CN112625285B - Organic functional film/ultrathin film and preparation method and application thereof - Google Patents
Organic functional film/ultrathin film and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of functional material films, and discloses an organic functional film/ultrathin film, and a preparation method and application thereof. The organic functional film/ultrathin film comprises a pretreatment substrate and an organic functional material deposited on the pretreatment substrate, wherein the organic functional material is uniformly deposited into the organic functional film, and the static contact angle of the pretreatment substrate is less than 65 degrees. The organic functional film/ultrathin film utilizes the organic atmosphere to induce the Magney effect between gas-liquid interfaces to control the directional flow of a liquid film and finally directionally deposit and form a film on a pretreated substrate. The invention provides a non-contact scheme which can prepare a large-area functional film and simultaneously realize the precise control and preparation of the shape and the thickness of the film.
Description
Technical Field
The invention relates to the field of organic functional material films, in particular to an organic film/ultrathin film and a preparation method and application thereof.
Background
Organic photovoltaic materials have found widespread use in Organic Light Emitting Diodes (OLEDs), Organic Field Effect Transistors (OFETs), solar cells (OPVs), sensors, photodetectors, and many other devices, and thus have received considerable attention in the scientific and industrial sectors. Compared with inorganic materials, organic materials have various advantages such as flexibility, large area, and low-cost manufacturing. The high-quality organic functional film is very important for preparing high-performance photoelectric devices.
At present, the preparation of organic functional thin films is mainly divided into two methods: gas phase processes and solution processes. The vapor phase method generally requires high vacuum conditions and long growth time, and the kinds of semiconductors suitable for vapor deposition are limited; the solution method is a simple and convenient technology suitable for processing various materials and large areas, and common methods comprise drop coating, spin coating, blade coating, dip-coating and the like. The drop coating is one of the simplest film-making methods, only solution drops are required to be naturally volatilized on a substrate, but the drop coating is sensitive to preparation conditions and is difficult to prepare a high-quality film. The spin coating operation is simple, the condition is mild, the uniformity and the thickness of the film are more controllable, but the method is not suitable for large-area preparation. The film prepared by blade coating needs to depend on various factors such as the surface property of a substrate, the type of solvent, the concentration of a solution, the temperature, the shearing speed and the like. The dipping and pulling method has low cost and simple preparation conditions, is easy to realize large-area preparation, but is easy to generate periodic stripes caused by Rayleigh instability. The existing film preparation methods have certain limitations, so that the development of a method for preparing a high-quality organic functional material film with high efficiency and low cost has important significance.
In contrast, a new preparation method based on the solution method can ensure efficiency and control cost. Essentially, the current solution method mainly regulates a gas-liquid interface through shearing force, and then prepares a high-quality organic functional material film. Effective shear forces can also be generated by utilizing gas-liquid interfacial tension, a phenomenon known as the marangoni effect. The gas-liquid interface is easy to adsorb active substances to cause local tension change, and the local tension change is macroscopically represented as infiltration or spreading. By locally and quantitatively releasing surface active substances (such as gas micromolecules), the control of local liquid film infiltration can be realized. The liquid film is induced to generate surface tension difference under the action of atmosphere, and the generation of a meniscus can provide a non-contact method for substance deposition. Based on this, we propose atmosphere-induced preparation of organic semiconductor thin films. The method spontaneously removes the infiltration through the surface tension difference of the liquid film, avoids the damage of external force to the appearance of the film, and is expected to realize wide application in large area.
Disclosure of Invention
The invention provides an organic functional film/ultrathin film, aiming at the problems of material waste, poor film uniformity, lack of accurate control on film thickness and nano structure and the like in the preparation of organic functional films in the prior art, and the organic functional film/ultrathin film is thin in thickness, small in roughness and capable of realizing large-area preparation.
In order to achieve the above object, the present invention provides an organic functional thin film/ultra-thin film comprising a pretreated substrate and an organic functional material deposited on the pretreated substrate, wherein the organic functional material is uniformly deposited as an organic functional thin film, and the pretreated substrate has a static contact angle of less than 65 °.
According to the present invention, the pretreated substrate is not particularly limited as long as the pretreated substrate has a static contact angle of less than 65 °, and preferably, the pretreated substrate is rigid or flexible; the pretreated substrate is transparent or opaque; preferably, the substrate is Si/SiO2One of a sheet, a glass sheet, a PEN film, a PET film, a quartz sheet, an aluminum sheet, or a copper sheet.
According to the invention, the preparation method of the pretreated substrate is one of silane coupling agent treatment, plasma treatment or ultraviolet irradiation treatment.
The specific conditions for the silane coupling agent treatment are not particularly limited in the present invention, and preferably, the silane coupling agent is at least one of perfluorosiloxane, dichlorosiloxane, vinylsiloxane, aminopropylsiloxane, and polydimethylsiloxane; the silane coupling agent treatment conditions are as follows: under the vacuum condition, the time is 2-6 h, and the temperature is 60-120 ℃.
In the present invention, specific conditions of the plasma treatment are not particularly limited, and preferably, the conditions of the plasma treatment include: the time is 60-300 s, the power is 50-200W, and more preferably, the time is 100-200 s, and the power is 100-150W.
The present invention is not particularly limited to specific conditions of the ultraviolet light treatment, and preferably, the conditions of the ultraviolet light treatment include: the illumination time is 12-20 h, the power is 300-500W, and more preferably, the illumination time is 14-16 h, and the power is 400-450W.
According to the present invention, the kind of the organic functional material is not particularly limited, and may be appropriately selected as needed, and preferably, the organic functional material is a conjugated/non-conjugated small molecule or a conjugated/non-conjugated polymer; further preferably, the organic functional material is one of porphyrin conjugated small molecules, perylene imide conjugated small molecules, naphthalimide conjugated small molecules, conjugated oligomer small molecules based on heteroatom five-membered rings (furan, pyrrole, thiophene and the like) and fused ring compounds thereof, conjugated polymers based on the conjugated units or non-conjugated polymers with a main chain of a flexible alkyl chain.
The invention also aims to provide a preparation method of the organic functional film/ultrathin film, which has the advantages of regulating and controlling the film appearance on the nanometer scale and realizing the preparation of the high-efficiency and uniform film.
In order to achieve the above object, the present invention provides a method for preparing an organic functional thin film/ultrathin film, comprising the steps of:
1) a gas source is vertical to the pretreated base material and keeps a certain height and distance;
2) dripping solution containing organic functional material on the pretreated base material and spreading the solution into a liquid film;
3) controlling the pretreated substrate to move close to the gas source at a specific speed, and realizing the deposition of the organic functional material film;
4) and annealing the prepared organic film to obtain the organic functional film/ultrathin film.
According to the invention, the gas source should be selected from polar, nonpolar or inert solvents with low surface tension and high vapor pressure, such as ethanol, isopropanol, n-butanol, chloroform or tetrahydrofuran.
According to the invention, the gas source is a tubular gas source or a planar gas source, and the diameter of the tubular gas source is more than 0.1 mm; the area of the planar gas source is less than 100cm2And the angle of the air source is 0-180 degrees.
According to the invention, the height is 0.1-5 mm; the distance is 1-10 cm.
According to the present invention, the organic functional material solution is composed of an organic functional material and a solvent.
According to the invention, the mass concentration of the organic functional material is 0.1-10%, preferably 0.5-2.5%.
According to the present invention, the kind of the solvent in the organic functional material solution is not particularly limited, and may be appropriately selected according to the need, and preferably, the solvent is one or a mixture of a polar solvent, a non-polar solvent or an inert solvent; further preferably, the solvent is one or a mixture of water, cyclohexanone, anisole, N-dimethylformamide and o-dichlorobenzene.
According to the invention, the driving force of the directional movement of the liquid film is that a low surface tension gas source diffuses into a high surface tension solution to cause the local surface tension difference of the solution to move towards the direction close to the gas source; the moving speed of the base material is 0.1-5.0 mm/s, and the temperature of the base material is 25-85 ℃.
According to the present invention, there is no particular limitation on the annealing conditions, and the annealing conditions are selected according to conventional technical means in the art, in order to remove residual solvent in the thin film and improve the crystallinity of the organic material, and preferably, the annealing temperature is 100 to 200 ℃ and the annealing time is 0.5 to 2 hours.
According to the invention, the thickness of the organic functional film/ultrathin film is 2 nm-2 μm.
It is a further object of the present invention to provide an application of the organic functional thin film/ultrathin film in an organic field effect transistor, an organic light emitting diode, an organic solar cell, a sensor or a photodetector.
Compared with the prior art, the invention has the following advantages:
(1) the invention utilizes the Marangoni effect of a gas-liquid interface to control the edge of a liquid film to generate a meniscus and control the uniform evaporation deposition film formation at a three-phase line.
(2) The scheme provided by the invention can realize the accurate control of the thickness of the organic material on the pretreated substrate, can be applied in a large area, and is convenient, rapid, non-contact and easy to assemble.
(3) The organic functional film provided by the invention has the roughness less than 2nm and the area more than 1cm2Can realize the accurate control of the thickness of the filmTherefore, the organic photoelectric material has wide application prospect in the field of organic photoelectricity.
Drawings
FIG. 1 is a schematic view of an experimental apparatus in example 1 of the present invention;
wherein: 1-gas source; 2-pretreated substrate; 3-meniscus induced by atmosphere; 4-organic functional thin film/ultrathin film.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1
(1) Preparation of pretreated substrates
Mixing Si/SiO2The sheet is subjected to ultrasonic cleaning with water, acetone, isopropanol and the like, and then is subjected to oxygen plasma treatment under the following treatment conditions: the time is 200s, the power is 100W, and pretreated Si/SiO with the static contact angle of 2 degrees is obtained2And (3) slicing.
(2) Preparation of gas sources
Selecting 30 sample application capillaries with the diameter of 0.3mm multiplied by 0.3mm, closely arranging the sample application capillaries into a capillary array (as shown in figure 1), controlling the gas source and pretreating Si/SiO2The angle of the sheet is 90 degrees, the height is 0.5mm, and saturated absolute ethyl alcohol is sucked in the air source.
(3) Preparation of organic functional film
Preparing an ethanol/water solution of poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS), wherein the mass concentration of the PEDOT: PSS is 1.1%, and the mass content of ethanol in a solvent accounts for 20%; then 20. mu.l of PEDOT: PSS solution was added dropwise to the pretreated Si/SiO obtained in step 1) 1 x 2cm using a micro-syringe2The liquid drops are diffused to form a uniform liquid film at the center of the sheet; moving the pretreated Si/SiO2The chip is gradually close to the gas source, the moving speed of the chip is controlled to be 1mm/s, the temperature is controlled to be 50 ℃, the liquid film is soaked to generate a hysteresis liquid film, and the organic film is obtained by deposition at the position of the three-phase line.
(4) Post-treatment
To the surface of warpPretreatment of organic thin films of Si/SiO2Annealing the sheet, wherein the annealing conditions comprise: the annealing temperature is 110 ℃, and the annealing time is 30min, thus obtaining PEDOT, namely PSS film S-1.
Example 2
(1) Preparation of pretreated substrates
Carrying out ultrasonic cleaning on a glass sheet by using water, acetone, isopropanol and the like, and then carrying out oxygen plasma treatment, wherein the treatment conditions comprise that: the time was 200s and the power was 100W, resulting in a pretreated glass sheet with a static contact angle of 2 °.
(2) Preparation of gas sources
Selecting the area of 1 x 1cm2The filter paper is a surface air source, the angle between the air source and the pretreated glass sheet is controlled to be 60 degrees, the height is controlled to be 0.5mm, and saturated isopropanol is sucked in the air source.
(3) Preparation of organic functional film
Preparing an ethanol/water solution of PEDOT (PSS), wherein the mass concentration of the PEDOT to the PSS is 1.1%, and the mass content of ethanol in a solvent accounts for 20%; then, a microinjector is used for sucking 20 mul of PEDOT, the PSS solution is dripped to the center of the pretreated glass sheet prepared in the step 1) of 1 x 2cm, and the liquid droplets are diffused to form a uniform liquid film; moving the glass sheet to approach the air source gradually, controlling the moving speed to be 1mm/s and the temperature to be 50 ℃, infiltrating the liquid film to generate a hysteresis liquid film, and depositing at the three-phase line to obtain the organic film.
(4) Post-treatment
Annealing the pretreated glass sheet of the organic thin film subjected to surface deposition, wherein the annealing conditions comprise: the annealing temperature is 120 ℃, the annealing time is 20min, and PEDOT, namely PSS film S-2 is obtained.
Example 3
(1) Preparation of pretreated substrates
Mixing Si/SiO2The sheet is subjected to ultrasonic cleaning with water, acetone, isopropanol and the like, and then is subjected to oxygen plasma treatment under the following treatment conditions: the time is 200s, the power is 100W, and pretreated Si/SiO with the static contact angle of 2 degrees is obtained2And (3) slicing.
(2) Preparation of gas sources
Selecting 30 pieces of 0.3mm in the book0.3mm sample capillaries closely arranged in capillary array (as shown in FIG. 1), the gas source and pretreated Si/SiO are controlled2The angle of the sheet is 90 degrees, the height is 0.5mm, and saturated absolute ethyl alcohol is sucked in the air source.
(3) Preparation of organic functional film
Preparing an aqueous solution of MESO-tetra (4-sulfonylphenyl) porphine manganese chloride (MnTPPS), wherein the mass concentration of the MnTPPS is 1.0%; then 20. mu.l of MnTPPS solution was pipetted into 1 x 2cm drops using a micro-syringe2Pretreated Si/SiO prepared in step 1)2The liquid drops are diffused to form a uniform liquid film at the center of the sheet; moving the pretreated Si/SiO2The chip is gradually close to an air source, the moving speed of the chip is controlled to be 1mm/s, the temperature is controlled to be 25 ℃, the liquid film is soaked to generate a hysteresis liquid film, and the organic film is obtained by deposition at the position of a three-phase line.
(4) Post-treatment
Pretreatment of surface-deposited organic thin films with Si/SiO2Annealing the sheet, wherein the annealing conditions comprise: the annealing temperature is 120 ℃, and the annealing time is 20min, so that the MnTPPS film S-3 is obtained.
Example 4
(1) Preparation of pretreated substrates
Mixing Si/SiO2The sheet is subjected to ultrasonic cleaning with water, acetone, isopropanol and the like, and then is subjected to oxygen plasma treatment under the following treatment conditions: the time is 200s, the power is 100W, and pretreated Si/SiO with the static contact angle of 2 degrees is obtained2And (3) slicing.
(2) Preparation of gas sources
Selecting the area of 1 x 1cm2The filter paper is used as a surface air source, and the air source is controlled to be in contact with the pretreated Si/SiO2The angle of the sheet is 90 degrees, the height is 0.5mm, and saturated absolute ethyl alcohol is sucked in the air source.
(3) Preparation of organic functional film
Preparing an ethanol/water solution of PEDOT (PSS), wherein the mass concentration of the PEDOT to the PSS is 1.1%, and the ethanol content in a solvent accounts for 20%; then 20. mu.l of PEDOT: PSS solution was added dropwise to the pretreated Si/SiO obtained in step 1) 1 x 2cm using a micro-syringe2At the center of the sheet, allowing the droplets to spreadForming a uniform liquid film; moving the pretreated Si/SiO2The chip is gradually close to the gas source, the moving speed of the chip is controlled to be 1mm/s, the temperature is controlled to be 50 ℃, the liquid film is soaked to generate a hysteresis liquid film, and the organic film is obtained by deposition at the position of the three-phase line.
(4) Post-treatment
Pretreatment of surface-deposited organic thin films with Si/SiO2Annealing the sheet, wherein the annealing conditions comprise: and annealing at the temperature of 120 ℃ for 10-20 min to obtain the PEDOT (PSS) film S-4.
Example 5
1) Preparation of pretreated substrates
Mixing Si/SiO2Ultrasonic cleaning with water, acetone, isopropanol and the like is carried out, and fluorosilane treatment is carried out firstly, wherein the treatment conditions comprise that: and (3) carrying out vacuum treatment at the temperature of 80-120 ℃ for 2-6 h, and then carrying out oxygen plasma treatment, wherein the treatment conditions comprise: the time is 20s, the power is 20W, and the pretreated Si/SiO with the static contact angle of about 60 degrees is obtained2And (3) slicing.
(2) Preparation of gas sources
Selecting 1 x 1cm2The filter paper is used as a surface air source, and the air source is controlled to be in contact with the pretreated Si/SiO2The angle of the sheet is 60 degrees, the height is 1.0mm, and saturated absolute ethyl alcohol is sucked in the air source.
(3) Preparation of organic functional film
Preparing 2, 7-dioctyl [1 ]]Benzothieno [3,2-B]Benzothiophenes (C)8-BTBT) in cyclohexanone, C8-mass concentration of BTBT 0.5-1.5%; then 20 μ l C was aspirated using a microsyringe8Dropwise addition of BTBT solution to 1 x 2cm of pretreated Si/SiO obtained in step 1)2The liquid drops are diffused to form a uniform liquid film at the center of the sheet; moving the pretreated Si/SiO2The chip is gradually close to an air source, the moving speed of the chip is controlled to be 1mm/s, the temperature is controlled to be 25 ℃, the liquid film is soaked to generate a hysteresis liquid film, and the organic film is obtained by deposition at the position of a three-phase line.
(4) Post-treatment
Pretreatment of surface-deposited organic thin films with Si/SiO2Annealing the sheet, wherein the annealing conditions comprise: the annealing temperature is 110-140 ℃, and annealing is carried outFor 10min to obtain C8BTBT film S-5.
Comparative example 1
An organic functional thin film is prepared according to the method of the embodiment 1, except that in the step (2), an organic gas source is removed, and a liquid film is naturally dried to form a film, so that an organic functional thin film D-1 is prepared, which comprises the following specific steps:
(1) preparation of pretreated substrates
Mixing Si/SiO2The sheet is subjected to ultrasonic cleaning with water, acetone, isopropanol and the like, and then is subjected to oxygen plasma treatment under the following treatment conditions: the time is 200s, the power is 100W, and pretreated Si/SiO with the static contact angle of 2 degrees is obtained2And (3) slicing.
(2) Preparation of organic functional film
Preparing an ethanol/water solution of poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS), wherein the mass concentration of the PEDOT: PSS is 1.1%, and the mass content of ethanol in a solvent accounts for 20%; then 20. mu.l of PEDOT: PSS solution was added dropwise to the pretreated Si/SiO obtained in step 1) 1 x 2cm using a micro-syringe2The liquid drops are diffused to form a uniform liquid film at the center of the sheet; the liquid film was allowed to dry naturally in air.
(3) Post-treatment
Pretreatment of surface-deposited organic thin films with Si/SiO2Annealing the sheet, wherein the annealing conditions comprise: the annealing temperature is 110 ℃, and the annealing time is 30min, thus obtaining PEDOT, namely PSS film S-1.
The morphology of the organic functional thin film provided in examples 1-5 and comparative example 1 was tested, and mainly included morphology and roughness. The roughness means: the surface has small intervals and small unevenness of peaks and valleys, belonging to microscopic geometric errors. The smaller the surface roughness, the smoother the surface. The test results are shown in Table 1.
TABLE 1 Properties of organic functional thin/ultra-thin films prepared in examples 1 to 5 and comparative example 1
Claims (19)
1. An organic functional film/ultrathin film is characterized by comprising a pretreatment substrate and an organic functional material deposited on the pretreatment substrate, wherein the organic functional material is uniformly deposited into the organic functional film, and the static contact angle of the pretreatment substrate is less than 65 degrees;
the preparation method of the organic functional film/ultrathin film comprises the following steps:
1) a gas source is vertical to the pretreated base material and keeps a certain height and distance;
the gas source is a polar solvent or a nonpolar solvent with low surface tension and high vapor pressure; the gas source is a tubular gas source or a planar gas source; the pipe diameter of the tubular gas source is greater than 0.1 mm; the area of the planar gas source is less than 100cm2(ii) a The angle of the gas source is 0-180 degrees; the height is 0.1-5 mm, and the distance is 1-10 cm;
2) dripping solution containing organic functional material on the pretreated base material and spreading the solution into a liquid film;
the organic functional material solution consists of an organic functional material and a solvent; the mass concentration of the organic functional material is 0.1-10%; the organic functional material is one of porphyrin conjugated micromolecules, perylene imide conjugated micromolecules, naphthalimide conjugated micromolecules, conjugated oligomer micromolecules based on heteroatom five-membered rings and fused ring compounds thereof, conjugated polymers based on the conjugated units or non-conjugated polymers with main chains being flexible alkyl chains;
3) controlling the pretreated substrate to move close to the gas source at a specific speed, and realizing the deposition of the organic functional material film;
the driving force of the directional movement of the liquid film is that a low surface tension gas source diffuses into a high surface tension solution to cause the local surface tension difference of the solution to move towards the direction close to the gas source; the moving speed of the pretreated base material is 0.1-5.0 mm/s;
4) and annealing the prepared organic film to obtain the organic functional film/ultrathin film.
2. The organic functional film/ultrathin film according to claim 1, wherein the pretreated substrate is rigid or flexible.
3. The organic functional film/ultrathin film according to claim 1, wherein the pretreated substrate is transparent or opaque.
4. The organic functional thin/ultrathin film as claimed in claim 1, wherein the substrate is Si/SiO2One of a sheet, a glass sheet, a PEN film, a PET film, a quartz sheet, an aluminum sheet, or a copper sheet.
5. The organic functional thin/ultrathin film as claimed in claim 1, wherein the pretreatment method of the substrate is one of silane coupling agent treatment, plasma treatment or ultraviolet irradiation treatment.
6. The organic functional film/ultrathin film according to claim 5, wherein the silane coupling agent is at least one of perfluorosiloxane, dichlorosiloxane, vinylsiloxane, aminopropylsiloxane, or polydimethylsiloxane.
7. The organic functional thin/ultrathin film as claimed in claim 5, wherein the silane coupling agent treatment conditions are: under the vacuum condition, the time is 2-6 h, and the temperature is 60-120 ℃.
8. The organic functional thin film/ultrathin film as claimed in claim 5, wherein the conditions of the plasma treatment include: the time is 60-300 s, and the power is 50-200W.
9. The organic functional thin film/ultrathin film as claimed in claim 5, wherein the conditions of the plasma treatment include: the time is 100-200 s, and the power is 100-150W.
10. The organic functional thin/ultrathin film according to claim 5, wherein the conditions of the ultraviolet light treatment include: the illumination time is 12-20 h, and the power is 300-500W.
11. The organic functional thin/ultrathin film according to claim 5, wherein the conditions of the ultraviolet light treatment include: the illumination time is 14-16 h, and the power is 400-450W.
12. The organic functional film/ultrathin film as claimed in claim 1, wherein the gas source in the step 1) is one of ethanol, isopropanol, n-butanol, chloroform or tetrahydrofuran.
13. The organic functional film/ultrathin film according to claim 1, wherein the solvent in the step 2) is one or a mixture of water, cyclohexanone, anisole, N-dimethylformamide and o-dichlorobenzene.
14. The organic functional thin film/ultrathin film as claimed in claim 1, wherein the mass concentration of the organic functional material in the step 2) is 0.5 to 2.5%.
15. The organic functional thin film/ultrathin film according to claim 1, wherein the five-membered ring in the step 2) is one of furan, pyrrole or thiophene.
16. The organic functional thin/ultrathin film as claimed in claim 1, wherein the temperature of the pretreated substrate in the step 3) is 25 to 85 ℃.
17. The organic functional thin film/ultra-thin film according to claim 1, wherein the annealing condition in the step 4) is not particularly limited, and the annealing is performed to remove residual solvent in the thin film and improve the crystallinity of the organic material.
18. The organic functional thin film/ultrathin film as claimed in claim 1, wherein the annealing temperature in the step 4) is 100 to 200 ℃ and the annealing time is 0.5 to 2 hours.
19. Use of an organic functional thin/ultrathin film according to claim 1 in an organic field effect transistor, an organic light emitting diode, a solar cell, a sensor or a photodetector.
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| CN106920583A (en) * | 2017-02-10 | 2017-07-04 | 中国科学院化学研究所 | A kind of nesa coating and its preparation method and application |
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| CN103665409A (en) * | 2013-11-12 | 2014-03-26 | 华南理工大学 | Preparation method of conductive poly(3,4-ethylenedioxythiophene) composite film |
| CN106920583A (en) * | 2017-02-10 | 2017-07-04 | 中国科学院化学研究所 | A kind of nesa coating and its preparation method and application |
| CN111584768A (en) * | 2020-05-27 | 2020-08-25 | 北京交通大学 | Method and device for preparing organic electroluminescent device film |
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