CN110079057B - Transparent conductive material, manufacturing method thereof and manufacturing method of transparent conductive film - Google Patents
Transparent conductive material, manufacturing method thereof and manufacturing method of transparent conductive film Download PDFInfo
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Abstract
The invention provides a transparent conductive material, a manufacturing method thereof and a manufacturing method of a transparent conductive film. The transparent conductive material is a PEDOT material with long alkyl side chains and hydroxyl and pyridine rings on the side chains, so that the water dispersibility of the transparent conductive material can be improved, the stretchability and the conductivity of the transparent conductive film prepared from the transparent conductive material can be improved, and the manufacturing cost of the transparent conductive film can be reduced.
Description
Technical Field
The invention relates to the technical field of display, in particular to a transparent conductive material and a manufacturing method thereof as well as a manufacturing method of a transparent conductive film.
Background
Liquid Crystal Displays (LCDs) have many advantages such as thin body, power saving, no radiation, and are widely used, for example: liquid crystal televisions, mobile phones, Personal Digital Assistants (PDAs), digital cameras, computer screens, notebook computer screens, or the like, are dominant in the field of flat panel displays.
Most of the existing liquid crystal displays in the market are backlight liquid crystal displays (lcds), which include a liquid crystal panel and a backlight module (backlight module). The liquid crystal panel operates on the principle that liquid crystal molecules are filled between a Thin film transistor Array Substrate (TFT Array Substrate) and a Color Filter Substrate (Color Filter, CF), and driving voltages are applied to the two substrates to control the rotation direction of the liquid crystal molecules, so that light rays of the backlight module are refracted out to generate a picture.
As an important component of the TFT-LCD, a metal oxide material, such as Indium Tin Oxide (ITO), is mainly used at present, and the material is formed by Physical Vapor Deposition (PVD). However, because indium is a rare metal, the price is high, and the indium storage capacity on the earth is far from meeting the increasing demand of people for transparent electrodes. Secondly, the physical vapor deposition method has expensive used equipment and higher maintenance cost; and the metal oxide material needs to be calcined at high temperature to process and optimize the crystal form so as to improve the conductivity, and finally, the metal oxide material is mostly ceramic material which is brittle and easy to break, so that the metal oxide material is not suitable for flexible display with large curvature and multiple bending.
In order to solve the above problems, it is proposed to use poly (3, 4-ethylenedioxythiophene): the proposal of preparing the transparent electrode by replacing a metal oxide semiconductor with a poly (4-styrene sulfonic acid) (PEDOT: PSS) material is that the current PEDOT: in general, in the preparation of PSS, neutral PEDOT is oxidized and de-electrized to form positively charged oxidized PEDOT, and PSS having good water solubility but poor conductivity is doped to form a polyion complex, which is dispersed in water. But the PSS has poor conductivity and a compact structure, so that the Pi-Pi accumulation formed by PEDOT is less, and the conductivity is greatly influenced; also for flexible applications, PEDOT: the conductive polymer formed by PSS is stretchable and does not satisfy a flexible display of a large curvature, multiple bending.
Disclosure of Invention
The invention aims to provide a transparent conductive material, which can improve the water dispersibility of the transparent conductive material, improve the stretchability and the conductivity of a transparent conductive film prepared from the transparent conductive material and reduce the manufacturing cost of the transparent conductive film.
The present invention also provides a method for manufacturing a transparent conductive material, which can improve water dispersibility of the transparent conductive material, improve stretchability and conductivity of the transparent conductive film manufactured from the transparent conductive material, and reduce manufacturing cost of the transparent conductive film. .
The invention also aims to provide a method for manufacturing the transparent conductive film, which can improve the stretchability and the conductivity of the transparent conductive film manufactured by the transparent conductive material and reduce the manufacturing cost of the transparent conductive film. .
In order to achieve the above object, the present invention provides a transparent conductive material having the following structure:
wherein n is the polymerization degree, and m is a positive integer of 6-13.
Alternatively, m is 8 or 9.
The invention also provides a manufacturing method of the transparent conductive material, which comprises the following steps:
step S1, providing a thiophene raw material, and reacting the thiophene raw material through a catalytic action to obtain a first material solution, wherein the thiophene raw material has the following structure:
wherein m is a positive integer of 6-13, and X is a halogen element;
the first material has the following structure:
wherein n is the degree of polymerization, and m is a positive integer of 6-13;
step S2, adding the first material solution into the pyridine-3-carboxylic acid chloride solution, and reacting to obtain a second material solution, wherein the second material has the following structure:
step S3, mixing the first material solution and the second material solution to obtain the transparent conductive material, where the transparent conductive material has the following structure:
the step S1 specifically includes: providing a thiophene raw material, reacting the thiophene raw material to form polyhalogenated thiophene under the catalytic action of a palladium complex in a protective gas atmosphere by using a Schlenk technology, and continuously reacting the polyhalogenated thiophene under the catalytic action of alkali to obtain a first material solution.
The step S2 specifically includes: adding pyridine-3-carboxylic acid chloride into a mixed solvent of toluene and alcohols to obtain a pyridine-3-carboxylic acid chloride solution, heating the pyridine-3-carboxylic acid chloride solution, gradually dripping a first material solution into the heated pyridine-3-carboxylic acid chloride solution, continuously stirring until the solution is clear after dripping, and separating and purifying to obtain a second material solution.
Alternatively, m is 8 or 9.
In step S3, the first material solution and the second material solution are mixed in a ratio of 10: 1-1: 10 by volume.
The invention also provides a manufacturing method of the transparent conductive film, which comprises the following steps:
step S10, providing a transparent conductive material having the following structure:
wherein n is the degree of polymerization, and m is a positive integer of 6-13;
step S20, providing a substrate, and coating the transparent conductive material on the substrate;
and step S30, baking and curing the transparent conductive material to obtain the transparent conductive film.
In step 20, the transparent conductive material is coated on the substrate by a spin coating process.
Between the step 10 and the step 20, a step of adjusting the viscosity and the solid content of the transparent conductive material so that the viscosity and the solid content of the transparent conductive material are consistent with a preset target viscosity and a preset target solid content is further included.
The invention has the beneficial effects that: the invention provides a transparent conductive material, which is a PEDOT material with long alkyl side chains and hydroxyl and pyridine rings on the side chains, and can improve the water dispersibility of the transparent conductive material, improve the stretchability and the conductivity of a transparent conductive film prepared from the transparent conductive material, and reduce the manufacturing cost of the transparent conductive film. The invention also provides a preparation method of the transparent conductive material, which can improve the water dispersibility of the transparent conductive material and improve the stretchability and the conductivity of the transparent conductive film prepared from the transparent conductive material. The invention also discloses a manufacturing method of the transparent conductive film, which can improve the tensile rate and the conductivity of the transparent conductive film and reduce the manufacturing cost of the transparent conductive film.
Drawings
For a better understanding of the nature and technical aspects of the present invention, reference should be made to the following detailed description of the invention, taken in conjunction with the accompanying drawings, which are provided for purposes of illustration and description and are not intended to limit the invention.
In the drawings, there is shown in the drawings,
FIG. 1 is a flow chart of a method of making a transparent conductive material of the present invention;
fig. 2 is a flowchart of a method for manufacturing a transparent conductive film according to the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
The invention provides a transparent conductive material, which has the following structure:
wherein n is the polymerization degree, and m is a positive integer of 6-13.
Firstly, the transparent conductive material has a side chain with a long alkyl chain, so that the dispersibility of PEDOT can be improved, compared with the prior art, PSS is not needed to help dispersion, and the reduction of the conductivity of the material due to the use of PSS is avoided; secondly, the side chain of the transparent conductive material is provided with hydroxyl and a pyridine ring, and the hydroxyl is mutually connected through the electron-withdrawing action of nitrogen atoms on pyridine on the hydroxyl, so that the transparent conductive film prepared by the transparent conductive material has stretchability; thirdly, the transparent conductive material is orderly arranged through the steric hindrance effect of the side chain to form large-range pi-pi accumulation, so that the high conductivity of the material is ensured; finally, when the transparent conductive material is adopted to manufacture the transparent conductive film, the manufacturing can be completed by a solution processing method, and compared with the traditional metal oxide material, the high-temperature manufacturing process is not needed, so that the equipment and material cost can be reduced, and the product reliability can be improved.
The chain length of the long alkyl chain can influence the dispersibility and conductivity of the transparent conductive material, and the chain is short, so that the dispersion of thiophene is not facilitated; longer chains lead to too bulky PEDOT, reduced pi-pi stacking and reduced conductivity, and m is preferably 8 or 9 in the invention, so that the transparent conductive material has optimal dispersibility and conductivity.
Referring to fig. 1, the present invention provides a method for manufacturing a transparent conductive material, including the following steps:
step S1, providing a thiophene raw material, and reacting the thiophene raw material through a catalytic action to obtain a first material solution, wherein the thiophene raw material has the following structure:
wherein m is a positive integer of 6-13, and X is a halogen element;
the first material has the following structure:
wherein n is the degree of polymerization, and m is a positive integer of 6-13;
specifically, the step S1 specifically includes: providing a thiophene raw material, using a Schlenk technology (an anhydrous and oxygen-free operation technology of double-row pipes), in a protective gas atmosphere, enabling the thiophene raw material to react under the catalytic action of a palladium (P) complex, namely C-H and C-X of the thiophene raw material are cross-coupled to form polyhalogenated thiophene, and then enabling the polyhalogenated thiophene to continue to react under the catalytic action of alkali, namely hydrolysis reaction of halogenated hydrocarbon to obtain a first material solution.
Preferably, the protective gas is nitrogen or argon, and X is bromine (Br).
For example, a typical first material solution manufacturing process includes: thiophene starting material (0.1g, 0.255mmol) and potassium carbonate (0.077g,0.56mmol) were degassed twice with argon in 3 ml of sulfoxide/toluene (1:1) and pd (dppf) (oac) (10mg) was added, and after stirring for 4 hours at 80 ℃ under argon, the reaction mixture was poured into water (30ml) and extracted with dichloromethane. Next, the organic layer was washed with water, and then dried to remove the solvent. The solvent-removed product was then purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (1:1) as eluent composition to yield a solid polyhalothiophene. Adding the above solid powder into alkaline aqueous solution (such as ethanol or sodium hydroxide), heating at 40 deg.C for 5min or standing for a long time, separating, and purifying to obtain first material solution.
The specific reaction process is as follows:
step S2, adding the first material solution into the pyridine-3-carboxylic acid chloride solution, and reacting to obtain a second material solution, wherein the second material has the following structure:
specifically, the step S2 specifically includes: adding pyridine-3-carboxylic acid chloride into a mixed solvent of toluene and alcohols to obtain a pyridine-3-carboxylic acid chloride solution, heating the pyridine-3-carboxylic acid chloride solution, gradually dripping a first material solution into the heated pyridine-3-carboxylic acid chloride solution, continuously stirring until the solution is clear after dripping, and separating and purifying to obtain a second material solution.
For example, a typical fabrication process for the second material solution is as follows: mixing 0.2mol of pyridine-3-carboxylic acid chloride with 100ml of a toluene and alcohol mixed solvent to obtain a first solution, heating the first solution at 50 ℃, slowly dripping the first material solution prepared in the step S1 for one hour, continuously stirring until the solution is clear after dripping, and then separating and purifying to obtain a second material solution.
Typical solvents to be mentioned for pyridine-3-carboxylic acid chlorides are: and the PEDOT has good solubility in water, ethanol, glycerol, isopropanol and sorbitol, so that the pyridine-3-carboxylic acid chloride in the second material solution can be well mixed with the first material by selecting the toluene and alcohol mixed solvent to prepare the first solution.
Step S3, mixing the first material solution and the second material solution to obtain the transparent conductive material, where the transparent conductive material has the following structure:
specifically, in the step S3, the first material solution and the second material solution are mixed in a volume ratio of 10: 1-1: 10, and stirring for 5-240 min to obtain the transparent conductive material.
First, the first material and the second material have side chains with long alkyl chains, so that the dispersibility of PEDOT can be improved, compared with the prior art, PSS is not needed to help dispersion, and the decrease of the conductivity of the materials due to the use of PSS is avoided; secondly, the side chain of the first material is provided with hydroxyl, the side chain of the second material is provided with a pyridine ring, and the side chain of the second material is connected with the pyridine ring through the electron-withdrawing action of nitrogen atoms on the pyridine in the second material on the hydroxyl on the first material, so that the transparent conductive film prepared by the transparent conductive material has stretchability; thirdly, the first material and the second material are orderly arranged through the steric hindrance of the side chain to form large-range pi-pi accumulation, so that the high conductivity of the materials is ensured; finally, when the transparent conductive material is adopted to manufacture the transparent conductive film, the manufacturing can be completed by a solution processing method, and compared with the traditional metal oxide material, the high-temperature manufacturing process is not needed, so that the equipment and material cost can be reduced, and the product reliability can be improved.
The chain length of the long alkyl chain can influence the dispersibility and conductivity of the transparent conductive material, and the chain is short, so that the dispersion of thiophene is not facilitated; longer chains lead to too bulky PEDOT, reduced pi-pi stacking and reduced conductivity, and m is preferably 8 or 9 in the invention, so that the transparent conductive material has optimal dispersibility and conductivity.
Referring to fig. 2, the present invention further provides a method for manufacturing a transparent conductive film, including the following steps:
step S10, providing a transparent conductive material having the following structure:
wherein n is the degree of polymerization, and m is a positive integer of 6-13;
step S20, providing a substrate, and coating the transparent conductive material on the substrate;
and step S30, baking and curing the transparent conductive material to obtain the transparent conductive film.
Specifically, in step 20, the transparent conductive material is coated on the substrate by using a spin coating process.
Specifically, between the step 10 and the step 20, a step of adjusting the viscosity and the solid content of the transparent conductive material so that the viscosity and the solid content of the transparent conductive material are consistent with a preset target viscosity and a target solid content is further included.
Specifically, a typical manufacturing process of the transparent conductive film of the present invention is as follows: and (3) applying the transparent conductive material. Sealing and stirring for 3-120min under the condition of constant-temperature water bath at 30-100 ℃ until the solution is uniform, continuously adding a solvent to reach the required viscosity and solid content, setting the rotation speed of a spin coating instrument to be 400-2500 r/min, setting the time T1 to be 2-10 s, and the time T2 to be 2-10 s, dripping the obtained transparent conductive material with the appropriate solid content on a substrate, spin-coating to prepare a wet film, pre-baking and post-baking curing at 40-120 ℃ to obtain the transparent conductive film, and further, continuously performing a patterning process on the transparent conductive film on the basis.
Firstly, the transparent conductive material has a side chain with a long alkyl chain, so that the dispersibility of PEDOT can be improved, compared with the prior art, PSS is not needed to help dispersion, and the reduction of the conductivity of the material due to the use of PSS is avoided; secondly, the side chain of the transparent conductive material is provided with hydroxyl and a pyridine ring, and the hydroxyl is mutually connected through the electron-withdrawing action of nitrogen atoms on pyridine on the hydroxyl, so that the transparent conductive film prepared by the transparent conductive material has stretchability; thirdly, the transparent conductive material is orderly arranged through the steric hindrance effect of the side chain to form large-range pi-pi accumulation, so that the high conductivity of the material is ensured; finally, when the transparent conductive material is adopted to manufacture the transparent conductive film, the manufacturing can be completed by a solution processing method, and compared with the traditional metal oxide material, the high-temperature manufacturing process is not needed, so that the equipment and material cost can be reduced, and the product reliability can be improved.
In summary, the invention provides a transparent conductive material, which is a PEDOT material having a long alkyl side chain and a hydroxyl group and a pyridine ring on the side chain, and can improve water dispersibility of the transparent conductive material, improve stretchability and conductivity of a transparent conductive film made of the transparent conductive material, and reduce manufacturing cost of the transparent conductive film. The invention also provides a preparation method of the transparent conductive material, which can improve the water dispersibility of the transparent conductive material and improve the stretchability and the conductivity of the transparent conductive film prepared from the transparent conductive material. The invention also discloses a manufacturing method of the transparent conductive film, which can improve the tensile rate and the conductivity of the transparent conductive film and reduce the manufacturing cost of the transparent conductive film.
As described above, it will be apparent to those skilled in the art that other various changes and modifications may be made based on the technical solution and concept of the present invention, and all such changes and modifications are intended to fall within the scope of the appended claims.
Claims (10)
1. A transparent conductive material having the structure:
wherein n is the polymerization degree, and m is a positive integer of 6-13.
2. The transparent conductive material according to claim 1, wherein m is 8 or 9.
3. A method for manufacturing a transparent conductive material is characterized by comprising the following steps:
step S1, providing a thiophene raw material, and reacting the thiophene raw material through a catalytic action to obtain a first material solution, wherein the thiophene raw material has the following structure:
wherein m is a positive integer of 6-13, and X is a halogen element;
the first material has the following structure:
wherein n is the degree of polymerization, and m is a positive integer of 6-13;
step S2, adding the first material solution into the pyridine-3-carboxylic acid chloride solution, and reacting to obtain a second material solution, wherein the second material has the following structure:
step S3, mixing the first material solution and the second material solution to obtain the transparent conductive material, where the transparent conductive material has the following structure:
4. the method for manufacturing a transparent conductive material according to claim 3, wherein the step S1 specifically includes: providing a thiophene raw material, reacting the thiophene raw material to form polyhalogenated thiophene under the catalytic action of a palladium complex in a protective gas atmosphere by using a Schlenk technology, and continuously reacting the polyhalogenated thiophene under the catalytic action of alkali to obtain a first material solution.
5. The method for manufacturing a transparent conductive material according to claim 3, wherein the step S2 specifically includes: adding pyridine-3-carboxylic acid chloride into a mixed solvent of toluene and alcohols to obtain a pyridine-3-carboxylic acid chloride solution, heating the pyridine-3-carboxylic acid chloride solution, gradually dripping a first material solution into the heated pyridine-3-carboxylic acid chloride solution, continuously stirring until the solution is clear after dripping, and separating and purifying to obtain a second material solution.
6. The method for manufacturing a transparent conductive material according to claim 3, wherein m is 8 or 9.
7. The method for manufacturing a transparent conductive material according to claim 3, wherein in step S3, the first material solution and the second material solution are mixed in a ratio of 10: 1-1: 10 by volume.
8. A method for manufacturing a transparent conductive film is characterized by comprising the following steps:
step S10, providing a transparent conductive material having the following structure:
wherein n is the degree of polymerization, and m is a positive integer of 6-13;
step S20, providing a substrate, and coating the transparent conductive material on the substrate;
and step S30, baking and curing the transparent conductive material to obtain the transparent conductive film.
9. The method of claim 8, wherein the step 20 comprises applying the transparent conductive material on the substrate by a spin coating process.
10. The method for manufacturing a transparent conductive film according to claim 8, further comprising, between step 10 and step 20, a step of adjusting the viscosity and solid content of the transparent conductive material so that the viscosity and solid content of the transparent conductive material are consistent with a preset target viscosity and target solid content.
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| TWI470002B (en) * | 2010-10-20 | 2015-01-21 | Sanyo Chemical Ind Ltd | And a method for producing a conductive film and a conductive film |
| CN102604334B (en) * | 2012-02-07 | 2013-08-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | Self-supporting transparent highly-conductive poly-3,4-ethylenedioxythiophene (PEDOT) film and preparation method of the film |
| CN104592499B (en) * | 2014-11-23 | 2017-11-14 | 北京航空航天大学 | Three bithiophene class conjugated polymer materials and preparation method and application |
| CN110079057B (en) * | 2019-04-30 | 2020-01-21 | 深圳市华星光电技术有限公司 | Transparent conductive material, manufacturing method thereof and manufacturing method of transparent conductive film |
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2019
- 2019-04-30 CN CN201910365448.6A patent/CN110079057B/en active Active
- 2019-09-03 WO PCT/CN2019/104164 patent/WO2020220548A1/en active Application Filing
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| CN110079057A (en) | 2019-08-02 |
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