CN103642058A - Method for preparing conductive polymer flexible film with improved conductivity - Google Patents
Method for preparing conductive polymer flexible film with improved conductivity Download PDFInfo
- Publication number
- CN103642058A CN103642058A CN201310575139.4A CN201310575139A CN103642058A CN 103642058 A CN103642058 A CN 103642058A CN 201310575139 A CN201310575139 A CN 201310575139A CN 103642058 A CN103642058 A CN 103642058A
- Authority
- CN
- China
- Prior art keywords
- dioxoethyl
- thiophene
- fexible film
- conduction
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 43
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 60
- 239000002253 acid Substances 0.000 claims abstract description 16
- 206010016654 Fibrosis Diseases 0.000 claims abstract description 10
- 230000004761 fibrosis Effects 0.000 claims abstract description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 136
- 229930192474 thiophene Natural products 0.000 claims description 68
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 229920006267 polyester film Polymers 0.000 claims description 23
- 239000000835 fiber Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000012725 vapour phase polymerization Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 150000007522 mineralic acids Chemical class 0.000 claims description 12
- 238000004528 spin coating Methods 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 238000007654 immersion Methods 0.000 claims description 11
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 10
- 239000004800 polyvinyl chloride Substances 0.000 claims description 10
- NBLHGCDPIWAGAS-UHFFFAOYSA-N 2-ethylthiolane-3,4-dione Chemical compound O=C1C(SCC1=O)CC NBLHGCDPIWAGAS-UHFFFAOYSA-N 0.000 claims description 7
- 238000005259 measurement Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 238000002309 gasification Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- IOVFHLJNAMPRHI-UHFFFAOYSA-N 2-oxo-2-thiophen-3-ylacetaldehyde Chemical compound O=CC(=O)C=1C=CSC=1 IOVFHLJNAMPRHI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 238000002791 soaking Methods 0.000 abstract description 14
- 230000008859 change Effects 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 abstract 4
- 238000012685 gas phase polymerization Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 96
- 239000000243 solution Substances 0.000 description 22
- 238000002834 transmittance Methods 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003176 fibrotic effect Effects 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Landscapes
- Non-Insulated Conductors (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Manufacturing Of Electric Cables (AREA)
- Laminated Bodies (AREA)
Abstract
The invention belongs to the field of high-conductivity polymer flexible films, and particularly relates to a method for preparing a conductive polymer flexible film with improved conductivity by changing a microstructure on the surface of the conductive polymer flexible film by using an acid soaking method. According to the invention, the high-conductivity PEDOT flexible film is prepared on the surface of the flexible substrate by a gas-phase polymerization method, and the surface of the PEDOT flexible film is subjected to fibrosis change by a simple acid soaking method at room temperature, so that the conductivity of the PEDOT flexible film is remarkably improved by more than 40%. The conductive polymer flexible film formed by the flexible substrate and the PEDOT flexible film with the surface being fiberized can be used in flexible photoelectric devices.
Description
Technical field
The invention belongs to high conductivity polymer fexible film field, particularly utilize the method for acid soak with the method for the conductive polymers fexible film of the preparation specific conductivity raising of the microstructure on change conductive polymers fexible film surface.
Background technology
In daily life, people more and more pay close attention to portability and the novelty of institute's use photoelectric device, so the flexibility of device becomes following development trend day by day.That the electrode materials of existing photoelectric device generally adopts is tin indium oxide (ITO), is characterized in that specific conductivity is high, perviousness good, yet due to its fragility, cannot be applied in flexible photoelectric device.In addition, rare earth element among ITO is expensive, resource-constrained, and therefore the research of new equivalent material has caused people's extensive concern.
Conductive polymers owing to having polymkeric substance and conductor concurrently, semi-conductive characteristic has caused people's broad research, particularly the method by vapour phase polymerization has obtained the film up to the above specific conductivity of 1000S/cm, at alternative ITO, becomes aspect fexible film electrode materials and has demonstrated good application prospect.Conductive polymers has flexible, the advantage of resistance to bending, but specific conductivity is compared ITO and is also had a certain distance, therefore, people are usually by the specific conductivity of adding some additives and further improving the polymeric film that vapour phase polymerization obtains by last handling process in the process of vapour phase polymerization, the report that the relevant method by aftertreatment improves film conductivity has: the people such as Levermore (Advanced Materials, 2007,19,2379-2385) by the post processing mode of 80 ℃ of high temperings, the PEDOT film that to have obtained specific conductivity be 1180S/cm.The people such as Xia (ACS Applied Materials & Interfaces, 2010,2,474-483) pass through poly-(3,4-dioxoethyl) thiophene/poly styrene sulfonate (PEDOT/PSS) film, under 160 ℃ of high temperature, carry out the method that acid is rinsed, by the specific conductivity of film from 0.2S cm
-1bring up to 103S cm
-1.The people such as Gleason (Journal of Materials Chemistry A, 2013,1, the method of 1334-1340) rinsing by PEDOT film being carried out under 150 ℃ of high temperature to acid, the specific conductivity of film has been improved more than 37%, and ascribed the raising of film conductivity to PEDOT film the change of polymer chain conformation has occurred higher than its second-order transition temperature in the situation that.These researchs generally adopt high temperature process, and condition is gentle not and expend the energy.
Summary of the invention
The object of this invention is to provide that a kind of method is simple, mild condition, the method for utilizing acid soak is with the method for the conductive polymers fexible film that changes the preparation specific conductivity of the microstructure on conductive polymers fexible film surface and improve.
The present invention is at normal temperatures, the post-treating method soaking by rare inorganic acid solution, utilize the Fibrotic variation of conductive polymers fexible film surface micro-structure, thereby increase the electronic mobility on conductive polymers fexible film surface, the final specific conductivity that improves conductive polymers fexible film that realizes.
The present invention is the method for utilizing vapour phase polymerization, by oxygenant ethanolic soln being spun to the surface of flexible substrates, then in reaction chamber, in room temperature, under condition of normal pressure, with 3, the gas of 4-dioxoethyl thiophene (EDOT) monomer carries out vapour phase polymerization, by controlling the reaction times, obtain the high conductivity of different thickness, poly-(3 of high permeability, 4-dioxoethyl) thiophene (PEDOT) fexible film, again by after the immersion treatment of mineral acid, can there is fibrosis and change in the microstructure on conductive polymers fexible film surface, there is tiny fiber, and the thickness of conductive polymers fexible film, transmitance remains unchanged, specific conductivity improves more than 40%.
The method of the conductive polymers fexible film that preparation specific conductivity of the present invention improves comprises the following steps:
A) by oxygenant powder ultrasonic dissolution in ethanolic soln, obtaining solid content is the ethanolic soln that contains oxygenant of 1～10wt%;
B) ethanolic soln that contains oxygenant step a) being obtained drips to the surface of flexible substrates, and the method (preferably the rotating speed of spin coating is 2000～4000r/min) by spin coating, makes the surface uniform of flexible substrates apply the ethanolic soln that one deck contains oxygenant;
The flexible substrates of the ethanolic soln that the surface-coated c) step b) being obtained contains oxygenant is placed in and is mounted with (3, 4-dioxoethyl) on the open container of thiophene monomer, and the flexible substrates of the ethanolic soln that contains oxygenant one facing to vessel port, then be placed in together in reaction chamber, the temperature of controlling in reaction chamber is 15～30 ℃, make (3 in container, 4-dioxoethyl) thiophene (EDOT) monomer evaporation gasification, make the ethanolic soln and 3 that contains oxygenant, 4-dioxoethyl thiophene monomer carries out vapour phase polymerization (preferably the time of vapour phase polymerization is 5～15 minutes), on the surface of flexible substrates, obtain conduction poly-(3, 4-dioxoethyl) thiophene (PEDOT) fexible film, then the deionized water that is 1:1 by volume ratio and the mixing solutions of ethanol wash,
D) there is to conduction poly-(3 on the surface obtaining after step c) washing, 4-dioxoethyl) flexible substrates of thiophene (PEDOT) fexible film is put into inorganic acid solution immersion (time of preferably soaking is 1～24 hour), make the microstructure generation fibrosis on poly-(3,4-dioxoethyl) thiophene (PEDOT) fexible film of conduction surface change (occurring tiny fiber); Then use deionized water rinsing, dry (can be to be dried about 30 minutes at 40 ℃ in temperature) obtains further poly-(3,4-dioxoethyl) thiophene (PEDOT) fexible film of conduction of the surface fiber of raising of specific conductivity in flexible substrates.
The thickness of described poly-(3,4-dioxoethyl) thiophene (PEDOT) fexible film of conduction is 50～115nm.
To described conduction poly-(3,4-dioxoethyl) thiophene (PEDOT) fexible film carried out afterwards with it specific conductivity, transmittance and thickness measurement before putting into inorganic acid solution immersion, specific conductivity before putting into inorganic acid solution immersion is 810～1800S/cm, and transmittance is 83%～95%; Specific conductivity after inorganic acid solution soaks one to one by 810～1800S/cm bring up to 1160～2600S/cm(as specific conductivity be 810 to bring up to 1160, specific conductivity is that 1800S/cm brings up to 2600S/cm); Thickness and the transmittance of poly-(3,4-dioxoethyl) thiophene (PEDOT) fexible film of described conduction after inorganic acid solution soaks remain unchanged.
Described flexible substrates is polypropylene film (PP), polyester film (PET) or polyvinyl chloride film (PVC).
Described oxygenant is iron trichloride or tosic acid iron.
The concentration of described mineral acid is 0.1～1.0mol/L.
Described mineral acid is sulfuric acid, hydrochloric acid or nitric acid.
Before the ethanolic soln that contains oxygenant is dripped to the surface of flexible substrates, the deionized water that can be first 1:1 by volume ratio and the mixing solutions of ethanol carry out ultrasonic cleaning (time of general ultrasonic cleaning is about 10 minutes) to flexible substrates, then with ethanolic soln, rinse, put into subsequently baking oven (temperature of general baking oven is 40 ℃) and dry, to obtain clean flexible substrates.
Method of the present invention is without vacuum, high temperature and any additive, under the condition of room temperature gentleness, by vapour phase polymerization (VPP) method, can prepare on the surface of flexible substrates the conduction poly-(3 of high conductivity, 4-dioxoethyl) thiophene (PEDOT) fexible film, and by the method for acid soak under simple room temperature, make to gather (3,4-dioxoethyl) there is fibrosis variation in thiophene (PEDOT) fexible film surface, the specific conductivity that has significantly improved poly-(3,4-dioxoethyl) thiophene (PEDOT) fexible film reaches more than 40%.Method of the present invention is simple, mild condition, is conducive to suitability for industrialized production.The conductive polymers fexible film being improved by the prepared specific conductivity of method of the present invention is poly-(3,4-dioxoethyl) the thiophene fexible film formation of conduction by flexible substrates and surface fiber.The conductive polymers fexible film that the PEDOT fexible film of prepared flexible substrates and its surface fiber forms can be used in flexible photoelectric device, as: as electrode materials, the electrode materials of flexible solar battery, the electrode materials of sensor etc. of the flexible Organic Light Emitting Diode of preparation (OLED).
Accompanying drawing explanation
Fig. 1. the SEM photo of poly-(3,4-dioxoethyl) thiophene (PEDOT) flexible thin-film material's of conduction of the high conductivity of the embodiment of the present invention 1 preparation surface topography.
Fig. 2. the SEM photo of poly-(3,4-dioxoethyl) thiophene (PEDOT) flexible thin-film material's of the high conductivity of comparative example 1 preparation surface topography.
Embodiment
Embodiment 1
A) by oxygenant FeCl
3powder ultrasonic is dissolved in ethanolic soln, and obtaining solid content is the FeCl that contains of 1wt%
3ethanolic soln;
What b) step a) is obtained contains FeCl
3ethanolic soln drip to the surface of PET substrate, by the method (preferably the rotating speed of spin coating is 2000r/min) of spin coating, make the surface uniform of PET substrate apply one deck and contain FeCl
3ethanolic soln;
C) surface-coated step b) being obtained contains FeCl
3the PET substrate of ethanolic soln be placed on the open container that is mounted with a certain amount of (3,4-dioxoethyl) thiophene monomer, and contain FeCl
3ethanolic soln PET substrate one facing to vessel port, be then placed in together in reaction chamber, the temperature of controlling in reaction chamber is 25 ℃, makes (3,4-dioxoethyl) thiophene monomer evaporation gasification in container, makes to contain FeCl
3ethanolic soln and 3,4-dioxoethyl thiophene monomer carry out vapour phase polymerization 5 minutes, on the surface of PET substrate, obtain poly-(3,4-dioxoethyl) the thiophene fexible film of conduction; Then the deionized water that is 1:1 by volume ratio and the mixing solutions of ethanol wash;
D) there is to conduction poly-(3 on the surface obtaining after step c) washing, 4-dioxoethyl) to put into concentration be that the dilute sulphuric acid of 1.0mol/L soaks 24 hours in the PET substrate of thiophene fexible film, make the microstructure generation fibrosis on poly-(3,4-dioxoethyl) the thiophene fexible film of conduction surface change (occurring tiny fiber); Then using deionized water rinsing, is at 40 ℃, to be dried about 30 minutes in temperature, obtains further poly-(3,4-dioxoethyl) thiophene fexible film of conduction of the surface fiber of raising of specific conductivity in PET substrate.
To surface obtained above, there is the PET substrate of poly-(3,4-dioxoethyl) the thiophene fexible film of conduction to carry out afterwards with it specific conductivity, transmittance and thickness measurement before putting into dilution heat of sulfuric acid immersion.Through specific conductivity, (adopt four point probe tester to measure conduction poly-(3,4-dioxoethyl) resistance on thiophene fexible film surface, thickness relationship according to surface resistivity and fexible film, the specific conductivity of calculating fexible film), thickness (the passing through atomic force microscope) test of transmittance (getting the light transmission rate to the most responsive 550nm place of human eye) and fexible film, poly-(3,4-dioxoethyl) the thiophene fexible film of this conduction putting into the thickness of the 50nm of dilution heat of sulfuric acid before and after soaking, 95% transmittance all remains unchanged; Specific conductivity after dilution heat of sulfuric acid soaks is that 810S/cm brings up to 1160S/cm by the specific conductivity before soaking.In the contained micropore in the surface of poly-(3,4-dioxoethyl) the thiophene fexible film of described conduction, comprise a large amount of fiber fines, the SEM photo of the surface topography of poly-(3,4-dioxoethyl) thiophene (PEDOT) fexible film of conduction as shown in Figure 1.
Embodiment 2
A) by oxygenant FeCl
3powder ultrasonic is dissolved in ethanolic soln, and obtaining solid content is the FeCl that contains of 10wt%
3ethanolic soln;
What b) step a) is obtained contains FeCl
3ethanolic soln drip to the surface of PET substrate, by the method (preferably the rotating speed of spin coating is 2000r/min) of spin coating, make the surface uniform of PET substrate apply one deck and contain FeCl
3ethanolic soln;
C) surface-coated step b) being obtained contains FeCl
3the PET substrate of ethanolic soln be placed on the open container that is mounted with a certain amount of (3,4-dioxoethyl) thiophene monomer, and contain FeCl
3ethanolic soln PET substrate one facing to vessel port, be then placed in together in reaction chamber, the temperature of controlling in reaction chamber is 15 ℃, makes (3,4-dioxoethyl) thiophene monomer evaporation gasification in container, makes to contain FeCl
3ethanolic soln and 3,4-dioxoethyl thiophene monomer carry out vapour phase polymerization 15 minutes, on the surface of PET substrate, obtain poly-(3,4-dioxoethyl) the thiophene fexible film of conduction; Then the deionized water that is 1:1 by volume ratio and the mixing solutions of ethanol wash;
D) there is to conduction poly-(3 on the surface obtaining after step c) washing, 4-dioxoethyl) to put into concentration be that the dilute hydrochloric acid of 0.1mol/L soaks 12 hours in the PET substrate of thiophene fexible film, make the microstructure generation fibrosis on poly-(3,4-dioxoethyl) the thiophene fexible film of conduction surface change (occurring tiny fiber); Then using deionized water rinsing, is at 40 ℃, to be dried about 30 minutes in temperature, obtains further poly-(3,4-dioxoethyl) thiophene fexible film of conduction of the surface fiber of raising of specific conductivity in PET substrate.
To surface obtained above, there is the PET substrate of poly-(3,4-dioxoethyl) the thiophene fexible film of conduction to carry out afterwards with it specific conductivity, transmittance and thickness measurement before putting into dilute hydrochloric acid solution immersion.Through specific conductivity, (adopt four point probe tester to measure conduction poly-(3,4-dioxoethyl) resistance on thiophene fexible film surface, thickness relationship according to surface resistivity and fexible film, the specific conductivity of calculating fexible film), thickness (the passing through atomic force microscope) test of transmittance (getting the light transmission rate to the most responsive 550nm place of human eye) and fexible film, poly-(3,4-dioxoethyl) the thiophene fexible film of this conduction putting into the thickness of the 90nm of dilute hydrochloric acid solution before and after soaking, 90% transmittance all remains unchanged; Specific conductivity after dilute hydrochloric acid solution soaks is that 1500S/cm brings up to 2200S/cm by the specific conductivity before soaking.In the contained micropore in the surface of poly-(3,4-dioxoethyl) the thiophene fexible film of described conduction, comprise a large amount of fiber fines.
Embodiment 3
A) by oxygenant tosic acid iron powder ultrasonic dissolution in ethanolic soln, obtaining solid content is the ethanolic soln that contains toluenesulphonic acids iron of 5wt%;
B) ethanolic soln that contains tosic acid iron step a) being obtained drips to the surface of PP substrate, by the method (rotating speed of spin coating is 4000r/min) of spin coating, makes the surface uniform of PP substrate apply the ethanolic soln that one deck contains toluenesulphonic acids iron;
The PP substrate of the ethanolic soln that the surface-coated c) step b) being obtained contains tosic acid iron is placed in and is mounted with a certain amount of (3, 4-dioxoethyl) on the open container of thiophene monomer, and the PP substrate of the ethanolic soln that contains tosic acid iron one facing to vessel port, then be placed in together in reaction chamber, the temperature of controlling in reaction chamber is 30 ℃, make (3 in container, 4-dioxoethyl) thiophene monomer evaporation gasification, make the ethanolic soln and 3 that contains tosic acid iron, 4-dioxoethyl thiophene monomer carries out vapour phase polymerization 10 minutes, on the surface of PP substrate, obtain conduction poly-(3, 4-dioxoethyl) thiophene fexible film, then the deionized water that is 1:1 by volume ratio and the mixing solutions of ethanol wash,
D) there is to conduction poly-(3 on the surface obtaining after step c) washing, 4-dioxoethyl) to put into concentration be that the dilute hydrochloric acid of 0.5mol/L soaks 1 hour in the PP substrate of thiophene fexible film, make the microstructure generation fibrosis on poly-(3,4-dioxoethyl) the thiophene fexible film of conduction surface change (occurring tiny fiber); Then using deionized water rinsing, is at 40 ℃, to be dried about 30 minutes in temperature, obtains further poly-(3,4-dioxoethyl) thiophene fexible film of conduction of the surface fiber of raising of specific conductivity in PP substrate.
To surface obtained above, there is the PP substrate of poly-(3,4-dioxoethyl) the thiophene fexible film of conduction to carry out afterwards with it specific conductivity, transmittance and thickness measurement before putting into dilute hydrochloric acid solution immersion.Through specific conductivity, (adopt four point probe tester to measure conduction poly-(3,4-dioxoethyl) resistance on thiophene fexible film surface, thickness relationship according to surface resistivity and fexible film, the specific conductivity of calculating fexible film), thickness (the passing through atomic force microscope) test of transmittance (getting the light transmission rate to the most responsive 550nm place of human eye) and fexible film, poly-(3,4-dioxoethyl) the thiophene fexible film of this conduction putting into the thickness of the 75nm of dilute hydrochloric acid solution before and after soaking, 88% transmittance all remains unchanged; Specific conductivity after dilute hydrochloric acid solution soaks is that 1800S/cm brings up to 2600S/cm by the specific conductivity before soaking.In the contained micropore in the surface of poly-(3,4-dioxoethyl) the thiophene fexible film of described conduction, comprise a large amount of fiber fines.
Embodiment 4
A) by oxygenant tosic acid iron powder ultrasonic dissolution in ethanolic soln, obtaining solid content is the ethanolic soln that contains toluenesulphonic acids iron of 5wt%;
B) ethanolic soln that contains tosic acid iron step a) being obtained drips to the surface of PVC substrate, by the method (rotating speed of spin coating is 3000r/min) of spin coating, makes the surface uniform of PVC substrate apply the ethanolic soln that one deck contains toluenesulphonic acids iron;
The PVC substrate of the ethanolic soln that the surface-coated c) step b) being obtained contains tosic acid iron is placed in and is mounted with a certain amount of (3, 4-dioxoethyl) on the open container of thiophene monomer, and the PVC substrate of the ethanolic soln that contains tosic acid iron one facing to vessel port, then be placed in together in reaction chamber, the temperature of controlling in reaction chamber is 30 ℃, make (3 in container, 4-dioxoethyl) thiophene monomer evaporation gasification, make the ethanolic soln and 3 that contains tosic acid iron, 4-dioxoethyl thiophene monomer carries out vapour phase polymerization 15 minutes, on the surface of PVC substrate, obtain conduction poly-(3, 4-dioxoethyl) thiophene fexible film, then the deionized water that is 1:1 by volume ratio and the mixing solutions of ethanol wash,
D) there is to conduction poly-(3 on the surface obtaining after step c) washing, 4-dioxoethyl) to put into concentration be that rare nitric acid of 0.1mol/L soaks 24 hours in the PET substrate of thiophene fexible film, make the microstructure generation fibrosis on poly-(3,4-dioxoethyl) the thiophene fexible film of conduction surface change (occurring tiny fiber); Then using deionized water rinsing, is at 40 ℃, to be dried about 30 minutes in temperature, obtains further poly-(3,4-dioxoethyl) thiophene fexible film of conduction of the surface fiber of raising of specific conductivity in PVC substrate.
To surface obtained above, there is the PVC substrate of poly-(3,4-dioxoethyl) the thiophene fexible film of conduction to carry out afterwards with it specific conductivity, transmittance and thickness measurement before putting into dilute nitric acid solution immersion.Through specific conductivity, (adopt four point probe tester to measure conduction poly-(3,4-dioxoethyl) resistance on thiophene fexible film surface, thickness relationship according to surface resistivity and fexible film, the specific conductivity of calculating fexible film), thickness (the passing through atomic force microscope) test of transmittance (getting the light transmission rate to the most responsive 550nm place of human eye) and fexible film, poly-(3,4-dioxoethyl) the thiophene fexible film of this conduction putting into the thickness of the 115nm of dilute nitric acid solution before and after soaking, 83% transmittance all remains unchanged; Specific conductivity after dilute nitric acid solution soaks is that 1280S/cm brings up to 1800S/cm by the specific conductivity before soaking.In the contained micropore in the surface of poly-(3,4-dioxoethyl) the thiophene fexible film of described conduction, comprise a large amount of fiber fines
Comparative example 1
Step a), b), c) all identical with embodiment 1
D) surface obtaining after step c) washing is had to the PET substrate of poly-(3,4-dioxoethyl) the thiophene fexible film of conduction, do not put into inorganic acid solution, but put into deionized water, soak 24 hours; And then with deionized water rinsing, in temperature, be at 40 ℃, to be dried about 30 minutes, in PET substrate, obtain film surface fibrosis variation does not occur, poly-(3,4-dioxoethyl) thiophene fexible film of conduction that specific conductivity decreases.
To surface obtained above, there is the PET substrate of poly-(3,4-dioxoethyl) the thiophene fexible film of conduction to carry out afterwards with it specific conductivity, transmittance and thickness measurement before putting into deionized water immersion.Through specific conductivity, (adopt four point probe tester to measure conduction poly-(3,4-dioxoethyl) resistance on thiophene fexible film surface, thickness relationship according to surface resistivity and fexible film, the specific conductivity of calculating fexible film), thickness (the passing through atomic force microscope) test of transmittance (getting the light transmission rate to the most responsive 550nm place of human eye) and fexible film, poly-(3,4-dioxoethyl) the thiophene fexible film of this conduction putting into the thickness of the 50nm of deionized water before and after soaking, 95% transmittance all remains unchanged; Specific conductivity after deionized water soaks is that 810S/cm is reduced to 720S/cm by the specific conductivity before soaking.In the contained micropore in the surface of poly-(3,4-dioxoethyl) the thiophene fexible film of described conduction, do not comprise fiber fines, the SEM photo of the surface topography of poly-(3,4-dioxoethyl) thiophene (PEDOT) film of conduction as shown in Figure 2.
Claims (10)
1. a method of preparing the conductive polymers fexible film of specific conductivity raising, is characterized in that, the method comprises the following steps:
A) by oxygenant powder ultrasonic dissolution in ethanolic soln, obtaining solid content is the ethanolic soln that contains oxygenant of 1～10wt%;
B) ethanolic soln that contains oxygenant step a) being obtained drips to the surface of flexible substrates, by the method for spin coating, makes the surface uniform of flexible substrates apply the ethanolic soln that one deck contains oxygenant;
The flexible substrates of the ethanolic soln that the surface-coated c) step b) being obtained contains oxygenant is placed in and is mounted with (3, 4-dioxoethyl) on the open container of thiophene monomer, and the flexible substrates of the ethanolic soln that contains oxygenant one facing to vessel port, then be placed in together in reaction chamber, the temperature of controlling in reaction chamber is 15～30 ℃, make (3 in container, 4-dioxoethyl) thiophene monomer evaporation gasification, make the ethanolic soln and 3 that contains oxygenant, 4-dioxoethyl thiophene monomer carries out vapour phase polymerization, on the surface of flexible substrates, obtain conduction poly-(3, 4-dioxoethyl) thiophene fexible film, then the deionized water that is 1:1 by volume ratio and the mixing solutions of ethanol wash,
D) there is the flexible substrates of poly-(3,4-dioxoethyl) the thiophene fexible film of conduction to put into inorganic acid solution on the surface obtaining after step c) washing and soak, the microstructure generation fibrosis on poly-(3,4-dioxoethyl) the thiophene fexible film of conduction surface is changed; Then use deionized water rinsing, dry, the conduction that obtains the surface fiber of specific conductivity raising in flexible substrates is gathered (3,4-dioxoethyl) thiophene fexible film.
2. method according to claim 1, is characterized in that: the thickness of described poly-(3,4-dioxoethyl) thiophene fexible film of conduction is 50～115nm.
3. method according to claim 1 and 2, it is characterized in that: to described conduction poly-(3,4-dioxoethyl) thiophene fexible film carried out afterwards with it conductivity measurement before putting into inorganic acid solution immersion, specific conductivity before putting into inorganic acid solution immersion is 810～1800S/cm, and the specific conductivity after inorganic acid solution soaks is brought up to 1160～2600S/cm by 810～1800S/cm one to one.
4. method according to claim 1, is characterized in that: the rotating speed of described spin coating is 2000～4000r/min.
5. method according to claim 1, is characterized in that: the time of described vapour phase polymerization is 5～15 minutes.
6. method according to claim 1, is characterized in that: described to put into the time that inorganic acid solution soaks be 1～24 hour.
7. according to the method described in claim 1 or 6, it is characterized in that: the concentration of described mineral acid is 0.1～1.0mol/L.
8. method according to claim 7, is characterized in that: described mineral acid is sulfuric acid, hydrochloric acid or nitric acid.
9. method according to claim 1, is characterized in that: described flexible substrates is polypropylene film, polyester film or polyvinyl chloride film.
10. method according to claim 1, is characterized in that: described oxygenant is iron trichloride or tosic acid iron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310575139.4A CN103642058B (en) | 2013-11-15 | 2013-11-15 | Method for preparing conductive polymer flexible film with improved conductivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310575139.4A CN103642058B (en) | 2013-11-15 | 2013-11-15 | Method for preparing conductive polymer flexible film with improved conductivity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103642058A true CN103642058A (en) | 2014-03-19 |
| CN103642058B CN103642058B (en) | 2015-11-04 |
Family
ID=50247356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310575139.4A Expired - Fee Related CN103642058B (en) | 2013-11-15 | 2013-11-15 | Method for preparing conductive polymer flexible film with improved conductivity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103642058B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418954A (en) * | 2015-11-25 | 2016-03-23 | 同济大学 | Preparation method of high-thermoelectric-property polymer film |
| CN105504326A (en) * | 2015-12-30 | 2016-04-20 | 中国科学院重庆绿色智能技术研究院 | Graphene-laminated composite doping method |
| CN106025183A (en) * | 2016-05-19 | 2016-10-12 | 上海理工大学 | Preparation method of carbon-based flexible film electrode for lithium ion batteries |
| CN106207096A (en) * | 2015-05-07 | 2016-12-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | Conducting polymer modified sulfur carbon composite electrode and preparation method |
| CN106229464A (en) * | 2016-07-27 | 2016-12-14 | 河南师范大学 | A kind of conductive polymer membrane and use the film modified anode pole piece of this conducting polymer |
| CN108929429A (en) * | 2018-06-27 | 2018-12-04 | 广东工业大学 | A kind of preparation method of the conductive polymer nanometer pipe with high length-diameter ratio |
| CN110130096A (en) * | 2019-05-30 | 2019-08-16 | 上海应用技术大学 | A kind of preparation method of flexible fiber fabric composite thermoelectric material |
| CN110628060A (en) * | 2019-09-29 | 2019-12-31 | 西安建筑科技大学 | Poly-3, 4-ethylenedioxythiophene modified film and preparation method and application thereof |
| CN113056498A (en) * | 2018-05-04 | 2021-06-29 | 图尔库大学 | Method for producing polymer film |
| US11378471B2 (en) * | 2019-11-26 | 2022-07-05 | Korea Institute Of Industrial Technology | Method of fabricating a conductive fabric, a multi-pressure sensor for a fiber type and a multi-pressure measuring method using the sensor |
| CN114974902A (en) * | 2022-06-22 | 2022-08-30 | 西安交通大学 | Method for preparing solid cathode of solid valve metal electrolytic capacitor by gas phase method |
| WO2023071203A1 (en) * | 2021-10-25 | 2023-05-04 | 隆基绿能科技股份有限公司 | Perovskite cell having hole transport layer of comb-like fiber structure and preparation method for perovskite cell |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781094A (en) * | 2009-01-16 | 2010-07-21 | 中国科学院理化技术研究所 | Method for directly preparing poly (3,4) dioxyethyl-thiophene film on surface of conductive glass |
| CN101815740A (en) * | 2007-07-09 | 2010-08-25 | 帝国创新有限公司 | Highly conductive and stable transparent conducting polymer films |
-
2013
- 2013-11-15 CN CN201310575139.4A patent/CN103642058B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101815740A (en) * | 2007-07-09 | 2010-08-25 | 帝国创新有限公司 | Highly conductive and stable transparent conducting polymer films |
| CN101781094A (en) * | 2009-01-16 | 2010-07-21 | 中国科学院理化技术研究所 | Method for directly preparing poly (3,4) dioxyethyl-thiophene film on surface of conductive glass |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106207096A (en) * | 2015-05-07 | 2016-12-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | Conducting polymer modified sulfur carbon composite electrode and preparation method |
| CN105418954B (en) * | 2015-11-25 | 2020-06-02 | 同济大学 | Preparation method of polymer film with high thermoelectric performance |
| CN105418954A (en) * | 2015-11-25 | 2016-03-23 | 同济大学 | Preparation method of high-thermoelectric-property polymer film |
| CN105504326A (en) * | 2015-12-30 | 2016-04-20 | 中国科学院重庆绿色智能技术研究院 | Graphene-laminated composite doping method |
| CN106025183B (en) * | 2016-05-19 | 2018-08-28 | 上海理工大学 | A kind of preparation method of the carbon-based fexible film electrode of lithium ion battery |
| CN106025183A (en) * | 2016-05-19 | 2016-10-12 | 上海理工大学 | Preparation method of carbon-based flexible film electrode for lithium ion batteries |
| CN106229464A (en) * | 2016-07-27 | 2016-12-14 | 河南师范大学 | A kind of conductive polymer membrane and use the film modified anode pole piece of this conducting polymer |
| CN106229464B (en) * | 2016-07-27 | 2020-07-03 | 河南师范大学 | Conductive polymer film and positive pole piece modified by conductive polymer film |
| CN113056498A (en) * | 2018-05-04 | 2021-06-29 | 图尔库大学 | Method for producing polymer film |
| CN108929429A (en) * | 2018-06-27 | 2018-12-04 | 广东工业大学 | A kind of preparation method of the conductive polymer nanometer pipe with high length-diameter ratio |
| CN110130096A (en) * | 2019-05-30 | 2019-08-16 | 上海应用技术大学 | A kind of preparation method of flexible fiber fabric composite thermoelectric material |
| CN110628060A (en) * | 2019-09-29 | 2019-12-31 | 西安建筑科技大学 | Poly-3, 4-ethylenedioxythiophene modified film and preparation method and application thereof |
| US11378471B2 (en) * | 2019-11-26 | 2022-07-05 | Korea Institute Of Industrial Technology | Method of fabricating a conductive fabric, a multi-pressure sensor for a fiber type and a multi-pressure measuring method using the sensor |
| WO2023071203A1 (en) * | 2021-10-25 | 2023-05-04 | 隆基绿能科技股份有限公司 | Perovskite cell having hole transport layer of comb-like fiber structure and preparation method for perovskite cell |
| CN114974902A (en) * | 2022-06-22 | 2022-08-30 | 西安交通大学 | Method for preparing solid cathode of solid valve metal electrolytic capacitor by gas phase method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103642058B (en) | 2015-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103642058B (en) | Method for preparing conductive polymer flexible film with improved conductivity | |
| CN102604334B (en) | Self-supporting transparent highly-conductive poly-3,4-ethylenedioxythiophene (PEDOT) film and preparation method of the film | |
| US10421873B2 (en) | Method for in-site synthesis of transparent conductive coating of poly(3,4-ethylenedioxythiophene)/nano silver | |
| CN113224239B (en) | In-situ generated water and thermal stable passivation layer and perovskite solar cell with same | |
| CN102718408A (en) | Method for preparing gas-sensitive film | |
| Sun et al. | Solution-processable, hypercrosslinked polymer via post-crosslinking for electrochromic supercapacitor with outstanding electrochemical stability | |
| CN106953014B (en) | Hybrid solar cell structure with copper phthalocyanine as hole transport layer and preparation method | |
| CN104733617A (en) | Method for manufacturing high-efficiency perovskite type solar cell through large crystal grain forming | |
| CN109860399B (en) | Self-sealing perovskite solar cell and preparation method | |
| CN113161042B (en) | Preparation method of sodium carboxymethylcellulose flexible transparent conductive film based on silver nanowires | |
| Chen et al. | Polymer Donor with a Simple Skeleton and Minor Siloxane Decoration Enables 19% Efficiency of Organic Solar Cells | |
| CN105336865B (en) | A kind of highly conductive polymer combination electrode and preparation method thereof | |
| Yao et al. | Flexible electrochromic poly (thiophene-furan) film via electrodeposition with high stability | |
| CN107674183B (en) | Containing naphthalene [1,2-c；5,6-c] two [1,2,5] thiadiazoles conjugated polymer and preparation method and application | |
| CN107827923B (en) | Novel pyrrole-3-formic acid-containing titanium oxygen cluster monomer C34H64O13N2Ti3And method for preparing the same | |
| CN103198934A (en) | Manufacturing method of composite membrane electrode materials | |
| KR101146832B1 (en) | Method for manufacturing high conductive organic film by solvent treatment and method for manufacturing organic solar cell having the organic film | |
| CN102134326B (en) | Preparation method of polyaniline/zinc oxide flexible composite electrode material | |
| CN110311037B (en) | Hole transport layer for flexible perovskite solar cell, and preparation method and application thereof | |
| CN109336852A (en) | A kind of non-fullerene electron transport material and its preparation method and use | |
| CN108383981B (en) | Conductive high-molecular copolymer nanotube, electrochromic layer thereof and preparation method of electrochromic device | |
| Maliakal | Characterization of dopant diffusion within semiconducting polymer and small-molecule films using infrared-active vibrational modes and attenuated total reflectance infrared spectroscopy | |
| Yan et al. | Effects of doping methods and dopant sizes on the performance of solar cells constructed with anchor-guided photoelectrochemical polymerization of thiophene | |
| CN103588986B (en) | Conductive polymer flexible film with flower-shaped microstructure and preparation method thereof | |
| KR102009045B1 (en) | Organic photovoltaic unit cell comprising organic material layer including chitosan |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151104 |