comprising a pretreatment of the flexible substrate before the step S6, wherein the pretreatment specifically comprises: firstly, absolute ethyl alcohol is used for cleaning the flexible substrate, and then activation treatment of oxygen plasma is carried out after drying, the power is 300-500W, the oxygen gas flow is 10-300 SCCM, and the treatment time is 3-300 min.
7. The method for preparing the oxidation-resistant copper nanowire transparent electrode according to claim 1, wherein the flexible substrate in the step S6 is made of one of polyethylene terephthalate (PET), polydimethylsiloxane, polymethyl methacrylate, polyurethane and polytetrafluoroethylene; the step S6 specifically includes: the flexible substrate is placed on a heating table to be preheated for 1-20 min, then the temperature of the heating table is controlled to be 50-120 ℃, and then high-pressure spraying is carried out to form a film.
8. The method for preparing the oxidation-resistant copper nanowire transparent electrode as claimed in claim 1, wherein in the step S8, the power of the argon plasma treatment is 300-500W, the argon flow is 10-300 SCCM, and the treatment time is 1-20 min; the vacuum storage pressure is-12 to-15 psi.
9. The method for preparing the oxidation-resistant copper nanowire transparent electrode according to claim 1, wherein in the step S9, the number of the cycle depositions of the atomic layer deposition is 50-500, and the thickness of the alumina protective layer is 5-50 nm.
10. An oxidation-resistant copper nanowire transparent electrode prepared by the preparation method of any one of claims 1 to 9.
11. Use of the copper nanowire transparent electrode of claim 10 in the field of transparent flexible electrodes.
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