CN112289500A - Preparation method of high-performance conductive cellulose membrane and product thereof - Google Patents
Preparation method of high-performance conductive cellulose membrane and product thereof Download PDFInfo
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- CN112289500A CN112289500A CN202010894185.0A CN202010894185A CN112289500A CN 112289500 A CN112289500 A CN 112289500A CN 202010894185 A CN202010894185 A CN 202010894185A CN 112289500 A CN112289500 A CN 112289500A
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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
Abstract
The invention provides a preparation method of a high-performance conductive cellulose membrane and a product thereof, wherein the method comprises the following steps: (1) dissolving zinc acetate in an ethanolamine and ethylene glycol monomethyl ether solvent, preparing a ZnO precursor solution through a chemical reaction, and spin-coating the ZnO precursor solution on a cellulose membrane substrate; (2) placing the cellulose membrane coated with the ZnO solution in a drying device for drying to obtain a cellulose-ZnO membrane; (3) taking a dry cellulose-ZnO film as a substrate, and plating an inorganic doped oxide conducting layer to obtain a high-performance conducting cellulose film; the thickness of the cellulose-ZnO film in the conductive cellulose film is 10-350 μm, and the thickness of the inorganic doped oxide conductive layer is 10-350 μm. According to the invention, the ZnO buffer layer is inserted into the inorganic conducting layer and the organic cellulose membrane to prepare the cellulose conducting film with high flexibility, high transparency and high conductivity; the preparation process is simple and easy to control, and the cellulose conductive film with uniform surface can be obtained, so that the high-valued application of cellulose is realized, and the quality of the conductive substrate is improved.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of photoelectric materials, in particular to a preparation method of a high-performance conductive cellulose membrane and a product thereof.
[ background of the invention ]
With the progress of modern technologies, the flexibility, foldability and wearability of electronic devices have become the development trend of future electronic technologies. Compared with the traditional electronic device, the flexible electronic equipment has good application prospect in the fields of communication, information, biomedicine, mechanical manufacturing, aerospace, national defense safety and the like due to the unique flexibility and ductility of the flexible electronic equipment. Flexible transparent conductive films are the basis for the fabrication of flexible electronic devices and therefore also need to possess unique properties, including light weight, deformability, nonfriability, good electrical conductivity, high optical transparency, good mechanical properties, thermal and chemical stability, and the like.
The common flexible transparent conductive film has the substrate of high polymer transparent film such as polyethylene terephthalate (PET) film, Polycarbonate (PC), polyvinyl chloride (PVC) and the like, and the film has the characteristics of light weight, ultra-thin property, good flexibility and the like. However, these high molecular organic polymers are difficult to recycle or naturally degrade, so that white garbage is easily formed, the ecological environment is seriously damaged, and the survival of human beings is threatened.
In order to realize sustainable development of resources, the need to replace fossil raw materials with new materials has been urgent. The cellulose is used as a cheap natural polymer material, has the advantages of wide source range, degradability, regeneration, environmental friendliness and the like, the prepared transparent flexible cellulose membrane substrate is more and more widely concerned, and the huge natural reserve can completely meet the requirements of electronic products on conductive film substrates.
The conductive material formed by the inorganic doped oxide has the advantages of high light transmittance, low resistivity, excellent thermal property and the like, and can be used for constructing a high-transparency conductive substrate with a cellulose film, but the conductive material constructed by the doped oxide is hard and lacks flexibility, and cannot be used for constructing a flexible conductive substrate and a flexible electronic device thereof. The doped oxide is directly deposited and grown on the flexible organic cellulose membrane substrate, a structure matched with the cellulose lattice is difficult to form, the doped oxide is easy to fall off from the cellulose substrate, and the performance of the conductive film is reduced.
[ summary of the invention ]
The technical problem to be solved by the invention is to provide a preparation method of a high-performance conductive cellulose membrane and a product thereof, wherein a ZnO buffer layer is inserted into an inorganic conductive layer and an organic cellulose membrane to prepare a cellulose conductive membrane with high flexibility, high transparency and high conductivity; the preparation process is simple and easy to control, and the cellulose conductive film with uniform surface can be obtained, so that the high-valued application of cellulose is realized, and the quality of the conductive substrate is improved.
The invention is realized by the following steps:
a preparation method of a high-performance conductive cellulose membrane comprises the following steps:
(1) dissolving zinc acetate in an ethanolamine and ethylene glycol monomethyl ether solvent, preparing a ZnO precursor solution through a chemical reaction, and spin-coating the ZnO precursor solution on a cellulose membrane substrate;
(2) placing the cellulose membrane coated with the ZnO solution in a drying device for drying to obtain a cellulose-ZnO membrane;
(3) taking a dry cellulose-ZnO film as a substrate, and plating an inorganic doped oxide conducting layer to obtain a high-performance conducting cellulose film;
the thickness of the cellulose-ZnO film in the conductive cellulose film is 10-350 μm, and the thickness of the inorganic doped oxide conductive layer is 10-350 μm.
Further, the ZnO precursor solution spin-coated on the cellulose membrane in the step (1) is 400-1000 ml; the number of spin-coating layers is single, 2, and 3; the spin coating method includes single-layer drying, spin coating, continuous spin coating and drying.
Further, the drying method in the step (2) includes drying in an air drying oven, drying in a vacuum drying oven, drying in a thermostatic chamber, and drying in a room at normal temperature.
Further, the conductive target material of the inorganic doped oxide conductive layer in the step (3) comprises aluminum doped zinc oxide AZO and indium tin oxide ITO, and the inorganic doped oxide conductive layer is prepared by a vacuum evaporation technology; the modes of sputtering the conducting layer by the vacuum evaporation technology comprise single-target sputtering and double-target sputtering, wherein the single-target sputtering time is 1-3 h; the sputtering time of the double targets is 0.5h-2 h.
Further, the high-performance conductive cellulose membrane prepared by the preparation method of the high-performance conductive cellulose membrane takes the cellulose membrane as a substrate, a ZnO buffer layer is compounded on the cellulose membrane substrate, and a layer of inorganic doped oxide conductive layer is plated on the ZnO buffer layer.
The invention has the following advantages:
according to the invention, the buffer layer which can be well combined with the organic cellulose substrate and the inorganic doped oxide is constructed between the organic cellulose substrate and the inorganic doped oxide, so that the flexible and transparent cellulose-based conductive film is constructed. Firstly, a ZnO precursor is grown on a cellulose membrane substrate by a sol-gel method, and a hydrogen bond network system of cellulose and ZnO is constructed through hydrolysis reaction, so that firm combination between the cellulose and the ZnO is realized. And then growing an inorganic doped oxide conductive material on the surface of the ZnO buffer layer, and forming firm combination between ZnO and the inorganic doped oxide based on the lattice matching property and good miscibility of the inorganic ZnO and the inorganic doped oxide, so that a structure of the cellulose substrate-the ZnO buffer layer-the inorganic conductive material is constructed, and finally high flexibility and high stability of the high-performance conductive cellulose film are realized.
Namely, the invention can prepare the cellulose conductive film with high flexibility, high transparency and high conductivity by inserting the ZnO buffer layer into the inorganic conductive layer and the organic cellulose film. The preparation process is simple and easy to control, and the quality of the conductive substrate is improved.
[ detailed description ] embodiments
The invention relates to a preparation method of a high-performance conductive cellulose membrane, which comprises the following steps:
(1) dissolving zinc acetate in an ethanolamine and ethylene glycol monomethyl ether solvent, preparing a ZnO precursor solution through a chemical reaction, and spin-coating the ZnO precursor solution on a cellulose membrane substrate;
(2) placing the cellulose membrane coated with the ZnO solution in a drying device for drying to obtain a cellulose-ZnO membrane;
(3) taking a dry cellulose-ZnO film as a substrate, and plating an inorganic doped oxide conducting layer to obtain a high-performance conducting cellulose film;
the thickness of the cellulose-ZnO film in the conductive cellulose film is 10-350 μm, and the thickness of the inorganic doped oxide conductive layer is 10-350 μm.
The volume of the ZnO precursor solution spin-coated on the cellulose membrane in the step (1) is 400-1000 ml; the number of spin-coating layers is single, 2, and 3; the spin coating method includes single-layer drying, spin coating, continuous spin coating and drying.
The drying mode in the step (2) comprises drying in an air drying oven, drying in a vacuum drying oven, drying in a thermostatic chamber and drying in a room temperature.
The conductive target material of the inorganic doped oxide conductive layer in the step (3) is aluminum doped zinc oxide AZO and indium tin oxide ITO, and the inorganic doped oxide conductive layer is prepared by a vacuum evaporation technology; the modes of sputtering the conducting layer by the vacuum evaporation technology comprise single-target sputtering and double-target sputtering, wherein the single-target sputtering time is 1-3 h; the sputtering time of the double targets is 0.5h-2 h.
The invention also relates to a high-performance conductive cellulose membrane prepared by the method, wherein the high-performance conductive cellulose membrane takes a cellulose membrane as a substrate, a ZnO buffer layer is compounded on the cellulose membrane substrate, and a layer of inorganic doped oxide conductive layer is plated on the ZnO buffer layer.
The technical solution of the present invention will be clearly and completely described with reference to the following detailed description. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1: preparation of high-performance conductive cellulose membrane
Step (1), measuring 400ml of ZnO solution by using a liquid transfer gun, and spin-coating the ZnO solution on the surface of a cellulose membrane for 40s by using a desktop spin coater 2000;
step (2), placing the cellulose membrane coated with the ZnO solution in a vacuum drying oven at 80 ℃ for drying to obtain a cellulose-ZnO membrane with the thickness of 80 um;
and (3) placing the obtained 80-um-thick cellulose-ZnO film in a magnetron sputtering cavity, vacuumizing to 2.5 x 10-4Pa, and sputtering the ITO target for 2 hours by using a single target to obtain the ITO conductive layer with the thickness of 270um, the resistance of 180 omega/sq and the transparency of 78%. The resistance of the high-performance conductive cellulose film is only increased by 1 percent after 50 times of bending treatment with the curvature radius of 3 mm.
Example 2: preparation of high-performance conductive cellulose membrane
Step (1), measuring 600ml of ZnO solution by using a liquid transfer gun, and spin-coating the ZnO solution on the surface of a cellulose membrane for 40s by a desktop spin coater 2000;
step (2), placing the cellulose membrane coated with the ZnO solution in a forced air drying oven at 80 ℃ for drying to obtain a cellulose-ZnO membrane with the thickness of 200 um;
and (3) placing the obtained 200-micrometer cellulose-ZnO film in a magnetron sputtering cavity, vacuumizing to 2.5 x 10-4Pa, and sputtering an AZO target material for 0.5h by using a double target, wherein the thickness of the obtained AZO conductive layer is 210 micrometers, the resistance is 115 omega/sq, and the transparency is 89%. The resistance of the high-performance conductive cellulose membrane is only increased by 0.1 percent after 100 times of bending treatment with the curvature radius of 4 mm.
Example 3: preparation of high-performance conductive cellulose membrane
Measuring 1000ml of ZnO solution by using a liquid transfer gun, and spin-coating the ZnO solution on the surface of a cellulose membrane for 40s by a desktop spin coater 2000;
placing the cellulose membrane coated with the ZnO solution in a constant temperature and humidity environment for drying to obtain a 270um thick cellulose-ZnO membrane;
and (3) placing the 270-um-thick cellulose-ZnO film in a magnetron sputtering cavity, vacuumizing to 2.5 x 10-4Pa, and sputtering an AZO target material for 3h by using a single target to obtain an AZO conductive layer with the thickness of 450um, the resistance of 145 omega/sq and the transparency of 75%. The resistance of the high-performance conductive cellulose film is only increased by 1.5 percent after being bent for 80 times and with the curvature radius of 2 mm.
Example 4: preparation of high-performance conductive cellulose membrane
Measuring 800ml of ZnO solution by using a liquid transfer gun, and spin-coating the ZnO solution on the surface of a cellulose membrane for 40s by a desktop spin coater 2000;
step (2), placing the cellulose membrane coated with the ZnO solution in a rotary mode in a normal-temperature environment, and drying to obtain a cellulose-ZnO membrane with the thickness of 300 microns;
and (3) placing the obtained 300-micron-thick cellulose-ZnO film in a magnetron sputtering cavity, vacuumizing to 2.5 x 10-4Pa, and sputtering the ITO target for 1h by using double targets to obtain the ITO conductive layer with the thickness of 230 microns, the resistance of 260 omega/sq and the transparency of 81%. The resistance of the high-performance conductive cellulose membrane is only increased by 3 percent after being bent for 200 times and with the curvature radius of 10 mm.
The method comprises the steps of generating a ZnO amorphous buffer layer on a cellulose membrane substrate by a sol-gel method, constructing a hydrogen bond network system of cellulose and ZnO through hydrolysis reaction, realizing firm combination between the cellulose and the ZnO, then growing an inorganic doped oxide conductive material on the surface of a ZnO buffer layer, forming firm combination between ZnO and the inorganic doped oxide based on lattice matching and good miscibility of the inorganic ZnO and the inorganic doped oxide, and constructing a structure of the cellulose substrate-the ZnO buffer layer-the inorganic conductive material, thereby finally realizing high flexibility and high stability of the high-performance conductive cellulose membrane.
Although specific embodiments of the invention have been described above, it will be understood by those skilled in the art that the specific embodiments described are illustrative only and are not limiting upon the scope of the invention, and that equivalent modifications and variations can be made by those skilled in the art without departing from the spirit of the invention, which is to be limited only by the appended claims.
Claims (5)
1. A preparation method of a high-performance conductive cellulose membrane is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving zinc acetate in an ethanolamine and ethylene glycol monomethyl ether solvent, preparing a ZnO precursor solution through a chemical reaction, and spin-coating the ZnO precursor solution on a cellulose membrane substrate;
(2) placing the cellulose membrane coated with the ZnO solution in a drying device for drying to obtain a cellulose-ZnO membrane;
(3) taking a dry cellulose-ZnO film as a substrate, and plating an inorganic doped oxide conducting layer to obtain a high-performance conducting cellulose film;
the thickness of the cellulose-ZnO film in the conductive cellulose film is 10-350 μm, and the thickness of the inorganic doped oxide conductive layer is 10-350 μm.
2. The method for preparing a high-performance conductive cellulose film according to claim 1, wherein: the volume of the ZnO precursor solution spin-coated on the cellulose membrane in the step (1) is 400-1000 ml; the number of spin-coating layers is single, 2, and 3; the spin coating method includes single-layer drying, spin coating, continuous spin coating and drying.
3. The method for preparing a high-performance conductive cellulose film according to claim 1, wherein: the drying mode in the step (2) comprises drying in an air drying oven, drying in a vacuum drying oven, drying in a thermostatic chamber and drying in a room temperature.
4. The method for preparing a high-performance conductive cellulose film according to claim 1, wherein: the conductive target material of the inorganic doped oxide conductive layer in the step (3) is aluminum doped zinc oxide AZO and indium tin oxide ITO, and the inorganic doped oxide conductive layer is prepared by a vacuum evaporation technology; the modes of sputtering the conducting layer by the vacuum evaporation technology comprise single-target sputtering and double-target sputtering, wherein the single-target sputtering time is 1-3 h; the sputtering time of the double targets is 0.5h-2 h.
5. A high performance electrically conductive cellulose film, characterized by: the high-performance electroconductive cellulose film is prepared based on the preparation method of the high-performance electroconductive cellulose film according to any one of claims 1 to 4; the high-performance conductive cellulose membrane takes a cellulose membrane as a substrate, a ZnO buffer layer is compounded on the cellulose membrane substrate, and a layer of inorganic doped oxide conductive layer is plated on the ZnO buffer layer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140272397A1 (en) * | 2011-10-26 | 2014-09-18 | Inha-Industry Partnership Institute | Zinc oxide-cellulose nanocomposite and preparation method thereof |
| CN105854949A (en) * | 2015-01-23 | 2016-08-17 | 中国科学院宁波材料技术与工程研究所 | Cellulose/nano zinc oxide composite material and preparation method and application thereof |
| CN110724307A (en) * | 2019-09-10 | 2020-01-24 | 沈阳化工大学 | Preparation method of renewable cellulose conductive film with stable flexible conductivity |
| CN111019180A (en) * | 2019-11-27 | 2020-04-17 | 福建农林大学 | Preparation method of green environment-friendly transparent conductive cellulose membrane and product thereof |
-
2020
- 2020-08-31 CN CN202010894185.0A patent/CN112289500A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140272397A1 (en) * | 2011-10-26 | 2014-09-18 | Inha-Industry Partnership Institute | Zinc oxide-cellulose nanocomposite and preparation method thereof |
| CN105854949A (en) * | 2015-01-23 | 2016-08-17 | 中国科学院宁波材料技术与工程研究所 | Cellulose/nano zinc oxide composite material and preparation method and application thereof |
| CN110724307A (en) * | 2019-09-10 | 2020-01-24 | 沈阳化工大学 | Preparation method of renewable cellulose conductive film with stable flexible conductivity |
| CN111019180A (en) * | 2019-11-27 | 2020-04-17 | 福建农林大学 | Preparation method of green environment-friendly transparent conductive cellulose membrane and product thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘茜等: "纤维素/ZnO复合膜的制备及其性能研究", 《中国造纸》 * |
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