CN109671845B - Method for improving photoelectric characteristics of flexible polymer transparent conductive film and application - Google Patents
Method for improving photoelectric characteristics of flexible polymer transparent conductive film and application Download PDFInfo
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- CN109671845B CN109671845B CN201811466825.7A CN201811466825A CN109671845B CN 109671845 B CN109671845 B CN 109671845B CN 201811466825 A CN201811466825 A CN 201811466825A CN 109671845 B CN109671845 B CN 109671845B
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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Abstract
The invention discloses a method for improving the photoelectric property of a flexible polymer transparent conductive film and application thereof, wherein a substrate cut into square blocks is ultrasonically cleaned for 10-15 minutes by deionized water, alcohol and deionized water respectively; mixing PH1000 and ethylene glycol according to a mass ratio of 93: 7, dripping a drop of F-containing adhesive into the mixed solution, and stirring for 6-8 hours to obtain PEDOT: (ii) a PSS suspension; spin coating or spray coating PEDOT on the substrate: PSS suspension, according to PEDOT: determining spin coating or spraying parameters according to the thickness and surface uniformity of the PSS film; the deposition of PEDOT: the substrate of PSS suspension was dried on a hot plate, according to the ratio of substrate and PEDOT: the nature of the PSS film determines the drying parameters; PEDOT on the dried substrate surface: the PSS film was subjected to mechanical pressure treatment. The flexible polymer transparent conductive film has good flexibility and transparent conductivity, and is suitable for application in the aspects of electrode materials or interface modification materials of flexible organic optoelectronic devices.
Description
Technical Field
The invention belongs to the technical field of organic optoelectronic devices, and particularly relates to a method for improving the photoelectric property of a flexible polymer transparent conductive film, the flexible polymer transparent conductive film with the improved photoelectric property obtained by the method, and application of the conductive film.
Background
The energy is the support of human survival and development, and in the past decades, the massive use of fossil energy (coal, oil and natural gas) causes serious harm to the environment in which human beings depend for survival, so that the search for renewable clean energy becomes extremely important. Since solar energy is clean, environment-friendly, pollution-free, high in utilization value, renewable and the like, the advantages determine the irreplaceable position in energy replacement, and a solar cell is a device for converting solar energy into electric energy, and in recent years, the solar cell is widely concerned and researched by scientists, and great research progress is achieved. So far, the photoelectric conversion efficiency of the crystalline silicon solar cell is the highest, and the preparation process and technology are the most mature, but the required high-quality silicon has complex preparation process and high price, so that the cost is too high, and the crystalline silicon solar cell is not suitable for being generally used. Therefore, Organic Solar Cells (OSCs) have been attracting attention and researched, and have unique advantages of low cost, good flexibility, large-area processing, etc., so that they are one of the most promising devices for solar energy conversion.
In recent years, due to the advantages of low cost and simple manufacturing process, various flexible organic optoelectronic devices capable of realizing mass production and the like are widely paid attention to and researched by scientists, particularly in the fields of flexible organic solar cells, flexible organic electroluminescent diodes and the like. The first Organic Light Emitting Diode (OLED) was developed by Kodak corporation in the United states since 1987, and thus, it has established a wide application prospect. The organic light-emitting diode has the advantages of wide visual angle, ultra-thinness, quick response, high luminous efficiency and the like, and is a globally accepted next-generation mainstream display; the organic light-emitting diode has the advantages of low power consumption, large-area film formation and the like, and can be used as an ideal plane light source for illumination; meanwhile, the organic light-emitting diode is an all-solid-state thin film device made of organic materials and amorphous materials, so that the organic light-emitting diode has good flexibility, and becomes an important technology in the field of wearable intelligent equipment. With the increasing demand of people for material life, the organic light emitting diode has great application potential in the fields of information display, lighting technology, flexible devices and the like.
The organic solar cell has a device structure that an organic active layer is clamped between a metal back electrode and a transparent electrode, sunlight penetrates through the transparent electrode to reach the organic active layer, the active layer absorbs partial photons to generate excitons, and the excitons are diffused and transferred in the active layer under the action of concentration gradient. Due to the work function difference between the positive and negative electrodes, a built-in electric field is created within the device, which separates excitons arriving at the donor and acceptor interfaces into electrons and holes, which are collected by the cathode and anode, respectively, to generate a current. The organic electroluminescent diode has the structure that organic layer holes and electrons are respectively injected from two ends of an anode and a cathode between a metal cathode and a transparent anode, the holes and the electrons meet in the organic layer to form excitons, the excitons release energy in the form of photons through radiation transition, and then the photons generated by the device are emitted through the transparent electrode. Because the work function (4.5-4.7 eV) of ITO (indium tin oxide) is between the LUMO and HOMO of most conductive polymers, and the ITO (indium tin oxide) has good conductivity and light transmittance, the ITO (indium tin oxide) is often used as a transparent electrode of an organic solar cell and an organic light-emitting diode. However, ITO belongs to metal oxide, has the biggest defect of poor flexibility and easy fragmentation, and is not suitable for the field of flexible organic optoelectronic devices.
PEDOT: PSS as a novel conductive polymer has good flexibility and transparent conductivity, can just make up for the defects of ITO, and becomes an electrode material or an interface modification material of a flexible organic optoelectronic device. However, the existing PEDOT: the PSS film has low conductivity and low transmittance in near infrared light, and the application of the PSS film in the field of flexible organic optoelectronic devices is limited. Ouyang et al treated PEDOT with concentrated sulfuric acid: the PSS film was treated to allow the ratio of PEDOT: the electrical conductivity of PSS films is high, but this approach yields PEDOT: the PSS film cannot be used as an electrode of a flexible organic solar cell because concentrated sulfuric acid has strong corrosivity, which may destroy the flatness of the flexible substrate, and is not favorable for the application of the film in the field of flexible optoelectronic devices.
Disclosure of Invention
The invention aims to provide a method for improving the photoelectric property of a flexible polymer transparent conductive film, aiming at improving the photoelectric property of the flexible polymer transparent conductive film without changing the ratio of PEDOT: under the premise of physicochemical structure and work function of the PSS film (flexible polymer transparent conductive film), the conductivity and near infrared transmittance of the film are improved, so that the film is more suitable for flexible organic optoelectronic devices.
The invention further aims to provide the flexible polymer transparent conductive film with improved photoelectric characteristics obtained by the method and application of the conductive film as an electrode material or an interface modification material of a flexible organic optoelectronic device.
The invention is realized by a method for improving the photoelectric property of a flexible polymer transparent conductive film, which comprises the following steps:
(1) ultrasonically cleaning the substrate cut into the square block shape for 10-15 minutes by using deionized water, alcohol and deionized water respectively;
(2) mixing PH1000 and ethylene glycol according to a mass ratio of 93: 7, dripping a drop of F-containing adhesive into the mixed solution, and stirring for 6-8 hours to obtain PEDOT: (ii) a PSS suspension;
(3) spin coating or spray coating PEDOT on the substrate: PSS suspension, according to PEDOT: determining spin coating or spraying parameters according to the thickness and surface uniformity of the PSS film;
(4) the deposition of PEDOT: the substrate of PSS suspension was dried on a hot plate, according to the ratio of substrate and PEDOT: the nature of the PSS film determines the drying parameters;
(5) PEDOT on the dried substrate surface: the PSS film was subjected to mechanical pressure treatment.
Preferably, in step (1), the substrate is a flexible substrate material.
Preferably, the substrate is a PET flexible substrate.
Preferably, in step (4), the drying parameters are specifically: the temperature of the hot plate is set to be 95-100 ℃, and the drying time is 5-7 min.
Preferably, in the step (5), the mechanical pressure treatment is pressure treatment by hydraulic pressure or roll pressing, and the pressure is 0Mpa to 30 Mpa.
The invention further discloses the flexible polymer transparent conductive film prepared by the method.
Preferably, the flexible polymer transparent conductive film is applied to the aspect of serving as an electrode material or an interface modification material of a flexible organic optoelectronic device.
Compared with the defects and shortcomings of the prior art, the invention has the following beneficial effects:
(1) PEDOT of the invention: after the PSS conductive film is subjected to mechanical pressure treatment, the conductivity is increased, the transmittance of the PSS conductive film to visible light is basically unchanged, the transmittance of the PSS conductive film to near infrared light with the wavelength of more than 600nm is increased, and the PEDOT with the film photoelectric characteristics greatly optimized is obtained: PSS transparent conductive film articles.
(2) The invention adopts a mechanical pressure treatment method, has simple operation and low cost, can be processed in a large area, is extremely suitable for large-area industrialized popularization, and ensures that the processed PEDOT: the PSS film is better applied to flexible organic optoelectronic devices.
Drawings
Figure 1 is PEDOT: a morphological schematic diagram of PSS; the left part shows PEDOT: the PSS particle is surrounded by a thin PSS surface layer, the PEDOT chain is depicted as a short rod, the magnification on the right gives the PEDOT: (ii) the molecular structure of PSS;
fig. 2 is PEDOT: raman spectra of the PSS film under different mechanical pressures;
fig. 3 is PEDOT: the PSS film has light transmittance in the near infrared range of 600nm to 1000nm under different mechanical pressures;
fig. 4 is PEDOT: the PSS films have improved thickness and conductivity ratio under different mechanical stress.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The purchased PET substrate was cut into 2cm × 2cm small squares, and ultrasonically cleaned with deionized water, alcohol, and deionized water for 15 minutes each.
Configuring PEDOT: the PSS suspension, in particular in the proportions 93% pH1000 and 7% ethylene glycol, was stirred for 8 hours with one drop of F-containing binder.
Spin coating PEDOT on PET substrate: the PSS suspension was spun twice at a spin speed of 1000rpm, a spin acceleration of 300rpm/s, a spin time of 40 s.
Drying on a hot plate at 95 deg.C for 6 min.
Testing the PEDOT: the PSS film has the conductivity and transmittance of 568.18S/cm and the light transmittance at 850nm of 68.40%.
Example 2
The purchased PET substrate was cut into 2cm × 2cm small squares, and ultrasonically cleaned with deionized water, alcohol, and deionized water for 15 minutes each.
Configuring PEDOT: the PSS suspension, in particular in the proportions 93% pH1000 and 7% ethylene glycol, was stirred for 8 hours with one drop of F-containing binder.
Spin coating PEDOT on PET substrate: the PSS suspension was spun twice at a spin speed of 1000rpm, a spin acceleration of 300rpm/s, a spin time of 40 s.
Drying on a hot plate at 95 deg.C for 6 min.
For PEDOT: the PSS film was subjected to mechanical pressure treatment of about 10 MPa.
Testing the PEDOT: the PSS film has the conductivity and the transmittance of 621.12S/cm, the conductivity is improved by 9.32 percent, and the light transmittance at 850nm is 69.25 percent.
Example 3
The purchased PET substrate was cut into 2cm × 2cm small squares, and ultrasonically cleaned with deionized water, alcohol, and deionized water for 15 minutes each.
Configuring PEDOT: the PSS suspension, in particular in the proportions 93% pH1000 and 7% ethylene glycol, was stirred for 8 hours with one drop of F-containing binder.
Spin coating PEDOT on PET substrate: the PSS suspension was spun twice at a spin speed of 1000rpm, a spin acceleration of 300rpm/s, a spin time of 40 s.
Drying on a hot plate at 95 deg.C for 6 min.
For PEDOT: the PSS film was subjected to mechanical pressure treatment of about 20 MPa.
Testing the PEDOT: the PSS film has the conductivity and the transmittance of 667.67S/cm, the conductivity is improved by 17.33%, and the light transmittance at 850nm is 70.32%.
Example 4
The purchased PET substrate was cut into 2cm × 2cm small squares, and ultrasonically cleaned with deionized water, alcohol, and deionized water for 15 minutes each.
Configuring PEDOT: the PSS suspension, in particular in the proportions 93% pH1000 and 7% ethylene glycol, was stirred for 8 hours with one drop of F-containing binder.
Spin coating PEDOT on PET substrate: the PSS suspension was spun twice at a spin speed of 1000rpm, a spin acceleration of 300rpm/s, a spin time of 40 s.
Drying on a hot plate at 95 deg.C for 6 min.
For PEDOT: the PSS film was subjected to a mechanical pressure of about 30 MPa.
Testing the PEDOT: the PSS film has the conductivity and the transmittance of 772.30S/cm, the conductivity is improved by 35.93 percent, and the light transmittance at 850nm is 71.41 percent.
Effects of the embodiment
The conventional PEDOT: the microstructure and the molecular formula of the PSS film are shown in figure 1, and a conductive hydrophobic PEDOT chain is copolymerized with an insulating hydrophilic PSS chain to form a water-soluble PEDOT: the PSS polymer can be used for preparing the PEDOTPSS transparent conductive film in a large area and high efficiency by solution-method film deposition means such as spin coating, spray coating and the like as previously described.
This example shows PEDOT on flexible PET substrate prepared according to examples 1, 2, 3, 4: the PSS transparent conductive film is subjected to simple mechanical pressure treatment, different mechanical strengths of 10MPa, 20MPa, 30MPa and the like are respectively applied to obtain a series of products, the chemical structure of the products is represented by a Raman spectrogram, as shown in figure 2, PEDOT after different mechanical pressure treatments: the PSS transparent conductive film articles exhibited the same structural signature, so it is believed that the mechanical pressure treatment did not change their chemical structure.
The series PEDOT obtained for the different mechanical strength treatments: the PSS transparent conductive film product is subjected to film photoelectric property test to obtain the results shown in figures 3 and 4. As shown in FIG. 3, the near-infrared band optical transmittance of the series of film products is obviously improved after mechanical treatment. As shown in FIG. 4, the film thickness of the series of film products is reduced along with the increase of the mechanical treatment strength, and the conductivity is obviously improved along with the increase of the mechanical treatment strength. Specifically, the PEDOT: the conductivity of the PSS transparent conductive film product is improved by over 35 percent.
The present invention is not limited to the above-described preferred embodiments, but rather, the present invention is intended to cover all modifications, equivalents, and improvements falling within the spirit and scope of the present invention.
Claims (7)
1. A method for improving the electro-optical properties of a flexible polymeric transparent conductive film, comprising the steps of:
(1) ultrasonically cleaning the substrate cut into the square block shape for 10-15 minutes by using deionized water, alcohol and deionized water respectively;
(2) mixing PH1000 and ethylene glycol according to a mass ratio of 93: 7, dripping a drop of F-containing adhesive into the mixed solution, and stirring for 6-8 hours to obtain PEDOT: (ii) a PSS suspension;
(3) spin coating or spray coating PEDOT on the substrate: PSS suspension, according to PEDOT: determining spin coating or spraying parameters according to the thickness and surface uniformity of the PSS film;
(4) the deposition of PEDOT: the substrate of PSS suspension was dried on a hot plate, according to the ratio of substrate and PEDOT: the nature of the PSS film determines the drying parameters;
(5) PEDOT on the dried substrate surface: the PSS film was subjected to mechanical pressure treatment.
2. The method for improving the photoelectric property of the flexible polymer transparent conductive film as claimed in claim 1, wherein in the step (1), the substrate is a flexible substrate material.
3. The method for improving the electro-optic properties of a flexible polymeric transparent conductive film according to claim 2, wherein the substrate is a PET flexible substrate.
4. The method for improving the photoelectric property of the flexible polymer transparent conductive film as claimed in claim 1, wherein in the step (4), the drying parameters are specifically: the temperature of the hot plate is set to be 95-100 ℃, and the drying time is 5-7 min.
5. The method for improving the electro-optical characteristics of the flexible polymer transparent conductive film according to claim 1, wherein in the step (5), the mechanical pressure treatment is a pressure treatment by hydraulic pressure or roll pressure, and the pressure is 20Mpa to 30 Mpa.
6. A flexible polymer transparent conductive film prepared by the method of any one of claims 1 to 5.
7. The flexible polymer transparent conductive film of claim 6 is applied as an electrode material or an interface modification material of a flexible organic optoelectronic device.
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| 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 |
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| 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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| 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 |
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