CN116693908A - PEDOT-PSS film with high conductivity and preparation method thereof - Google Patents
PEDOT-PSS film with high conductivity and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims abstract description 57
- 239000002608 ionic liquid Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 33
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- 238000005516 engineering process Methods 0.000 claims abstract description 6
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 2
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 2
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
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- MIFGTXFTLQVWJW-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;2-hydroxypropanoate Chemical compound CC(O)C([O-])=O.C[N+](C)(C)CCO MIFGTXFTLQVWJW-UHFFFAOYSA-M 0.000 description 1
- DVGVMQVOCJNXNJ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;4-methylbenzenesulfonate Chemical compound C[N+](C)(C)CCO.CC1=CC=C(S([O-])(=O)=O)C=C1 DVGVMQVOCJNXNJ-UHFFFAOYSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
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- 238000002390 rotary evaporation Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
Abstract
The invention belongs to the technical field of material preparation and laser processing, and discloses a PEDOT (polyether-ether-ketone) PSS film with high conductivity and a preparation method thereof. The method comprises the following steps: PEDOT, filtering the PSS aqueous solution; adding an ionic liquid to partially remove PSS in PEDOT PSS in a phase separation mode to obtain a mixed solution; spin-coating the mixed solution on a planar substrate and primarily drying; and further carrying out phase separation on the dried PEDOT-PSS film in a laser environment to remove PSS and improve mechanical properties, so as to obtain the PEDOT-PSS film with high conductivity. The PEDOT-PSS film with high conductivity has high conductivity, excellent water stability and mechanical property, is more rapid than the traditional drying annealing mode, can be subjected to patterning treatment according to requirements through a laser technology, is not damaged due to immersion in liquid, does not need toxic additives in the preparation process, does not need post-treatment and detoxification, and has excellent biocompatibility.
Description
Technical Field
The invention belongs to the technical field of material preparation and laser processing, and particularly relates to a PEDOT (polyether-ether-ketone) PSS film with high conductivity and a preparation method thereof.
Background
In recent years, flexible conductive materials have attracted considerable attention in academia and industry due to their potential applications in electromagnetic shielding materials, flexible sensor devices, supercapacitors, and the like. The flexible conductive material mainly comprises a metal-based or carbon-based material with a morphology of nano particles, nano wires, nano sheets or three-dimensional porous structures, and a conductive polymer. Compared with metal or carbon-based materials, conductive polymers (e.g., polyaniline (PAN), poly (3, 4 ethylenedioxythiophene); polystyrene sulfonate (PEDOT: PS), polypyrrole) have a smaller Young's modulus, a wide variety of processing modes, and a controllable film thickness and conductivity, and are therefore considered ideal materials for constructing soft body bioelectronic devices.
Among them, PEDOT: PSS has been widely used in photovoltaic cells, displays, transistors and various physical and biological sensors due to its characteristics of controllable conductivity, excellent biocompatibility, and high transparency in the visible light range. In aqueous colloidal dispersion solutions, PEDOT: PSS tends to form a micellar microstructure consisting of a core rich in hydrophobic PEDOT and a shell rich in hydrophilic PSS, wherein the PEDOT domain and PSS domain, respectively, result in lower stretchability and higher hydrophilicity, which will affect their conductivity and stability in physiological environments. To facilitate subsequent operations, phase separation methods have been developed to properly regulate these molecular interactions, enabling a correct redistribution of the network between the conductive hydrophobic PEDOT-rich domain and the soft hydrophilic PSS-rich domain to improve conductivity, as well as other mechanical properties.
In the prior art, the way of improving the properties of PEDOT and PSS is mainly to introduce sulfuric acid, ionic liquid or surfactant to weaken the ionic bond acting force between the positively charged PEDOT and the negatively charged PSS, and recrystallize the PEDOT-enriched nanofiber by combining a high-temperature annealing or electric field application method, so that the PEDOT-enriched domains are physically interconnected due to pi-pi stacking effect. However, the solvents introduced in these techniques have a certain biotoxicity and have the problems of relatively complex process, which all lead to the adverse effects of application and rapid preparation of biological tissues, so that it is necessary to develop a PEDOT: PSS film with good biocompatibility, rapid and simple preparation process and more excellent performance.
Disclosure of Invention
The invention aims to solve the problems and provides a PEDOT: PSS film with high conductivity and a preparation method thereof.
According to the technical scheme of the invention, the preparation method of the PEDOT/PSS film with high conductivity comprises the following steps:
(1) Filtering the PEDOT-PSS aqueous solution, and dripping the ionic liquid into the filtered PEDOT-PSS aqueous solution to obtain a mixed solution, wherein the mass ratio of the ionic liquid to the mixed solution is 1:4-1:1;
(2) Stirring the mixed solution to form a uniform solution, transferring the uniform solution to a planar substrate by a spin coating method, and performing primary drying to form a film;
(3) And (3) processing the dried film by using a laser processing technology to further induce phase separation, so as to obtain the PEDOT/PSS film with high conductivity.
According to a specific embodiment of the present invention, the method may specifically comprise the steps of:
(1) Filtering the PEDOT/PSS aqueous solution through a water system needle filter to remove large particle parts;
(2) Dropwise adding an ionic liquid into the PEDOT-PSS aqueous solution obtained in the step (1), and partially removing PSS in the PEDOT-PSS through phase separation to obtain a mixed solution, wherein the mass ratio of the ionic liquid to the mixed solution is 1:4-1:1;
(3) Stirring the mixed solution obtained in the step (2) to form a uniform solution;
(4) Uniformly dispersing the uniform solution obtained in the step (3) on a plane substrate by a spin coating method, and heating, drying and forming a film in an oven;
(5) And (3) selectively annealing the dried film obtained in the step (4) by using laser and inducing phase separation, and further removing part of PSS in the PEDOT-PSS to obtain the PEDOT-PSS film.
The thickness of the PEDOT/PSS film is 1-15 mu m. The conductivity is 64.35S/cm-138S/cm.
Preferably, in the PEDOT/PSS aqueous solution, the solid content of the PEDOT/PSS is 1.0-1.3 wt% and the model is PH 1000;
preferably, the ionic liquid is a choline carboxylate ionic liquid, a mesylate ionic liquid or other hydroxyl-containing ionic liquids with good biocompatibility, such as 1- (2, 3-dihydroxyl) propyl-3-methylimidazolium tetrafluoroborate, N- (2, 3-dihydroxypropyl) pyridine hexafluorophosphate and 1- (2, 3-dihydroxyl) propyl-3-methylimidazolium chloride;
as a further preferred feature, the choline carboxylate ionic liquid is prepared by dropping the corresponding acid into an aqueous choline solution at a specific gravity of 1:1; the acid is an acid having good biocompatibility and containing a carboxylic acid group, such as any one of citric acid, lactic acid, and acetic acid.
Preferably, ultrasonic stirring is adopted for stirring, and the treatment time is 15-30 min;
preferably, the planar substrate adopts glass, silicon wafer, PET, SBS, PDMS and the like;
as a further preferable mode, the rotation speed used for spin coating is 1500-5000 rpm/min, the drying temperature is 60-80 ℃, the environment is vacuum, and the time is 15-30 min;
preferably, the laser processing technology can adopt an ultraviolet laser, a continuous wave laser and the like for laser processing;
further preferably, the laser power is 0.03 to 0.1W, the speed is 100 to 300mm/s, and the line spacing is 0.01 to 0.03mm;
as a further preferred option, the PEDOT: PSS film of different shape patterns can be patterned by laser processing.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The PEDOT-PSS conductive polymer film prepared by the method has simple, efficient and sensitive synthesis steps, and the conductive polymer film can be prepared by patterning under the further phase separation action caused by the selective annealing of laser.
(2) Unlike the prior art of solvent combined drying annealing, the conductive polymer film prepared by adopting the ionic liquid combined laser processing technology has stronger mechanical property, better self-supporting property and 64.35S/cm-138S/cm conductivity.
(3) The PEDOT-PSS conductive polymer film prepared by the invention has excellent water stability and mechanical property, is not damaged due to being soaked in liquid, does not need toxic additives in the preparation process, does not need post-treatment for detoxification, and has excellent biocompatibility.
Drawings
FIG. 1 is a schematic diagram showing the process of preparing PEDOT: PSS film according to the present invention;
FIG. 2 is a graph showing the comparison of PEDOT: PSS film properties prepared in accordance with the present invention;
FIG. 3 is a schematic diagram of PEDOT: PSS films prepared according to the present invention on various substrates;
FIG. 4 is a schematic diagram of patterned PEDOT: PSS films on various substrates after laser selective annealing made in accordance with the present invention.
FIG. 5 is a graph showing the comparison of water stability of PEDOT: PSS films prepared in accordance with the present invention;
fig. 6 is a schematic view of a laser processing platform prepared according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and examples, but the scope of the present invention is not limited to the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
In order to achieve the above object, according to the present invention, there is provided a highly conductive PEDOT-PSS film having a thickness of 1 μm to 15 μm and an electrical conductivity of 64.35S/cm to 138S/cm.
As shown in FIG. 1, according to an embodiment of the present invention, the method for preparing the highly conductive PEDOT/PSS film comprises the steps of:
step 1, filtering an original solution of the model PH 1000, wherein the solid content of PEDOT and PSS is 1.0-1.3 wt% through a filter with the aperture of 0.45 mu m;
step 2, dropwise adding a choline carboxylate ionic liquid or a mesylate ionic liquid with good biocompatibility into the PEDOT-PSS aqueous solution in the step 1, and partially removing PSS in the PEDOT-PSS to obtain a mixed solution, wherein the mass of the ionic liquid relative to the mixed solution is 1:4-1:1;
step 3, stirring the mixed solution obtained in the step 2 to form a uniform solution, wherein the stirring method is ultrasonic stirring, and the time is 10-30 min;
step 4, transferring the uniform solution obtained in the step 3 to a plane substrate through a spin coating method, wherein the spin coating speed is 1500-5000 rpm/min, and placing the substrate in a vacuum environment for preliminary drying at 60-80 ℃ for 15-30 min after spin coating;
and 5, placing the dried film obtained in the step 4 on a laser processing platform, utilizing the thermal effect and the electric field effect of laser to induce phase separation to further remove partial PSS in the PEDOT PSS, wherein the power is 0.03-0.1W, the speed is 100-300 mm/s, the line spacing is 0.01-0.03 mm, and the high-conductivity PEDOT PSS film is obtained after processing.
Preferably, the choline carboxylate ionic liquid in the step 2 is prepared by dripping the corresponding carboxylic acid (1:1) into aqueous choline bicarbonate solution, and the mixture is stirred at room temperature for 6-12 hours. The resulting product was then washed three times with diethyl ether to remove unreacted acid. Finally, excess water and traces of diethyl ether were removed by rotary evaporation. In this step, instead of using a choline carboxylate ionic liquid, a methanesulfonate ionic liquid, or other hydroxyl-containing ionic liquid having good biocompatibility, may be used. In the embodiment, the carboxylic acid is preferably lactic acid and p-toluenesulfonic acid, the prepared choline carboxylate ionic liquid is choline lactate and choline p-toluenesulfonate, and the ionic liquid/PEDOT: PSS mixed solution can be prepared by replacing lactic acid and p-toluenesulfonic acid with other carboxylic acids.
Preferably, the planar substrate in the step 4 is made of glass, silicon wafer, PET, SBS, PDMS and other materials, and is sequentially washed by ultrasonic for 10-30 min with a detergent, deionized water and ethanol before use, washed repeatedly for three times, and then soaked and stored in ethanol for standby.
Preferably, the laser in the step 5 is an ultraviolet laser or a continuous wave laser.
According to the method, after the PEDOT-PSS aqueous solution is filtered, the ionic liquid is added to partially remove PSS in the PEDOT-PSS in a phase separation mode, so that a mixed solution is obtained; spin-coating the mixed solution on a planar substrate and primarily drying; and further carrying out phase separation on the dried PEDOT-PSS film in a laser environment to remove PSS and improve mechanical properties, so as to obtain the PEDOT-PSS film with high conductivity. The PEDOT-PSS film with high conductivity has high conductivity, excellent water stability and mechanical property, is more rapid than the traditional drying annealing mode, can be subjected to patterning treatment according to requirements through a laser technology, is not damaged due to immersion in liquid, does not need toxic additives in the preparation process, does not need post-treatment and detoxification, and has excellent biocompatibility.
Example 1A method for preparing a highly conductive PEDOT: PSS film, comprising the steps of:
(1) Selecting a PEDOT-PSS solution with the model of PH 1000, wherein the solid phase content is 1.3wt%, the mass ratio of the PEDOT to the PSS is 2:5, and filtering the PEDOT-PSS solution to a container for standby by a needle-type water system microporous filter membrane with the size of 0.45 mu m;
(2) Dropping a choline carboxylate ionic liquid with good biocompatibility into the aqueous solution of PEDOT and PSS in the step (1), and partially removing the PSS in the PEDOT and the PSS to obtain a mixed solution, wherein the mass of the ionic liquid relative to the mixed solution is 1:4, and the calculation does not consider the PEDOT: water in PSS dispersion, therefore, the final mass ratio between PEDOT: PSS and ionic liquid mass in the dried composite was determined;
(3) Stirring the mixed solution obtained in the step 2 to form a uniform solution, wherein the stirring method is ultrasonic stirring, and the time is 10min;
(4) Transferring 80 mu L of the uniform solution obtained in the step 3 to a planar substrate by a spin coating method, wherein the spin coating speed is 1500rpm/min, placing the planar substrate in a vacuum environment after spin coating, and primarily drying at 60 ℃ for 15min, wherein the planar substrate is subjected to plasma treatment for 3min before use;
(5) And (3) placing the dried film obtained in the step (4) on a laser processing platform, utilizing the thermal effect and the electric field effect of laser to induce phase separation to further remove part of PSS in PEDOT PSS, wherein a continuous wave laser is selected as the laser, the power is 0.03W, the speed is 100mm/s, the line spacing is 0.01mm, and the high-conductivity PEDOT PSS film is obtained after processing.
Example 2A method for preparing a highly conductive PEDOT: PSS film, comprising the steps of:
(1) Selecting a PEDOT-PSS solution with the model of PH 1000, wherein the solid phase content is 1.3wt%, the mass ratio of the PEDOT to the PSS is 2:5, and filtering the PEDOT-PSS solution to a container for standby by a needle-type water system microporous filter membrane with the size of 0.45 mu m;
(2) Dripping the methanesulfonate ionic liquid with good biocompatibility into the PEDOT-PSS aqueous solution in the step 1, partially removing the PSS in the PEDOT-PSS to obtain a mixed solution, wherein the mass of the ionic liquid relative to the mixed solution is 1:4, and calculating without considering the water in the PEDOT-PSS dispersion, so that the final mass ratio between the PEDOT-PSS and the mass of the ionic liquid in the dry composite material is determined;
(3) Stirring the mixed solution obtained in the step 2 to form a uniform solution, wherein the stirring method is ultrasonic stirring, and the time is 10min;
(4) Transferring the uniform solution obtained in the step 3 to a planar substrate through a spin coating method, wherein the spin coating speed is 1500rpm/min, and placing the substrate in a vacuum environment for preliminary drying at 60 ℃ for 15min after spin coating;
(5) Placing the dried film obtained in the step 4 on a laser processing platform, utilizing the thermal effect and the electric field effect of laser to induce phase separation to further remove part of PSS in the PEDOT, wherein the laser is a continuous wave laser with the power of 0.03W, the speed of 100mm/s and the line spacing of 0.01mm, and obtaining the high-conductivity PEDOT PSS film after processing;
comparative example 1A method for preparing PEDOT: PSS film, comprising the steps of:
(1) Selecting a PEDOT-PSS solution with the model of PH 1000, wherein the solid phase content is 1.3wt%, the mass ratio of the PEDOT to the PSS is 2:5, and filtering the PEDOT-PSS solution to a container for standby by a needle-type water system microporous filter membrane with the size of 0.45 mu m;
(2) After plasma treatment for 1-3 min before the planar substrate is used, 80 mu L of PEDOT/PSS solution is taken to spin-coat on the planar substrate at the rotating speed of 1500rpm to prepare a PEDOT/PSS film, and the film is kept still in a vacuum environment at 60 ℃ and dried for 30min to form a film.
(3) And (3) placing the dried film obtained in the step (2) into an oven, and annealing for 30min at 120 ℃ to obtain the PEDOT: PSS film.
Comparative example 2A method for producing PEDOT: PSS film comprising the steps of:
(1) Steps (1) to (4) are the same as steps (1) to (4) of example 1;
(2) And (3) placing the dried film obtained in the step (4) in an oven, and annealing at 120 ℃ for 30min to obtain the PEDOT/PSS film.
Comparative example 3 a method for preparing a PEDOT: PSS film, comprising the steps of:
(1) Steps (1) to (4) are the same as steps (1) to (4) of example 2;
(2) And (3) placing the dried film obtained in the step (4) in a laser environment, and annealing at 120 ℃ for 30min to obtain the PEDOT/PSS film.
Examples 1 and 2 a highly conductive PEDOT: PSS conductive film was prepared by adding different ionic liquid materials, and the conductivity of the PEDOT: PSS conductive film prepared by mixing the methanesulfonate ionic liquid was better by testing the conductivity.
| Film to be measured | Square resistor (omega/sq) | Conductivity (S/cm) |
| PEDOT: PSS film obtained in comparative example 1 | 1000 | 0.0125 |
| PEDOT PSS film obtained in comparative example 2 | 64.9 | 15.31 |
| PEDOT PSS film obtained in comparative example 3 | 16 | 70.19 |
| PEDOT PSS film obtained in example 1 | 42 | 64.35 |
| PEDOT PSS film obtained in example 2 | 14 | 89.28 |
Example 3
(1) Step (1), as in step (1) of example 2;
(2) Dripping the methanesulfonate ionic liquid with good biocompatibility into the aqueous solution of PEDOT and PSS in the step 1, and partially removing the PSS in the PEDOT and the PSS to obtain a mixed solution, wherein the mass of the ionic liquid relative to the mixed solution is 2:3, and the calculation does not consider the PEDOT: water in PSS dispersion, therefore, the final mass ratio between PEDOT: PSS and ionic liquid mass in the dried composite was determined;
(3) And (3) to (5) the steps (3) to (5) in example 2 are the same, and the high-conductivity PEDOT: PSS film is obtained. The square resistance was 13.4. Omega/sq and the conductivity was 93.28S/cm.
Example 4
(1) Step (1), as in step (1) of example 2;
(2) Dripping the methanesulfonate ionic liquid with good biocompatibility into the aqueous solution of PEDOT and PSS in the step 1, and partially removing the PSS in the PEDOT and the PSS to obtain a mixed solution, wherein the mass of the ionic liquid relative to the mixed solution is 1:1, and the calculation does not consider the PEDOT: water in PSS dispersion, therefore, the final mass ratio between PEDOT: PSS and ionic liquid mass in the dried composite was determined;
(3) And (3) to (5) the steps (3) to (5) in example 2 are the same, and the high-conductivity PEDOT: PSS film is obtained. The square resistance was 11.58. Omega/sq and the conductivity was 107.94S/cm.
Examples 3 and 4 used different concentrations of methanesulfonate ionic liquid for mixing, other conditions remained consistent, and the prepared PEDOT: PSS films were better in conductivity and better in strain performance on flexible planar substrates at 1:1 concentrations.
Example 5
(1) Steps (1) to (4) are the same as steps (1) to (4) in example 4;
(2) And (3) placing the dried film obtained in the step (4) on a laser processing platform, utilizing the thermal effect and the electric field effect of laser to induce phase separation to further remove part of PSS in PEDOT PSS, wherein a continuous wave laser is selected as the laser, the power is 0.03W, the speed is 100-300 mm/s, the line spacing is 0.03mm, and the high-conductivity PEDOT PSS film is obtained after processing. At a speed of 100mm/S, the sheet resistance is optimally 10.5 Ω/sq and the conductivity is 119.04S/cm.
Example 6
(1) Steps (1) to (4) are the same as steps (1) to (4) in example 4;
(2) And (3) placing the dried film obtained in the step (4) on a laser processing platform, utilizing the thermal effect and the electric field effect of laser to induce phase separation to further remove part of PSS in PEDOT PSS, using a continuous wave laser with the power of 0.05W, the speed of 100-300 mm/s and the line spacing of 0.03mm, and processing to obtain the high-conductivity PEDOT PSS film. At a speed of 100mm/S, the sheet resistance is optimally 10 Ω/sq and the conductivity is 125S/cm.
Example 7
(1) Steps (1) to (4) are the same as steps (1) to (4) in example 4;
(2) And (3) placing the dried film obtained in the step (4) on a laser processing platform, utilizing the thermal effect and the electric field effect of laser to induce phase separation to further remove part of PSS in PEDOT PSS, using a continuous wave laser with the power of 0.01W, the speed of 100-300 mm/s and the line spacing of 0.03mm, and processing to obtain the high-conductivity PEDOT PSS film. At a speed of 100mm/S, the sheet resistance is optimally 9 Ω/sq and the conductivity is 138.88S/cm.
In examples 5 to 7, different laser processing powers, speeds and line pitches were used, and other conditions were kept consistent, and PEDOT: PSS films prepared at a power of 0.01W, a speed of 100mm/S and a line pitch of 0.03mm were excellent in conductivity, 9. OMEGA/sq in sheet resistance, and 138.88S/cm in conductivity.
Claims (10)
1. The preparation method of the PEDOT/PSS film with high conductivity is characterized by comprising the following steps of:
(1) Filtering the PEDOT-PSS aqueous solution, and dripping the ionic liquid into the filtered PEDOT-PSS aqueous solution to obtain a mixed solution, wherein the mass ratio of the ionic liquid to the mixed solution is 1:4-1:1;
(2) Stirring the mixed solution to form a uniform solution, transferring the uniform solution to a planar substrate by a spin coating method, and performing primary drying to form a film;
(3) And (3) processing the dried film by using a laser processing technology to further induce phase separation, so as to obtain the PEDOT/PSS film with high conductivity.
2. The method according to claim 1, wherein the high conductivity PEDOT/PSS film has a thickness of 1 μm to 15 μm and a conductivity of 64.35S/cm to 138S/cm.
3. The method according to claim 1, wherein in the step (1), the raw aqueous solution of PEDOT and PSS is passed through an aqueous filter.
4. The method of claim 1, wherein in step (1), the ionic liquid is choline carboxylate ionic liquid, mesylate ionic liquid, or other hydroxyl-containing ionic liquid with good biocompatibility.
5. The method according to claim 4, wherein the choline carboxylate ionic liquid is prepared by dropping an acid having good biocompatibility and containing a carboxylic acid group into an aqueous choline bicarbonate solution.
6. The method according to claim 1, wherein in the step (2), the mixed solution is uniformly stirred in an ultrasonic environment for 15 to 30 minutes.
7. The method according to claim 1, wherein in the step (2), the spin coating is performed at a rotation speed of 1500rpm/min to 5000rpm/min.
8. The method according to claim 1, wherein in the step (2), the drying environment is vacuum, the temperature is 60 to 80 ℃ and the time is 15 to 30min.
9. The method of claim 1, wherein in step (3), the laser processing technique is performed while forming the patterned PEDOT: PSS film as required.
10. A high conductivity PEDOT: PSS film produced by the method according to any one of claims 1 to 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090152503A1 (en) * | 2005-04-27 | 2009-06-18 | Fujikura Ltd. | Conductive Material, Conductive Film, and Production Method Thereof |
| KR20190066344A (en) * | 2017-12-05 | 2019-06-13 | 한국생산기술연구원 | Method for improving conductivity of PEDOT:PSS thin film |
| CN112635671A (en) * | 2020-12-19 | 2021-04-09 | 南京理工大学 | Femtosecond laser modification-based resistance reduction method for conductive polymer PEDOT (PEDOT-PSS) |
| CN113594346A (en) * | 2021-06-30 | 2021-11-02 | 南方科技大学 | Organic thermoelectric film and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090152503A1 (en) * | 2005-04-27 | 2009-06-18 | Fujikura Ltd. | Conductive Material, Conductive Film, and Production Method Thereof |
| KR20190066344A (en) * | 2017-12-05 | 2019-06-13 | 한국생산기술연구원 | Method for improving conductivity of PEDOT:PSS thin film |
| CN112635671A (en) * | 2020-12-19 | 2021-04-09 | 南京理工大学 | Femtosecond laser modification-based resistance reduction method for conductive polymer PEDOT (PEDOT-PSS) |
| CN113594346A (en) * | 2021-06-30 | 2021-11-02 | 南方科技大学 | Organic thermoelectric film and preparation method thereof |
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