CN109671845A - A kind of method and application improving flexible polymer transparent conductive film photoelectric characteristic - Google Patents
A kind of method and application improving flexible polymer transparent conductive film photoelectric characteristic Download PDFInfo
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- CN109671845A CN109671845A CN201811466825.7A CN201811466825A CN109671845A CN 109671845 A CN109671845 A CN 109671845A CN 201811466825 A CN201811466825 A CN 201811466825A CN 109671845 A CN109671845 A CN 109671845A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a kind of methods and application for improving flexible polymer transparent conductive film photoelectric characteristic, by the way that the substrate deionized water, alcohol, the deionized water that are cut into square block to be respectively cleaned by ultrasonic 10~15 minutes；It is in mass ratio to instill a drop adhesive containing F into mixed liquor after 93:7 is mixed, stir 6~8 hours, obtain PEDOT:PSS suspension by PH1000, ethylene glycol；Spin coating or spraying PEDOT:PSS suspension on substrate, determine spin coating or spray parameters according to the thickness of PEDOT:PSS film and surface uniformity；The substrate that deposited PEDOT:PSS suspension is dry on hot plate, drying parameter is determined according to the property of substrate and PEDOT:PSS film；Mechanical pressure processing is carried out to the PEDOT:PSS film of the substrate surface after drying.The flexible polymer electrically conducting transparent is thin to have flexible and transparent conductivity well, suitable for the application in terms of flexible organic opto-electronic device electrode material or modifying interface material.
Description
Technical field
The invention belongs to organic optoelectronic device technical field more particularly to a kind of improvement flexible polymer electrically conducting transparent are thin
Flexible polymer transparent conductive film after the improvement photoelectric characteristic that the method for film photoelectric characteristic, this method obtain and this lead
The application of conductive film.
Background technique
The energy is the support of human survival and development, in the past few decades, fossil energy (coal, petroleum, natural gas)
It is a large amount of to use, serious harm is caused to environment for the survival of mankind, therefore find a kind of reproducible clean energy resource change
It obtains particularly important.It due to solar energy clean and environmental protection, does not pollute, it is renewable energy etc. that utility value is high, these advantages determine
Its status that do not replace in energy replacement, solar battery are to realize that solar energy is converted to the device of electric energy, in recent years,
Extensive concern and research by scientist, achieve huge progress.Up to the present, the light of crystal silicon solar batteries
Photoelectric transformation efficiency highest, preparation process and technology are also the most mature, but required high quality silicon, and preparation process is complicated, valence
Lattice are expensive, cause its cost excessively high, should not generally use.Therefore, people begin to focus on and study organic solar batteries
(OSC), because its have the advantages that it is at low cost, flexible, can large area processing etc. it is unique, become before solar energy conversion most has
One of device of scape.
In recent years, due to low cost, manufacture craft is simple, it can be achieved that the advantages that producing in enormous quantities various flexible organic photoelectrics
Extensive concern and research of the sub- device by scientist, especially flexible organic solar batteries and flexible organic electro-luminescence two
The fields such as pole pipe.After first organic electroluminescent LED (OLED) was developed from 1987 by U.S.'s Kodak Company,
Just its wide application prospect has been established.Since organic electroluminescent LED has wide viewing angle, ultra-thin, response is fast, and shine effect
The advantages that rate is high is the generally acknowledged next-generation main flow display in the whole world；Organic electroluminescent LED has small power consumption, can large area
The advantages that film forming, can be used as ideal planar light source for illuminating；Simultaneously organic electroluminescent LED be with organic material and
The all solid state thin-film device of one kind of amorphous materials production, thus there is flexibility well, this becomes wearable intelligence
Important technology in apparatus field.Demand with people to material life is continuously improved, and organic electroluminescent LED will be
Information shows that the fields such as lighting engineering and flexible device have very big application potential.
The device architecture of organic solar batteries is that organic active layer is accompanied between metal back electrode and transparent electrode, the sun
Light reaches organic active layer through transparent electrode, and active layer absorbs partial photonic and generates exciton, since concentration gradient acts on, exciton
It spreads and migrates in active layer.Due to the work function difference of positive and negative electrode, built in field can be generated in device, this built-in electricity
Field can make to reach the exciton dissociation at donor and acceptor interface into electrons and holes, and electrons and holes are received by cathode and anode respectively
Defecate collection produces electric current.The device architecture of organic electroluminescent LED is that organic layer is accompanied between metallic cathode and transparent anode
Hole and electronics are injected from anode and cathode both ends respectively, and hole and electronics meet and form exciton in organic layer, and exciton is logical
Overshoot transition, is released energy in the form of photon, and the photon that then device generates is projected by transparent electrode.Due to ITO (oxygen
Change indium tin) work function (4.5~4.7eV) between the LUMO and HOMO of most of conducting polymers, and have it is good
Conductivity and light transmittance are commonly used as the transparent electrode of organic solar batteries and organic electroluminescent LED.However ITO belongs to
In metal oxide, maximum disadvantage is flexible poor, and easy fragmentation is not suitable for flexible organic opto-electronic device field.
PEDOT:PSS has flexible and transparent conductivity well as a kind of novel conducting polymer, just can be with
The shortcomings that making up ITO becomes flexible organic opto-electronic device electrode material or modifying interface material.However, existing PEDOT:PSS
The conductivity of film is lower, relatively low in the transmitance of near infrared light, limits it in flexible organic opto-electronic device field
Using.Ouyang et al. is handled PEDOT:PSS film with the concentrated sulfuric acid, keeps the conductivity of PEDOT:PSS film very high, but
It is the electrode that the obtained PEDOT:PSS film of this method cannot act as flexible organic solar batteries, because the concentrated sulfuric acid has
There is strong corrosive, the planarization of flexible substrate can be destroyed, is unfavorable for application of the film in flexible optoelectronic part field.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for improving flexible polymer transparent conductive film photoelectric characteristic, it is intended to
How under the premise of not changing the physico-chemical structure and work function of PEDOT:PSS film (flexible polymer transparent conductive film),
The conductivity of film and the transmitance of near infrared light are improved, it is made to be more suitable for flexible organic opto-electronic device.
The flexible polymer for obtaining improving photoelectric characteristic a further object of the present invention is to provide the above method is transparent
Conductive film and the conductive film are as answering in terms of flexible organic opto-electronic device electrode material or modifying interface material
With.
The invention is realized in this way a method of improve flexible polymer transparent conductive film photoelectric characteristic, the party
Method the following steps are included:
(1) the substrate deionized water for being cut into square block, alcohol, deionized water are respectively cleaned by ultrasonic 10~15 minutes；
It (2) is in mass ratio to instill a drop adhesive containing F into mixed liquor after 93:7 is mixed, stir by PH1000, ethylene glycol
6~8 hours are mixed, PEDOT:PSS suspension is obtained；
(3) on substrate spin coating or spraying PEDOT:PSS suspension, it is equal according to the thickness of PEDOT:PSS film and surface
Even property determines spin coating or spray parameters；
(4) substrate that deposited PEDOT:PSS suspension is dry on hot plate, according to substrate and PEDOT:PSS film
Property determine drying parameter；
(5) mechanical pressure processing is carried out to the PEDOT:PSS film of the substrate surface after drying.
Preferably, in step (1), the substrate is flexible substrate material.
Preferably, the substrate is PET flexible substrate.
Preferably, in step (4), the drying parameter specifically: hot plate temperature is set as 95~100 DEG C, when dry
Between be 5~7min.
Preferably, in step (5), the mechanical pressure processing is to pass through hydraulic or roll-in to carry out pressure treatment, the pressure
It forces by force as 0Mpa~30Mpa.
The present invention further discloses the flexible polymer transparent conductive films that the above method is prepared.
Preferably, the flexible polymer transparent conductive film as flexible organic opto-electronic device electrode material or
Application in terms of modifying interface material.
Compared with the prior art the shortcomings that and deficiency, the invention has the following advantages:
(1) PEDOT:PSS conductive film of the present invention is after mechanical pressure processing, and conductivity increases, to the transmission of visible light
Rate is basically unchanged, and is increased to the transmitance for the near infrared light that wavelength is 600nm or more, is obtained what optical and electrical properties were greatly optimized
PEDOT:PSS transparent conductive film product
(2) present invention use mechanical pressure processing method, it is easy to operate, it is low in cost, can large area processing, pole is adapted to
Large area industrialization promotion makes the PEDOT:PSS film after processing preferably be applied to flexible organic opto-electronic device.
Detailed description of the invention
Fig. 1 is the morphology schematic diagram of PEDOT:PSS；Left part shows PEDOT:PSS particle by a thin PSS table
Surface layer is surrounded, and PEDOT chain is depicted as stub, and the amplification on right side gives the molecular structure of PEDOT:PSS；
Fig. 2 is raman spectrum of the PEDOT:PSS film under different mechanical pressures；
Fig. 3 is that PEDOT:PSS film penetrates the light in 600nm~1000nm near infrared range under different mechanical pressures
Rate；
Fig. 4 is the raising ratio of thickness and conductivity of the PEDOT:PSS film under different mechanical pressures.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Embodiment 1
The PET substrate of purchase is cut into the small cube of 2cm × 2cm, with deionized water, alcohol, each ultrasound of deionized water
Cleaning 15 minutes.
PEDOT:PSS suspension is configured, a drop need to be added dropwise in the ethylene glycol for the PH1000 and 7% that specific ratio is 93%
Adhesive containing F stirs 8 hours.
The spin coating PEDOT:PSS suspension on PET substrate, spin speed are set as 1000rpm, and spin coating acceleration is set as
300rpm/s, spin-coating time are set as 40s, and spin coating is twice.
Dry on hot plate, drying temperature is set as 95 DEG C, drying time 6min.
Test the conductivity and transmitance of PEDOT:PSS film, conductivity 568.18S/cm, the light transmission at 850nm
Rate is 68.40%.
Embodiment 2
The PET substrate of purchase is cut into the small cube of 2cm × 2cm, with deionized water, alcohol, each ultrasound of deionized water
Cleaning 15 minutes.
PEDOT:PSS suspension is configured, a drop need to be added dropwise in the ethylene glycol for the PH1000 and 7% that specific ratio is 93%
Adhesive containing F stirs 8 hours.
The spin coating PEDOT:PSS suspension on PET substrate, spin speed are set as 1000rpm, and spin coating acceleration is set as
300rpm/s, spin-coating time are set as 40s, and spin coating is twice.
Dry on hot plate, drying temperature is set as 95 DEG C, drying time 6min.
The mechanical pressure processing of about 10Mpa is carried out to PEDOT:PSS film.
The conductivity and transmitance of PEDOT:PSS film are tested, conductivity 621.12S/cm improves 9.32%,
Light transmittance at 850nm is 69.25%.
Embodiment 3
The PET substrate of purchase is cut into the small cube of 2cm × 2cm, with deionized water, alcohol, each ultrasound of deionized water
Cleaning 15 minutes.
PEDOT:PSS suspension is configured, a drop need to be added dropwise in the ethylene glycol for the PH1000 and 7% that specific ratio is 93%
Adhesive containing F stirs 8 hours.
The spin coating PEDOT:PSS suspension on PET substrate, spin speed are set as 1000rpm, and spin coating acceleration is set as
300rpm/s, spin-coating time are set as 40s, and spin coating is twice.
Dry on hot plate, drying temperature is set as 95 DEG C, drying time 6min.
The mechanical pressure processing of about 20Mpa is carried out to PEDOT:PSS film.
The conductivity and transmitance of PEDOT:PSS film are tested, conductivity 667.67S/cm improves 17.33%,
Light transmittance at 850nm is 70.32%.
Embodiment 4
The PET substrate of purchase is cut into the small cube of 2cm × 2cm, with deionized water, alcohol, each ultrasound of deionized water
Cleaning 15 minutes.
PEDOT:PSS suspension is configured, a drop need to be added dropwise in the ethylene glycol for the PH1000 and 7% that specific ratio is 93%
Adhesive containing F stirs 8 hours.
The spin coating PEDOT:PSS suspension on PET substrate, spin speed are set as 1000rpm, and spin coating acceleration is set as
300rpm/s, spin-coating time are set as 40s, and spin coating is twice.
Dry on hot plate, drying temperature is set as 95 DEG C, drying time 6min.
The mechanical pressure processing of about 30Mpa is carried out to PEDOT:PSS film.
The conductivity and transmitance of PEDOT:PSS film are tested, conductivity 772.30S/cm improves 35.93%,
Light transmittance at 850nm is 71.41%.
Effect example
Common PEDOT:PSS film microstructure and molecular formula are as shown in Figure 1, conductive hydrophobic PEDOT chain and insulation are hydrophilic
PSS chain copolymerization, form water-soluble PEDOT:PSS polymer, it is thin by solwution methods such as spin coating, sprayings as described in front
Film deposition approach, can large area, high efficiency preparation PEDOTPSS transparent conductive film.
This example is passed through what is prepared according to example 1,2,3,4 by the PEDOT:PSS transparent conductive film of substrate of flexible PET
Simple and mechanical pressure treatment imposes the different mechanical strengths such as 10MPa, 20MPa, 30MPa respectively, obtains series of products, pass through
Its chemical structure of Raman spectral characterization, such as Fig. 2, treated that PEDOT:PSS transparent conductive film product is in for different mechanical pressures
Existing identical architecture signals, therefore it is believed that mechanical pressure handles and has not been changed its chemical structure.
Film photoelectric physical property is carried out to the Series P EDOT:PSS transparent conductive film product that different mechanical strengths are handled
Test obtain the result that Fig. 3, Fig. 4 are presented.Such as Fig. 3, the series thin film product near infrared band optical transmittance is in machinery
After processing, there is more apparent raising.Such as Fig. 4, which increases with mechanical treatment intensity and is reduced, conductance
Rate is also obviously improved with the increase of mechanical treatment intensity.Specifically, the PEDOT:PSS is transparent under the processing of 30MPa magnitude mechanical
Conductive film product conductivity promotes 35% or more.
The upper only presently preferred embodiments of the present invention, is not intended to limit the invention, all in spirit of the invention
With any modifications, equivalent replacements, and improvements made within principle etc., should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of method for improving flexible polymer transparent conductive film photoelectric characteristic, which is characterized in that this method includes following
Step:
(1) the substrate deionized water for being cut into square block, alcohol, deionized water are respectively cleaned by ultrasonic 10~15 minutes；
It (2) is in mass ratio that a drop adhesive containing F, stirring 6 are instilled into mixed liquor after 93:7 is mixed by PH1000, ethylene glycol
~8 hours, obtain PEDOT:PSS suspension；
(3) on substrate spin coating or spraying PEDOT:PSS suspension, according to the thickness and surface uniformity of PEDOT:PSS film
Determine spin coating or spray parameters；
(4) substrate that deposited PEDOT:PSS suspension is dry on hot plate, according to the property of substrate and PEDOT:PSS film
Matter determines drying parameter；
(5) mechanical pressure processing is carried out to the PEDOT:PSS film of the substrate surface after drying.
2. improving the method for flexible polymer transparent conductive film photoelectric characteristic as described in claim 1, which is characterized in that
In step (1), the substrate is flexible substrate material.
3. improving the method for flexible polymer transparent conductive film photoelectric characteristic as claimed in claim 2, which is characterized in that institute
Stating substrate is PET flexible substrate.
4. improving the method for flexible polymer transparent conductive film photoelectric characteristic as described in claim 1, which is characterized in that
In step (4), the drying parameter specifically: hot plate temperature is set as 95~100 DEG C, and drying time is 5~7min.
5. improving the method for flexible polymer transparent conductive film photoelectric characteristic as described in claim 1, which is characterized in that
In step (5), mechanical pressure processing to carry out pressure treatment by hydraulic or roll-in, the pressure pressure be 0Mpa~
30Mpa。
6. the flexible polymer transparent conductive film that the described in any item methods of Claims 1 to 5 are prepared.
7. flexible polymer transparent conductive film as claimed in claim 6 as flexible organic opto-electronic device electrode material or
Application in terms of modifying interface material.
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| CN201811466825.7A CN109671845B (en) | 2018-12-03 | 2018-12-03 | Method for improving photoelectric characteristics of flexible polymer transparent conductive film and application |
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| CN201811466825.7A CN109671845B (en) | 2018-12-03 | 2018-12-03 | Method for improving photoelectric characteristics of flexible polymer transparent conductive film and application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372898A (en) * | 2019-07-05 | 2019-10-25 | 江西科技师范大学 | A kind of preparation method of transparent high conductive organic flexible PEDOT:PSS film |
| CN113643855A (en) * | 2021-06-18 | 2021-11-12 | 南京邮电大学 | Preparation method and application of flexible transparent electrode |
| CN114320133A (en) * | 2022-01-27 | 2022-04-12 | 兰州大学 | Intelligent window and preparation method thereof |
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| CN102800487A (en) * | 2012-08-08 | 2012-11-28 | 中国科学院理化技术研究所 | Electrode material with 3D nanometer structure for super capacitor and application thereof |
| WO2014090394A1 (en) * | 2012-12-10 | 2014-06-19 | Stichting Materials Innovation Institute (M2I) | Organic electronic device with a translucent top electrode and method for depositing such an electrode |
| CN104170130A (en) * | 2012-11-19 | 2014-11-26 | 株式会社Lg化学 | Cathode active material composition and lithium secondary battery comprising same |
| CN104893640A (en) * | 2015-06-16 | 2015-09-09 | 华中科技大学 | Conductive adhesive as well as preparation method and application method thereof |
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2018
- 2018-12-03 CN CN201811466825.7A patent/CN109671845B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102800487A (en) * | 2012-08-08 | 2012-11-28 | 中国科学院理化技术研究所 | Electrode material with 3D nanometer structure for super capacitor and application thereof |
| CN104170130A (en) * | 2012-11-19 | 2014-11-26 | 株式会社Lg化学 | Cathode active material composition and lithium secondary battery comprising same |
| WO2014090394A1 (en) * | 2012-12-10 | 2014-06-19 | Stichting Materials Innovation Institute (M2I) | Organic electronic device with a translucent top electrode and method for depositing such an electrode |
| CN104893640A (en) * | 2015-06-16 | 2015-09-09 | 华中科技大学 | Conductive adhesive as well as preparation method and application method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372898A (en) * | 2019-07-05 | 2019-10-25 | 江西科技师范大学 | A kind of preparation method of transparent high conductive organic flexible PEDOT:PSS film |
| CN113643855A (en) * | 2021-06-18 | 2021-11-12 | 南京邮电大学 | Preparation method and application of flexible transparent electrode |
| CN114320133A (en) * | 2022-01-27 | 2022-04-12 | 兰州大学 | Intelligent window and preparation method thereof |
| CN114320133B (en) * | 2022-01-27 | 2023-09-22 | 兰州大学 | Smart window and preparation method thereof |
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