CN114038623A - Silver nanowire-biological material composite transparent conductive film and preparation method and application thereof - Google Patents
Silver nanowire-biological material composite transparent conductive film and preparation method and application thereof Download PDFInfo
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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 discloses a silver nanowire-biological material composite transparent conductive film and a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing a silver nanowire solution (AgNWs solution) and a biological material solution; cleaning the substrate to obtain a pretreated substrate; firstly, coating AgNWs solution on a pretreated substrate in a scraping mode, and then heating and curing to form an AgNWs film; and then coating a biological material solution on the AgNWs thin film, and then heating and curing to form the AgNWs/biological material composite transparent conductive thin film. By adopting the method, the environment-friendly biological modification material can be utilized, so that the metal nanowire transparent conductive film can obtain a flat film surface, excellent mechanical stability, resistance to water-oxygen corrosion, acid corrosion, high temperature and other performances on the premise of keeping good photoelectric performance.
Description
Technical Field
The invention belongs to the technical field of electronic devices, and particularly relates to a silver nanowire-biological material composite transparent conductive film, and a preparation method and application thereof.
Background
ITO (indium tin oxide) has high visible light transmittance and high conductivity, and often occupies a large market share as an electrode of devices such as OLEDs, solar cells, touch screens and sensors. However, the indium resource is scarce, the indium is brittle, the preparation process is complex, and the application of the indium in the field of flexible electronics is greatly limited. Researchers have been working on developing second generation flexible transparent electrodes, such as flexible transparent conductive materials like carbon-based materials, metal nanowires, ultra-thin metal and conductive polymer electrodes.
Among these flexible transparent electrode materials, silver nanowires (AgNWs) are considered as the most promising transparent electrode material to replace ITO. The silver nanowire has excellent conductivity, higher light transmittance and good bending resistance. However, AgNWs also has its own disadvantages: stacking among nanowires can cause the surface roughness of a nanowire network to be large, and the short circuit of a device is often caused; in addition, AgNWs are easy to oxidize when exposed to air environment, and if the AgNWs are in high-temperature and high-humidity environment, the oxidation condition of the AgNWs is more serious, and the performance of the AgNWs conductive network can be greatly broken.
At present, a plurality of documents report that a silver nanowire composite electrode is prepared by a modification method, the surface roughness of the silver nanowire electrode is improved, and the stability of the electrode is improved. For example, Lee et al use a layer-by-layer self-assembly (LBL) method to deposit graphene oxide GO on a silver nanowire thin film, and obtain a composite electrode with good mechanical stability, but GO with a certain thickness can reduce the photoelectric properties of the silver nanowire electrode (adv. mater. 2015, 27, 2252-; kim et al prepared a ZnO/AgNWs/ZnO composite electrode of a three-layer structure by sputtering zinc oxide (ZnO), which had high mechanical and thermal stability, but also the ZnO coating layer decreased the transmittance of the silver nanowire film (ACS Nano 2013, 7, 2, 1081-. The methods are difficult to realize that the stability of the silver nanowire electrode is improved, the photoelectric performance of the electrode is not influenced, and in addition, the modification materials adopted in the methods are not biocompatible environment-friendly materials. Recently, Jin et al modified the nanowire electrode with chitosan to prepare a composite electrode with a flat surface, but chitosan decomposed and blackened at a certain temperature, resulting in a decrease in the transmittance of the composite electrode (ACS appl. mater. Interfaces 2017, 9, 4733-. Therefore, it is necessary to develop a new biocompatible material to prepare a high-quality silver nanowire composite transparent electrode.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a silver nanowire-biological material composite transparent conductive film, a preparation method and application thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a silver nanowire-biological material composite transparent conductive film comprises the following steps:
step 1, preparation of silver nanowire solution
Mixing a silver nanowire dispersion liquid serving as a precursor solution with a solvent A to obtain an AgNWs solution, wherein the concentration of AgNWs in the AgNWs solution is 1-10 mg/mL, and the solvent A is absolute ethyl alcohol, isopropanol or deionized water;
step 2, preparation of biomaterial solution
Mixing a biological material with a solvent B, and then carrying out ultrasonic homogenization to obtain a biological material solution with the concentration of 5-60 mg/mL, wherein the solvent B is absolute ethyl alcohol, isopropanol, deionized water, acetone or ethylene glycol, and the biological material is an oxidation-resistant natural material;
step 3, pretreatment of the transparent substrate
Cleaning the substrate to obtain a pretreated substrate;
step 4, preparation of AgNWs/biological material composite film
Firstly coating AgNWs solution on a pretreated substrate, curing for 10-20 min at 80-120 ℃ to form an AgNWs film, then coating a biological material solution on the AgNWs film, and curing for 10-30 min at 40-100 ℃ to form the AgNWs/biological material composite transparent conductive film.
The improvement is that the natural material with oxidation resistance in the step 2 is propolis, vitamin C, tea polyphenol or phytic acid.
The substrate in step 3 is glass, polyethylene terephthalate PET, polyimide PI, ultraviolet curing optical cement NOA63, polyvinyl alcohol PVA, polymethyl siloxane PDMS, polyurethane acrylate PUA or hydrogel.
The improvement is that the specific steps of the transparent substrate pretreatment in the step 3 are as follows: ultrasonically cleaning the substrate for 20-30 min by respectively using a detergent, deionized water, ethanol and acetone, and then carrying out surface treatment for 5-20 min by using an ultraviolet ozone cleaning instrument (UV/ozone) at the power of 45W.
As a modification, the transparent substrate is pretreated by plasma treatment for 30-100s in the step 3.
The coating method in step 3 is preferably blade coating, meyer bar coating, slit coating, spray coating or spin coating.
The silver nanowire-biological material composite transparent conductive film is prepared based on any one of the preparation methods.
The silver nanowire-biological material composite transparent conductive film is applied to a flexible transparent electrode.
Has the advantages that:
compared with the prior art, the silver nanowire-biological material composite transparent conductive film and the preparation method and application thereof have the following advantages:
1) according to the invention, the biological material with oxidation resistance is coated on the surface of the silver nanowire film as a protective layer by a solution method, so that the oxidation resistance, thermal stability, mechanical stability and surface flatness of the silver nanowire film are greatly improved on the basis of keeping the original photoelectric property of the silver nanowire film, and the silver nanowire film is greatly improved in multiple properties;
2) the invention adopts natural biological materials to modify the nanowire electrode, has simple and environment-friendly preparation process, helps to reduce pollution in industrial production, and is suitable for industrial production.
Drawings
FIG. 1 shows the sheet resistance and transmittance of AgNWs thin films and AgNWs/propolis composite thin films, wherein (a) is sheet resistance and (b) is transmittance;
FIG. 2 is a comparison of the sheet resistance change of AgNWs thin films and AgNWs/propolis composite thin films after being placed in an environment with a temperature of 60 ℃ and a humidity of 85% for 700 hours;
FIG. 3 is a comparison of the microscopic topography of the AgNWs film and the AgNWs/propolis composite film after being placed in an environment with a temperature of 60 ℃ and a humidity of 85% for 700 hours;
FIG. 4 is a comparison of changes in sheet resistance between the AgNWs film and the AgNWs/propolis composite film after being heated in a 180 ℃ hot stage for a certain period of time;
FIG. 5 is a comparison of the change of sheet resistance after bending AgNWs thin film and AgNWs/propolis composite thin film for a certain number of times under the condition of a bending radius of 2 mm;
FIG. 6 shows the performance of a flexible white OLED device fabricated using the AgNWs/propolis composite film.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
the used substrate is polyethylene terephthalate PET, polyimide PI, ultraviolet curing optical cement NOA63, polyvinyl alcohol PVA, polymethyl siloxane PDMS, polyurethane acrylate PUA or hydrogel;
the preparation process of the biological material solution comprises the following steps: and mixing the biological material with a solvent B, and then carrying out ultrasonic homogenization, wherein the solvent is absolute ethyl alcohol, isopropanol, deionized water, acetone or ethylene glycol.
Example 1
A preparation method of a silver nanowire-biological material composite transparent conductive film comprises the following steps:
1) preparing a silver nanowire solution and a propolis solution:
taking the AgNWs solution as a precursor solution, and adding isopropanol to dilute the silver nanowire dispersion solution to finally obtain silver nanowire ink (AgNWs solution); the AgNWs concentration is 2 mg/mL, and the solvent A is isopropanol;
mixing propolis with solvent B, performing ultrasonic treatment to obtain a mixture, wherein the concentration of propolis is 10 mg/mL, the solvent B is absolute ethyl alcohol, and centrifuging to filter out insoluble impurities to obtain a propolis solution.
2) And (3) pretreating the PET transparent film substrate:
ultrasonically cleaning a PET film (the thickness is 125 mu m) with an optical glass cleaner, deionized water, ethanol and acetone for 30 min respectively, and then carrying out surface treatment on the surface of the PET film for 5 min at the power of 45W by using an ultraviolet ozone cleaning instrument UV/ozone to obtain a pretreated substrate;
3) and preparing the AgNWs/propolis composite transparent conductive film:
coating a layer of silver nanowire wet film on the pretreated substrate by a blade coater with a scraper, and curing for 20min at 100 ℃ to form an AgNWs film;
and coating a propolis solution with the concentration of 10 mg/mL on the AgNWs film, spin-coating to form a film, and curing at 50 ℃ for 20min to obtain the AgNWs/propolis composite film.
Example 2
A preparation method of a silver nanowire-biological material composite transparent conductive film comprises the following steps:
1) preparing a silver nanowire solution and a vitamin C solution:
taking the AgNWs solution as a precursor solution, and adding isopropanol to dilute the silver nanowire dispersion solution to finally obtain silver nanowire ink (AgNWs solution); the AgNWs concentration was 5 mg/mL.
Mixing vitamin C with a solvent B, and then performing ultrasonic treatment to obtain a mixture, wherein the concentration of the vitamin C is 30 mg/mL, and the solvent B is absolute ethyl alcohol;
2) and pretreating the PDMS transparent film substrate:
carrying out plasma treatment on the PDMS substrate for 60 s to obtain a pretreated substrate;
3) and preparing the AgNWs/vitamin C composite transparent conductive film:
coating a layer of silver nanowire wet film on the pretreated substrate by a blade coater with a scraper, and curing for 20min at 120 ℃ to form an AgNWs thin film;
and coating a vitamin C solution with the concentration of 30 mg/mL on the AgNWs film, spin-coating to form a film, and curing at 50 ℃ for 20min to obtain the AgNWs/vitamin C composite film.
Example 3
The AgNWs/propolis composite conductive film prepared in example 1 is used as an example, and AgNWs conductive films are prepared at the same time, and performances of the AgNWs/propolis composite conductive films are compared.
The square resistance and the transmittance of the two conductive films are tested, and the result is shown in figure 1, the propolis hardly influences the photoelectric property of the AgNWs conductive film, and the square resistance is 20-30 omega/sq under the condition that the transmittance of the AgNWs/propolis composite conductive film in a visible light range exceeds 90%.
The oxidation resistance stability of the two conductive films is tested, the two electrodes are placed in an environment with the temperature of 60 ℃ and the humidity of 85%, the change value of the sheet resistance is measured, and the microscopic morphology is observed after the test is finished, as shown in fig. 2 and 3. Fig. 2 shows the change of sheet resistance, and it can be seen that the conductivity of the AgNWs film extremely decreases after being left for 300 hours in a high-temperature and high-humidity environment, while the conductivity of the AgNWs/propolis composite film hardly changes after being left for 700 hours; fig. 3 shows the microscopic morphology of the two electrodes after 700 hours of storage, and it can be seen from the two upper graphs that the nanowires are corroded after 700 hours of storage of the AgNWs film in a high-temperature and high-humidity environment, the nanowire network is broken and damaged, and the AgNWs/propolis composite film still maintains good morphological characteristics and network integrity after 700 hours of storage.
The thermal stability of the two conductive films was tested by placing the two electrodes on a hot table at 180 ℃ and heating, and measuring the change in sheet resistance. Specifically, as shown in fig. 4, the AgNWs film lost conductivity after 5 minutes of heating, compared to the AgNWs/propolis composite film with only a slight increase in sheet resistance after 60 minutes of heating.
The mechanical stability of the two conductive films is tested, and the change of the sheet resistance is tested after the AgNWs film and the AgNWs/propolis composite film are bent for a certain number of times under the condition that the bending radius is 2 mm. Specifically, as shown in fig. 5, after 2000 times of bending, the sheet resistance of the AgNWs film starts to increase significantly, and the sheet resistance continues to increase with the increase of the bending times, while after 10000 times of bending tests, the AgNWs/propolis composite film has only slight changes in sheet resistance, and shows excellent mechanical flexibility.
The flexible white light device is prepared by using a commercial ITO conductive film (glass substrate) and an AgNWs/propolis composite film (PET substrate), and the device performance is specifically shown in FIG. 6. The device based on the AgNWs/propolis flexible electrode has higher current efficiency (56.6 cd/A) compared with the device based on the commercial rigid ITO electrode (40.8 cd/A).
In conclusion, the silver nanowire-biomaterial composite transparent conductive film, the preparation method and the application thereof coat the biomaterial with oxidation resistance on the surface of the silver nanowire film as the protective layer by the solution method, greatly improve the oxidation resistance, thermal stability, mechanical stability and surface flatness of the silver nanowire film on the basis of keeping the original photoelectric property, greatly improve the performances of the silver nanowire film, and are suitable for industrial production.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.
Claims (8)
1. A preparation method of a silver nanowire-biological material composite transparent conductive film is characterized by comprising the following steps:
step 1, preparing a silver nanowire solution: mixing a silver nanowire dispersion liquid serving as a precursor solution with a solvent A to obtain an AgNWs solution, wherein the concentration of AgNWs in the AgNWs solution is 1-10 mg/mL, and the solvent A is absolute ethyl alcohol, isopropanol or deionized water;
step 2, preparing a biological material solution: mixing a biological material with a solvent B, and then carrying out ultrasonic homogenization to obtain a biological material solution with the concentration of 5-60 mg/mL, wherein the solvent B is absolute ethyl alcohol, isopropanol, deionized water, acetone or ethylene glycol, and the biological material is an oxidation-resistant natural material;
step 3, pretreatment of the transparent substrate: cleaning the substrate to obtain a pretreated substrate;
step 4, preparing the AgNWs/biological material composite film: firstly coating AgNWs solution on a pretreated substrate, curing for 10-20 min at 80-120 ℃ to form an AgNWs film, then coating a biological material solution on the AgNWs film, and curing for 10-30 min at 40-100 ℃ to form the AgNWs/biological material composite transparent conductive film.
2. The method for preparing the silver nanowire-biomaterial composite transparent conductive film according to claim 1, wherein the method comprises the following steps: in the step 2, the natural material with oxidation resistance is propolis, vitamin C, tea polyphenol or phytic acid.
3. The method for preparing the silver nanowire-biomaterial composite transparent conductive film according to claim 2, wherein the method comprises the following steps: in the step 3, the substrate is glass, polyethylene terephthalate (PET), polyimide PI, ultraviolet curing optical cement NOA63, polyvinyl alcohol (PVA), polymethyl siloxane (PDMS), polyurethane acrylate (PUA) or hydrogel.
4. The method for preparing the silver nanowire-biomaterial composite transparent conductive film according to claim 1, wherein the method comprises the following steps: the pretreatment of the transparent substrate in the step 3 comprises the following specific steps: ultrasonically cleaning the substrate for 20-30 min by using a detergent, deionized water, ethanol and acetone respectively, and then carrying out surface treatment for 5-20 min by using an ultraviolet ozone cleaning instrument under the power of 45W.
5. The method for preparing the silver nanowire-biomaterial composite transparent conductive film according to claim 1, wherein the method comprises the following steps: the transparent substrate is pretreated by plasma for 30-100s in step 3.
6. The method for preparing the silver nanowire-biomaterial composite transparent conductive film according to claim 1, wherein the method comprises the following steps: the coating mode in the step 3 is scraper coating, Meyer bar blade coating, slit coating, spray coating or spin coating.
7. A silver nanowire-biomaterial composite transparent conductive film prepared based on the preparation method of any one of claims 1 to 6.
8. Use of the silver nanowire-biomaterial composite transparent conductive film of claim 1 or claim 7 on a flexible transparent electrode.
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Cited By (2)
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| CN114883513A (en) * | 2022-03-30 | 2022-08-09 | 南京邮电大学 | Fabric electrode and rapid preparation method and application thereof |
| CN115433420A (en) * | 2022-08-31 | 2022-12-06 | 河南师范大学 | Polyvinyl alcohol/silver nanowire friction nanometer generator |
Citations (9)
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| CN115433420B (en) * | 2022-08-31 | 2023-09-12 | 河南师范大学 | Friction nano generator based on polyvinyl alcohol/silver nanowire |
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