CN115376757B - Antioxidant copper nanowire transparent electrode and preparation method and application thereof - Google Patents
Antioxidant copper nanowire transparent electrode and preparation method and application thereof Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 167
- 239000010949 copper Substances 0.000 title claims abstract description 167
- 239000002070 nanowire Substances 0.000 title claims abstract description 167
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000003647 oxidation Effects 0.000 claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005507 spraying Methods 0.000 claims abstract description 26
- 229910052786 argon Inorganic materials 0.000 claims abstract description 19
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 18
- 238000009832 plasma treatment Methods 0.000 claims abstract description 14
- 239000011241 protective layer Substances 0.000 claims abstract description 13
- 238000000151 deposition Methods 0.000 claims abstract description 12
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- 235000006708 antioxidants Nutrition 0.000 claims description 12
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- 239000011248 coating agent Substances 0.000 claims description 10
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- -1 polyethylene terephthalate Polymers 0.000 claims description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 9
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 235000015165 citric acid Nutrition 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
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- 239000002904 solvent Substances 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 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
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 238000001994 activation Methods 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
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- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
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- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 9
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- 238000001878 scanning electron micrograph Methods 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000003064 anti-oxidating effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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Classifications
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
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 copper nanowire stock solution, spraying the copper nanowire stock solution at high pressure to form a film, pickling, carrying out argon plasma treatment, and finally depositing an alumina protective layer on a copper nanowire conductive network through an Atomic Layer Deposition (ALD) technology to form a heterostructure with copper nanowires as cores and alumina as shells, so that the copper nanowire transparent electrode with strong oxidation resistance is obtained. The alumina deposited by the atomic layer is compact, good in isolation effect and strong in oxidation resistance; the thickness of the introduced alumina shell is in a uniform nano level, and the light transmittance and the sheet resistance of the transparent electrode are hardly affected; the argon plasma treatment can play a role in welding the copper nanowire conductive network, so that the contact resistance is greatly reduced, and the conductivity is improved.
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
Metal nanowires are receiving attention in the field of flexible display electronics for their excellent optical, electrical, mechanical and thermal properties. Among the plurality of metal nanowires, the copper nanowire has obvious advantages in production cost and has great economic research value. But the newly synthesized copper nanowire surface is adhered with a coating agent and a metal oxide, which influence the conduction of a copper nanowire network; the metallic property of the copper is more active, when the copper reaches the nanometer 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 rapidly increased in a short time, the defect is obvious, and the development and the application of the copper nanowire conductive network are greatly limited.
In the prior art, chinese patent publication No. CN108707997A discloses a preparation method of a reduced graphene oxide coated copper nanowire composite material, wherein reduced graphene oxide is adopted to coat copper nanowires, oxidation resistance is improved in a short period, but the process is too complex and complicated, and the reduced graphene oxide has good conductivity, and if the copper nanowires are coated for a long period, electrochemical reaction can occur, and instead, corrosion of the copper nanowires is accelerated. Chinese patent publication No. CN106536094a discloses silver-coated copper nanowires and a method for preparing the same, which synthesizes copper nanowires by using a chemical method of piperazine (C 4H10N2) and/or hexamethylenediamine (C 6H16N2), and then coats them with silver by using a chemical plating method, thereby preventing oxidation of the copper nanowires, the above method greatly improves oxidation resistance, but the chemical plating method is difficult to control the thickness of silver plating layer, and large-sized silver particles are easily generated, which greatly affects optical properties after film formation, and expensive cost also limits large-scale popularization thereof. Therefore, the antioxidation treatment method of the copper nanowire in the prior art has certain effect, but the defects of uneven antioxidation coating layer on the surface of the copper nanowire, serious decrease of light transmittance, weak antioxidation, excessively complex operation and the like always exist.
Therefore, research on a copper nanowire transparent electrode with high transparency, low sheet resistance and strong oxidation resistance, and a preparation method and application thereof are needed.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing an anti-oxidation copper nanowire transparent electrode, which is to deposit an alumina protective layer on a copper nanowire conductive network by ALD technology to prepare a copper nanowire transparent electrode with high transparency, low sheet resistance and high oxidation resistance, so as to solve all or part of the problems in the prior art.
In order to achieve the above purpose, the invention provides a preparation method of an antioxidant copper nanowire transparent electrode, which comprises the following steps:
S1: taking copper nanowire stock solution prepared by a liquid phase method, adopting a nonpolar organic solvent to wash and centrifugally separate, and dissolving the obtained copper nanowire in absolute ethyl alcohol to obtain copper nanowire dispersion liquid;
S2: diluting the copper nanowire dispersion liquid obtained in the step S1 by deionized water, and carrying out ultrasonic treatment;
S3: adding an organic acid solution into the solution obtained in the step S2, and simultaneously performing ultrasonic treatment to remove a 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 redissolving the copper nanowire in absolute ethyl alcohol;
s5: repeating the diluting in the step S2 and the suction filtration purification and redissolution process of the filter membrane in the step S4 for a time to obtain copper nanowire spraying liquid for standby;
S6: performing high-pressure spraying film forming on the spraying liquid obtained in the step S5 on the flexible substrate, and simultaneously heating and evaporating the 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 using absolute ethyl alcohol for rinsing, and then carrying out vacuum drying 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 (3) depositing an alumina 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 the step S1 is at least one of petroleum ether, n-hexane, toluene and benzene; and (2) 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 copper nanowire dispersion liquid diluted in the step S2, the weight percentage of the copper nanowires is 0.002-0.030 wt%, and the ultrasonic time in the step S2 is 0.5-60 min.
Preferably, in the 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 0.1-10wt%; 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 size of the filter membrane adopted in the step S4 is 220 nm-8 μm; the copper nanowire dispersion liquid obtained by redissolving in the step S4 has the weight percentage of copper nanowire of 0.010-0.150 wt%; and in the copper nanowire spraying liquid obtained in the step S5, the weight percentage of the copper nanowire is 0.010-0.150 wt%.
Preferably, the method further comprises a pretreatment of the flexible substrate before the step S6, wherein the pretreatment is specifically: the flexible substrate is firstly cleaned by absolute ethyl alcohol, and then is subjected to activation treatment by oxygen plasma after being dried, wherein the power is 300-500W, the oxygen gas flow is 10-300 SCCM, and the treatment time is 3-300 min.
Preferably, in the step S6, the flexible substrate is made of one of polyethylene terephthalate (PET), polydimethylsiloxane, polymethyl methacrylate, polyurethane and polytetrafluoroethylene; the step S6 specifically includes: firstly, placing the flexible substrate on a heating table for preheating for 1-20 min, then controlling the temperature of the heating table to be 50-120 ℃, and then spraying at high pressure 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 the step S9, the number of cyclic deposition times of atomic layer deposition is 50 to 500, and the thickness of the alumina protective layer is 5 to 50nm.
The invention also provides an antioxidant copper nanowire transparent electrode prepared by the preparation method.
The invention also provides application of the copper nanowire transparent electrode in the field of transparent flexible electrodes.
The invention adopts the technical proposal has the advantages that:
The preparation method of the oxidation-resistant copper nanowire transparent electrode comprises the steps of cleaning and purifying copper nanowire stock solution, spraying the copper nanowire stock solution at high pressure to form a film, pickling, carrying out argon plasma treatment, and finally depositing an alumina protective layer on a copper nanowire conductive network through an Atomic Layer Deposition (ALD) technology to form a heterostructure with copper nanowires as inner cores and alumina as shells, so that the copper nanowire transparent electrode with strong oxidation resistance is obtained. The invention adopts a high-pressure spraying coating process, and simultaneously the bottom is heated and evaporated to remove the solvent, thus obtaining a uniformly dispersed copper nanowire network; 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 in a uniform nano level, and the light transmittance and the sheet resistance of the transparent electrode are hardly affected; the argon plasma treatment can play a role in welding the copper nanowire conductive network, so that the contact resistance is greatly reduced, and the conductivity is improved. 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 invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the change rate (R/R 0) of the copper nanowire transparent electrode of example 1 and example 2 with time when the electrode is stored at room temperature;
FIG. 2 is an SEM image of a copper nanowire transparent electrode of example 1 of the present invention after being stored at room temperature for 14 days;
FIG. 3 is an SEM image of a copper nanowire transparent electrode of example 2 of the present invention after being stored at room temperature for 14 days;
FIG. 4 is a graph showing the change rate (R/R 0) of the sheet resistance of the copper nanowire transparent electrode of example 3 or example 4 according to the present invention with time when the electrode is stored at 85℃and 85% relative humidity;
FIG. 5 is an SEM image of a copper nanowire transparent electrode of 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 a copper nanowire transparent electrode of example 4 of the present invention stored at 85℃and 85% relative humidity for 80 minutes.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of an antioxidant copper nanowire transparent electrode, which comprises the following steps:
S1: taking copper nanowire stock solution prepared by a liquid phase method, adopting a nonpolar organic solvent to wash and centrifugally separate, and dissolving the obtained copper nanowire in absolute ethyl alcohol to obtain copper nanowire dispersion liquid;
S2: diluting the copper nanowire dispersion liquid obtained in the step S1 by deionized water, and carrying out ultrasonic treatment;
S3: adding an organic acid solution into the solution obtained in the step S2, and simultaneously performing ultrasonic treatment to remove a 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 redissolving the copper nanowire in absolute ethyl alcohol;
s5: repeating the diluting in the step S2 and the suction filtration purification and redissolution process of the filter membrane in the step S4 for a time to obtain copper nanowire spraying liquid for standby;
S6: performing high-pressure spraying film forming on the spraying liquid obtained in the step S5 on the flexible substrate, and simultaneously heating and evaporating the 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 using absolute ethyl alcohol for rinsing, and then carrying out vacuum drying 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 (3) depositing an alumina 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 steps S3 and S7, the organic acid solution is used for pickling or acid treatment to remove the coating agent, and the principle of pickling to remove the coating agent is as follows: in the process of synthesizing copper nanowires, cu 2+ (mainly from CuO) on the surfaces of the copper nanowires is complexed with-NH 2 in a coating agent to form a complex, and conventional cleaning cannot be completely removed; citric acid is introduced to generate a chemical reaction CuO+2H +＝H2O+Cu2+, the metal oxide falls off from the surface of the copper nanowire, and the coating agent also falls off along with the metal oxide. The coating agent on the surface of the copper nanowire can be completely removed after 2 times of acid washing.
In the step S6, a high-pressure spraying coating process is adopted, and simultaneously, the heating treatment is performed, and the solvent is removed by evaporation, so as to obtain a uniformly dispersed copper nanowire network.
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: the surface energy of the copper nanowire is improved by the argon plasma air flow, so that copper atoms are diffused on the surface; in addition, at the junction of the contact points of the copper nanowires, a surface plasma resonance effect exists, so that the absorption of electrons to light energy is greatly increased, the temperature at the junction is increased, and local nano welding is realized, wherein the temperature of nano welding is far lower than the melting point of the material.
In the step S9, an alumina protective layer is deposited on the copper nanowire conductive network by adopting an atomic layer deposition technology, so that a heterostructure with the copper nanowire as an inner core and alumina as an outer shell is formed, the compact alumina outer shell plays a role in blocking oxygen and water vapor, the condition of oxidation corrosion of the copper nanowire is destroyed, the isolation effect is good, the duration 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 in a uniform nano level, and the light transmittance and the sheet resistance of the transparent electrode are hardly affected.
Preferably, the nonpolar solvent in the step S1 is one or more of petroleum ether, normal hexane, toluene and benzene; for the copper nanowire dispersion liquid obtained in the step S1, the weight percentage of the copper nanowires is 0.010-0.150 wt%;
preferably, the weight percentage of the copper nanowire is 0.002-0.030 wt% for the copper nanowire dispersion liquid obtained in the step S2, and the ultrasonic time in the step S2 is 0.5-60 min.
Preferably, in the steps S3 and S7, the organic acid solution is an aqueous solution of an organic acid, and is configured 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 0.1-10wt%; 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 membrane used in step S4 has a pore size of 220nm to 8. Mu.m; for the copper nanowire dispersion liquid obtained in the step S4, the weight percentage of the copper nanowires is 0.010-0.150 wt%; and (3) in the copper nanowire spraying liquid obtained in the step S5, the weight percentage of the copper nanowire is 0.010-0.150 wt%.
Preferably, in step S6, the flexible substrate needs to be pretreated, where the pretreatment is specifically: the flexible substrate is firstly cleaned by absolute ethyl alcohol, and then is subjected to activation treatment by oxygen plasma after being dried, wherein the power is 300-500W, the oxygen gas flow is 10-300 SCCM, and the treatment time is 3-300 min.
Preferably, 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: firstly, placing the flexible substrate on a heating table for preheating for 1-20 min, then controlling the temperature of the heating table to be 50-120 ℃, and then spraying at high pressure 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 the step S9, the number of deposition cycles of atomic layer deposition is 50 to 500, and the thickness of the alumina layer is 5 to 50nm.
The preparation method of the oxidation-resistant copper nanowire transparent electrode comprises the steps of cleaning and purifying copper nanowire stock solution, spraying the copper nanowire stock solution at high pressure to form a film, pickling, carrying out argon plasma treatment, and finally depositing an alumina protective layer on a copper nanowire conductive network through an Atomic Layer Deposition (ALD) technology to form a heterostructure with copper nanowires as inner cores and alumina as shells, so that the copper nanowire transparent electrode with strong oxidation resistance is obtained. The invention adopts a high-pressure spraying coating process, and simultaneously carries out heating treatment and evaporation to remove the solvent, thus obtaining a uniformly dispersed copper nanowire network; 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 in a uniform nano level, and the light transmittance and the sheet resistance of the transparent electrode are hardly affected; the argon plasma treatment can play a role in welding the copper nanowire conductive network, so that the contact resistance is greatly reduced, and the conductivity is improved.
The invention also provides an antioxidative copper nanowire transparent electrode prepared by the preparation method, which has strong antioxidative property, and excellent electrical property, optical property and bending resistance, so that the transparent electrode has great potential in the field of flexible display electronics.
The invention also provides application of the copper nanowire transparent electrode in the field of transparent flexible electrodes.
Example 1
An oxidation-resistant copper nanowire transparent electrode, the preparation method comprises the following steps:
S1: taking copper nanowire stock solution prepared by a liquid phase method, adopting normal hexane for cleaning and centrifugally separating, and dissolving the obtained copper nanowire in absolute ethyl alcohol to obtain copper nanowire dispersion liquid, 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 nanowire is 0.002wt%, and carrying out ultrasonic treatment for 3min;
S3: adding 10mL of citric acid solution (the preparation of the citric acid solution comprises that 1.000g of citric acid, 9.000g of deionized water and 40.000g of absolute ethyl alcohol are taken to obtain a citric acid solution with the weight percentage of 2.000 wt%) into the solution obtained in the step S2 for pickling, and simultaneously carrying out ultrasonic treatment for 3min to remove a coating agent on the surface of the copper nanowire;
S4: filtering and purifying the solution obtained in the step S3 by adopting a filter membrane with the aperture of 5 microns, and then redissolving the obtained copper nanowire in absolute ethyl alcohol;
S5: repeating the diluting in the step S2 and the suction filtration purification and redissolving process of the filter membrane in the step S4 to obtain spraying liquid for standby, wherein the weight percentage of the copper nanowires in the spraying liquid is 0.100 percent;
S6: performing high-pressure spraying film formation on the spraying liquid obtained in the step S5 on PET, heating (placing the flexible substrate PET on a heating table at 80 ℃), heating and evaporating to remove the solvent to obtain a copper nanowire film; wherein, before high-pressure spraying, the PET is 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 to soak for 1min (the acid solution used in the step is the same as the acid solution used in the step S3), then rinsing with absolute ethyl alcohol, and then drying in vacuum to primarily obtain a copper nanowire transparent electrode;
S8: carrying out 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, and the copper nanowire transparent electrode with good conductivity is obtained, and then, the copper nanowire transparent electrode is stored in vacuum, and the storage pressure is-13 psi for standby;
S9: and (3) depositing aluminum oxide on the surface of the transparent electrode of the copper nanowire obtained in the step S8 by using an Atomic Layer Deposition (ALD) technology, wherein the number of deposition cycles is 50, and the deposition thickness is about 5nm, so that the transparent electrode of the antioxidant copper nanowire 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 is not performed in the preparation method, the Atomic Layer Deposition (ALD) step is not performed, and the copper nanowire has no aluminum oxide 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 double condition (85 ℃ C., 85% relative humidity) and the sheet resistance 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 double condition (85 ℃ C., 85% relative humidity) and the sheet resistance was measured periodically.
FIG. 1 is a graph showing the change rate (R/R 0) of the sheet resistance of the two copper nanowire transparent electrodes of example 1 and example 2 according to the present invention with time when they are stored at room temperature. The comparative analysis shows that the oxidation resistance of the copper nanowire transparent electrode is very strong when the aluminum oxide layer is isolated and protected, the sheet resistance of the copper nanowire transparent electrode without the protective layer is increased rapidly in a short time after 14 days.
Fig. 2 is an SEM image of the transparent electrode of the copper nanowire in example 1 of the present invention after being stored at room temperature for 14 days, from which it can be seen that the surface is bright without signs of oxidation when the copper nanowire is insulated with an alumina layer.
Fig. 3 is an SEM image of the transparent electrode for copper nanowires in example 2 of the present invention after being stored at room temperature for 14 days, from which it can be seen that coarse oxide particles grow on the surface of the copper nanowires.
FIG. 4 is a graph showing the change rate (R/R 0) of the sheet resistance of the two copper nanowire transparent electrodes in the embodiment 3 and the embodiment 4 with time when the two copper nanowire transparent electrodes are stored under the condition of 85 ℃ and 85% relative humidity, and the comparison 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 an alumina layer, the sheet resistance of the copper nanowire transparent electrode is almost unchanged after 15 days under the double 85 treatment condition, and the sheet resistance of the copper nanowire transparent electrode without a protective layer is fast increased after 80 minutes under the double 85 treatment condition, and the sheet resistance exceeds the measuring range.
Fig. 5 is an SEM image of the transparent electrode of the copper nanowire in example 3 of the present invention after being stored at 85 ℃ and 85% relative humidity for 15 days, from which it can be seen that the copper nanowire is still bright in surface and has no sign of oxidation even under double 85 conditions when the copper nanowire is insulated with an alumina layer.
FIG. 6 is an SEM image of a transparent electrode for copper nanowires in example 4 of the present invention after being stored at 85℃and 85% relative humidity for 80 minutes, from which it can be seen that the surface oxidation degree of the copper nanowires is extremely severe, and a large amount of coarse oxide particles are grown.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (11)
1. The preparation method of the oxidation-resistant copper nanowire transparent electrode is characterized by comprising the following steps of:
S1: taking copper nanowire stock solution prepared by a liquid phase method, adopting a nonpolar organic solvent to wash and centrifugally separate, and dissolving the obtained copper nanowire in absolute ethyl alcohol to obtain copper nanowire dispersion liquid;
S2: diluting the copper nanowire dispersion liquid obtained in the step S1 by deionized water, and carrying out ultrasonic treatment;
S3: adding an organic acid solution into the solution obtained in the step S2, and simultaneously performing ultrasonic treatment to remove a 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 redissolving the copper nanowire in absolute ethyl alcohol;
s5: repeating the diluting in the step S2 and the suction filtration purification and redissolution process of the filter membrane in the step S4 for a time to obtain copper nanowire spraying liquid for standby;
S6: performing high-pressure spraying film forming on the spraying liquid obtained in the step S5 on the flexible substrate, and simultaneously heating and evaporating the 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 using absolute ethyl alcohol for rinsing, and then carrying out vacuum drying 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 (3) depositing an alumina 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 an antioxidant copper nanowire transparent electrode according to claim 1, wherein the nonpolar organic solvent in the step S1 is at least one of petroleum ether, n-hexane, toluene and benzene; and (2) 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 an antioxidant copper nanowire transparent electrode according to claim 1, wherein the weight percentage of copper nanowires in the diluted copper nanowire dispersion 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 an oxidation-resistant copper nanowire transparent electrode according to claim 1, wherein in the steps S3 and S7, the organic acid solution is an aqueous solution of an organic acid selected from at least one 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 0.1-10 wt%; 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 an oxidation-resistant copper nanowire transparent electrode according to claim 1, wherein the pore diameter of the filter membrane adopted in the step S4 is 220 nm-8 μm; the copper nanowire dispersion liquid obtained by redissolving in the step S4 has the weight percentage of copper nanowire of 0.010-0.150 wt%; and in the copper nanowire spraying liquid obtained in the step S5, the weight percentage of the copper nanowire is 0.010-0.150 wt%.
6. The method for preparing an oxidation-resistant copper nanowire transparent electrode according to claim 1, further comprising a pretreatment of the flexible substrate prior to the step S6, wherein the pretreatment is specifically: the flexible substrate is firstly cleaned by absolute ethyl alcohol, and then is subjected to activation treatment by oxygen plasma after being dried, wherein 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 an oxidation-resistant copper nanowire transparent electrode according to claim 1, wherein the flexible substrate in the step S6 is one of polyethylene terephthalate (PET), polydimethylsiloxane, polymethyl methacrylate, polyurethane and polytetrafluoroethylene; the step S6 specifically includes: firstly, placing the flexible substrate on a heating table for preheating for 1-20 min, then controlling the temperature of the heating table to be 50-120 ℃, and then spraying at high pressure to form a film.
8. The method for preparing an antioxidant copper nanowire transparent electrode according to 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 an oxidation-resistant copper nanowire transparent electrode according to claim 1, wherein in the step S9, the number of cyclic deposition times of atomic layer deposition is 50-500 times, 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 according to claim 10 in the field of transparent flexible electrodes.
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| CN108707997A (en) * | 2018-05-29 | 2018-10-26 | 哈尔滨工业大学深圳研究生院 | Redox graphene coats the preparation method of copper nano-wire conducing composite material |
| CN110783025A (en) * | 2019-09-27 | 2020-02-11 | 江苏科技大学海洋装备研究院 | Oxidation-resistant conductive copper nanowire film and preparation method and application thereof |
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| CN108707997A (en) * | 2018-05-29 | 2018-10-26 | 哈尔滨工业大学深圳研究生院 | Redox graphene coats the preparation method of copper nano-wire conducing composite material |
| CN110783025A (en) * | 2019-09-27 | 2020-02-11 | 江苏科技大学海洋装备研究院 | Oxidation-resistant conductive copper nanowire film and preparation method and application thereof |
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