CN106947321B - Ink for manufacturing buffer layer, preparation method and application - Google Patents

Ink for manufacturing buffer layer, preparation method and application Download PDF

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Publication number
CN106947321B
CN106947321B CN201710258766.3A CN201710258766A CN106947321B CN 106947321 B CN106947321 B CN 106947321B CN 201710258766 A CN201710258766 A CN 201710258766A CN 106947321 B CN106947321 B CN 106947321B
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ink
poly
buffer layer
electrochemical cell
polymer additive
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CN106947321A (en
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李胜夏
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Shanghai Mi Fang Electronics Ltd
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Shanghai Mi Fang Electronics Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/135—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising mobile ions
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • 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
    • 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
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The present disclosure relates to an ink for making a buffer layer of a flexible organic light-emitting electrochemical cell, a preparation method and an application thereof, and a buffer layer prepared by the ink, wherein the ink for making the buffer layer of the flexible organic light-emitting electrochemical cell comprises: poly (vinyl cinnamate), poly (9, 9-dioctylfluorene), polymer additives, and organic solvents; wherein the concentration of poly (vinyl cinnamate) in the ink is 5-40mg/mL, the concentration of poly (9, 9-dioctylfluorene) is 0.5-5mg/mL, and the weight ratio of the polymer additive to the ink is 1-10 wt%. The ink disclosed by the invention can be used for printing a buffer layer between the light-emitting layer and the cathode, and the buffer layer can be used for blocking the permeation of silver ink and transmitting electrons, so that the ink-jet printing of the cathode is realized, and free patterned light emission is realized under the condition without a mask plate.

Description

Ink for manufacturing buffer layer, preparation method and application
Technical Field
The disclosure relates to the technical field of organic light-emitting electrochemical cells, in particular to ink for manufacturing a buffer layer of a flexible organic light-emitting electrochemical cell, a preparation method and application of the ink, and the buffer layer prepared by the ink.
Background
In recent years, the organic light-emitting thin film device prepared by the all-solution method has been widely researched, and compared with the traditional evaporation method, the organic light-emitting thin film device has the advantages of high speed, energy conservation, high material utilization rate and the like. Most of the current research on devices prepared by a solution method is single-layer or multi-layer solution preparation, but the full solution preparation cannot be realized, one of the most critical problems in the full solution preparation is the problem of mutual dissolution and permeation among solutions of each layer, an orthogonal solvent is often used between an upper layer and a lower layer, and a buffer layer in contact with electrode ink can be crosslinked by itself, so that the effect of each layer is not influenced, and the performance of each layer can be improved.
Conventional Organic Light Emitting Diode (OLED) devices mainly include organic small molecule light emitting diodes and polymer light emitting diodes. Compared with a Light emitting diode, an Organic Light-emitting electrochemical cell (OLEC) has a different Light emitting mechanism, so that the Organic Light-emitting electrochemical cell has some unique advantages, such as a lower operating voltage, a higher electron/photon conversion efficiency, a higher power efficiency, and the like. More importantly, organic light-emitting electrochemical cells do not require lower work function materials as the cathode, and these low work function electrode materials tend to be unstable in air. Meanwhile, a light-emitting layer in the organic light-emitting electrochemical cell can generate a p-n junction in situ, and injection of electrons and holes from two electrodes for light emission is facilitated. Therefore, compared with an organic light-emitting diode, the organic light-emitting electrochemical cell has lower requirements on the roughness of the surface of the electrode material, and is beneficial to large-scale production.
The preparation process of the organic light-emitting electrochemical cell (OLEC) is relatively simple, the luminescent layer is generally prepared by adopting a spin coating process, the electrode is also prepared by adopting a vacuum evaporation process, and the currently commercialized silver ink is mainly water-based or alcohol-based ink, can dissolve or permeate the luminescent layer in the organic light-emitting electrochemical cell, so that the device is subjected to electric leakage, and particularly relates to a device which is used as the luminescent layer and aims at a transition metal complex.
Disclosure of Invention
The purpose of the present disclosure is: the first aspect provides an ink for manufacturing a buffer layer of a flexible organic light-emitting electrochemical cell, the second aspect provides a preparation method of the ink for manufacturing the buffer layer of the flexible organic light-emitting electrochemical cell, the third aspect provides a method for manufacturing the buffer layer of the flexible organic light-emitting electrochemical cell by adopting the ink provided by the first aspect of the disclosure, and the fourth aspect provides a buffer layer of the flexible organic light-emitting electrochemical cell manufactured by the method for manufacturing the buffer layer of the flexible organic light-emitting electrochemical cell provided by the third aspect of the disclosure, and the disclosure can realize the printing of the buffer layer by the ink for manufacturing the buffer layer of the flexible organic light-emitting electrochemical cell.
In order to achieve the above object, in a first aspect of the present disclosure, there is provided an ink for fabricating a buffer layer of a flexible organic light-emitting electrochemical cell, comprising: poly (vinyl cinnamate), poly (9, 9-dioctylfluorene), polymer additives, and organic solvents; wherein the concentration of poly (vinyl cinnamate) in the ink is 5-40mg/mL, the concentration of poly (9, 9-dioctyl fluorene) is 0.5-5mg/mL, the weight ratio of the polymer additive in the ink is 1-10 wt%, and the weight average molecular weight of the polymer additive is 10000-50000.
Optionally, the organic solvent is at least one selected from toluene, anisole, N-dimethylformamide or chlorobenzene, and the polymer additive is polystyrene and/or polymethyl methacrylate.
Optionally, the organic solvent is toluene and/or anisole.
Optionally, the weight ratio of the poly (vinyl cinnamate) to the poly (9, 9-dioctylfluorene) is (5-20): 1.
in a second aspect of the present disclosure, there is provided a method for preparing an ink for making a buffer layer of a flexible organic light-emitting electrochemical cell, comprising: mixing poly (vinyl cinnamate), poly (9, 9-dioctyl fluorene) and a polymer additive with an organic solvent to obtain ink; wherein the concentration of poly (vinyl cinnamate) in the ink is 5-40mg/mL, the concentration of poly (9, 9-dioctyl fluorene) is 0.5-5mg/mL, the weight ratio of the polymer additive in the ink is 1-10 wt%, and the weight average molecular weight of the polymer additive is 10000-50000.
Optionally, the organic solvent is at least one selected from toluene, anisole, N-dimethylformamide or chlorobenzene, and the polymer additive is polystyrene and/or polymethyl methacrylate.
Optionally, the organic solvent is toluene and/or anisole.
Optionally, the weight ratio of the poly (vinyl cinnamate) to the poly (9, 9-dioctylfluorene) is (5-20): 1.
optionally, the method further includes: mixing poly (vinyl cinnamate), poly (9, 9-dioctyl fluorene) and polymer additive with organic solvent, and stirring, ultrasonic treating and filtering in sequence.
Optionally, the stirring time is 0.5-1 hour, the ultrasonic time is 1-10min, the ultrasonic frequency is 20-40kHz, and the filtering precision is 0.1-0.5 micron.
In a third aspect of the present disclosure, there is provided a method for fabricating a buffer layer of a flexible organic light-emitting electrochemical cell by using the ink provided in the first aspect of the present disclosure, including: manufacturing an ink film; wherein, the mode of making the ink film is at least one selected from ink-jet printing, screen printing, spin coating and blade coating; and placing the obtained ink film under ultraviolet light to enable the inside of the ink film to generate a crosslinking reaction.
Optionally, the ink film is made by inkjet printing and/or screen printing.
In a fourth aspect of the present disclosure, there is provided a flexible organic light-emitting electrochemical cell buffer layer made by the method for making a flexible organic light-emitting electrochemical cell buffer layer provided in the third aspect of the present disclosure.
The present disclosure provides inks for making buffer layers of flexible organic light-emitting electrochemical cells by formulating the composition of the inks, by printing a buffer layer between the light-emitting layer and the cathode that both blocks the penetration of silver ink and transmits electrons, thereby achieving ink-jet printing of the cathode, and achieving free patterned light emission without a mask.
In addition, the buffer layer provided by the present disclosure has an electron transport property, a solvent used does not destroy a transition metal complex-based light emitting layer, a thin film formed by ink jet can be crosslinked by itself, ink sprayed later does not permeate, and the buffer layer is not dissolved even if the upper layer is heated.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
In the prior art, an active layer (light-emitting layer) film is prepared on an Indium Tin Oxide (ITO) electrode, and then a silver electrode or an aluminum electrode is vapor-deposited. The top electrode mainly adopts a vacuum evaporation method, the equipment is expensive, the preparation time is long, and most of the top electrode needs to be operated in a glove box. In addition, the evaporation electrode needs a mask plate with various patterns, and the mask plate with high-precision patterning is very expensive. The buffer layer refers to one or more layers between an active layer (light-emitting layer) and an electrode in a thin film electronic device, and can be divided into an anode buffer layer and a cathode buffer layer, and the buffer layer is mainly used for transmitting electrons or holes.
In a first aspect of the present disclosure, there is provided an ink for making a buffer layer of a flexible organic light-emitting electrochemical cell, comprising: poly (vinyl cinnamate), poly (9, 9-dioctylfluorene), polymer additives, and organic solvents; wherein the concentration of poly (vinyl cinnamate) in the ink is 5-40mg/mL, the concentration of poly (9, 9-dioctylfluorene) is 0.5-5mg/mL, and the weight ratio of the polymer additive in the ink is 1-10 wt%; preferably, the concentration of poly (vinyl cinnamate) in the ink is 10-20mg/mL, the concentration of poly (9, 9-dioctylfluorene) is 1-3mg/mL, the weight ratio of the polymer additive in the ink is 3-6 wt%, and the weight average molecular weight of the polymer additive is 10000-50000.
According to the first aspect of the present disclosure, in order to realize the all-solution preparation, even the all-inkjet printing preparation of an organic light-emitting electrochemical cell (OLEC) device, the present disclosure is directed to an organic light-emitting electrochemical cell using a transition metal complex as a light-emitting layer, and an organic buffer layer ink orthogonal to the light-emitting layer is prepared through a large number of experiments, and mainly comprises a semiconductor polymer and a UV-crosslinkable polymer, and in addition, other additives can be added, so that the ink provided by the present disclosure can isolate the permeation of an upper layer solution after film formation, and simultaneously has certain electronic conduction characteristics, and in use, good film formation performance can be obtained through spin coating, blade coating, screen printing or inkjet printing.
According to a first aspect of the present disclosure, the organic solvent is used to dissolve poly (vinyl cinnamate), poly (9, 9-dioctylfluorene) and polymer additives. The proper boiling point, viscosity and surface tension of the organic solvent are critical to enabling ink jet printing, and not all solvents work very well. The present inventors have found through a large number of experiments that an organic solvent having a boiling point of not more than 200 ℃, further, an organic solvent selected from at least one of toluene, anisole, N-dimethylformamide, or chlorobenzene, preferably toluene and/or anisole, has a good inkjet printing effect.
According to the first aspect of the present disclosure, the polymer additive can play a role in regulating the viscosity and surface tension of the ink, so that the ink can form good films with different thicknesses on the active layer. The polymer additive may be polystyrene and/or polymethylmethacrylate. The weight average molecular weight of the polymer additive is 10000-50000, and if the weight average molecular weight of the polymer additive is too low, the viscosity of the ink is insufficient, and the surface tension is too low, the ink-jet effect is poor; if the weight average molecular weight of the polymer additive is too high, the viscosity of the system increases, and the printer head may be clogged, and ink may not be ejected.
According to the first aspect of the present disclosure, the inventors have found through a large number of experiments that the concentration of the Poly (vinyl cinnamate) (Poly (vinyl cinamate), PVCN), which is a photo-crosslinking polymer, is 5 to 40mg/mL, the concentration of Poly (9, 9-dioctylfluorene) (Poly (9, 9-di-n-octylfluornyl), PFO), which is a conductive polymer, is 0.5 to 5mg/mL, and the weight ratio of the two is preferably (5 to 20): 1, a buffer layer with good performance can be obtained. The film prepared by the ink can be crosslinked under the irradiation of ultraviolet light, and effectively prevents the permeation of the upper electrode ink.
According to the first aspect of the present disclosure, viscosity and surface tension are important performance indicators that determine ink ejection quality of an ink. If the viscosity of the ink is too high, the ink cannot be ejected, and the nozzle is blocked; if the viscosity of the ink is too low, ink dripping or ink dripping may occur. If the surface tension of the ink is too large, the ink cannot be ejected or the ink after ink jet does not easily wet the substrate, and if the surface tension of the ink is too small, satellite ink droplets, ink drops, or ink drips may occur. The inventor of the present disclosure found through experiments that the viscosity and surface tension of the ink are in the following ranges, and the ink jet quality is better: the viscosity of the ink is preferably in the range of 2 to 30 Centipoise (CPS), more preferably 3 to 5 CPS, and when the viscosity of the ink is less than 2 CPS, there is a large probability that ink dripping or ink running occurs, and when the viscosity of the ink is more than 20 CPS, there is a large probability that a head is clogged. Further, the surface tension is preferably 20 to 40 dynes/cm (dynes/cm), more preferably 25 to 35 dynes/cm. When the surface tension of the ink is less than 20 dyne/cm, satellite ink droplets are likely to occur, and when the surface tension of the ink is greater than 40 dyne/cm, ink ejection is not likely to occur.
In a second aspect of the present disclosure, there is provided a method for preparing an ink for making a buffer layer of a flexible organic light-emitting electrochemical cell, comprising: mixing poly (vinyl cinnamate), poly (9, 9-dioctyl fluorene) and a polymer additive with an organic solvent to obtain ink; wherein the concentration of poly (vinyl cinnamate) in the ink is 5-40mg/mL, the concentration of poly (9, 9-dioctylfluorene) is 0.5-5mg/mL, and the weight ratio of the polymer additive in the ink is 1-10 wt%; preferably, the concentration of poly (vinyl cinnamate) in the ink is 10-20mg/mL, the concentration of poly (9, 9-dioctylfluorene) is 1-3mg/mL, the weight ratio of the polymer additive in the ink is 3-6 wt%, and the weight average molecular weight of the polymer additive is 10000-50000.
According to a second aspect of the present disclosure, the organic solvent is used to dissolve poly (vinyl cinnamate), poly (9, 9-dioctylfluorene) and polymer additives. The proper boiling point, viscosity and surface tension of the organic solvent are critical to enabling ink jet printing, and not all solvents work very well. The inventor finds that the boiling point of the organic solvent is not suitable to exceed 200 ℃ through a large amount of experiments. Further, the organic solvent having a good ink jet printing effect may be at least one selected from toluene, anisole, N-dimethylformamide, or chlorobenzene, and is preferably toluene and/or anisole.
According to the second aspect of the present disclosure, the polymer additive can play a role in regulating the viscosity and surface tension of the ink, so that the ink can form good films with different thicknesses on the active layer. The polymer additive may be at least one selected from polystyrene or polymethylmethacrylate, and is preferably polystyrene and/or polymethylmethacrylate. The weight average molecular weight of the polymer additive is 10000-50000, and if the weight average molecular weight of the polymer additive is too low, the viscosity of the ink is insufficient, and the surface tension is too low, the ink-jet effect is poor; if the weight average molecular weight of the polymer additive is too high, the viscosity of the system increases, and the printer head may be clogged, and ink may not be ejected.
According to the second aspect of the present disclosure, the inventors have found through a large number of experiments that when the concentration of the Poly (vinyl cinnamate) (Poly (vinyl cinamate), PVCN) as the photo-crosslinking polymer is 5 to 40mg/mL, and the concentration of Poly (9, 9-dioctylfluorene) (Poly (9, 9-di-n-octylfluornyl), PFO) as the conductive polymer is 0.5 to 5mg/mL, the weight ratio of the two is preferably (5 to 20): 1, a buffer layer with good performance can be obtained. The film prepared by the ink can be crosslinked under the irradiation of ultraviolet light, and effectively prevents the permeation of the upper electrode ink.
According to the second aspect of the present disclosure, the method may further include: mixing poly (vinyl cinnamate), poly (9, 9-dioctyl fluorene) and polymer additive with organic solvent, and stirring, ultrasonic treating and filtering in sequence. Stirring, ultrasound and filtration are techniques well known to those skilled in the art, stirring and ultrasound are used to disperse the components in the ink and reduce sedimentation, the stirring time may be 0.5 to 1 hour, the ultrasound frequency may be 20 to 40kHz, and the time may be 1 to 10 min; the filtering process is used to filter the precipitated portions of the ink, prevent the printer head from being clogged, and improve the printing effect, and the filtering accuracy may be 0.1 to 0.5 μm.
In a third aspect of the present disclosure, there is provided a method for fabricating a buffer layer of a flexible organic light-emitting electrochemical cell by using the ink provided in the first aspect of the present disclosure, including: manufacturing an ink film; wherein, the mode of making the ink film is at least one of ink-jet printing, screen printing, spin coating or blade coating; and placing the obtained ink film under ultraviolet light to enable the inside of the ink film to generate a crosslinking reaction.
According to the third aspect of the present disclosure, it is preferable that the ink film is heated to remove the organic solvent, and then irradiated under a UV lamp for crosslinking, and generally irradiated for 5 to 20min to achieve a good crosslinking effect, without removing the residual solvent in a special environment such as a vacuum drying oven, a nitrogen glove box, or the like, or without performing post-treatment under a light source condition such as an infrared lamp, a laser, or the like.
According to the third aspect of the present disclosure, if an ink film is produced by doctor blade coating, varying the concentration and the doctor blade conditions (e.g., speed, temperature of the cliche, height of the doctor blade, etc.) can give an ink film having a thickness of 50nm to 1 μm; if the ink film is manufactured by spin coating, the ink film with the thickness of 20-300nm can be obtained by changing the concentration and the spin coating rotating speed.
According to the third aspect of the present disclosure, the buffer layer can be prepared by using the ink of the present disclosure in various ways, and for the purpose of realizing the free patterning preparation of the buffer layer without a mask plate, the way of preparing the ink thin film is preferably ink jet printing and/or screen printing, more preferably continuous ink jet printing, the voltage during ink jet is preferably not more than 20V, and the thickness of the ejected thin film is generally 300nm-1 μm.
In a fourth aspect of the present disclosure, there is provided a flexible organic light-emitting electrochemical cell buffer layer made by the method for making a flexible organic light-emitting electrochemical cell buffer layer provided in the third aspect of the present disclosure.
According to the fourth aspect of the present disclosure, if the buffer layer is prepared by ink-jet printing or screen printing, the pattern of the buffer layer provided by the fourth aspect of the present disclosure can be freely selected, and the pattern precision and definition are better than those of the buffer layer prepared by the spin coating or doctor blade coating method in the prior art.
In addition to preparing the buffer layer, the inks of the present disclosure can also be used as an external crosslinker for coatings in render coatings, and can also be used to prepare crosslinkable semiconducting material films in wearable devices.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby. Unless otherwise specified, the reagents used in the present disclosure are all commercially available, and the use is not affected by the difference of commercial grades. In the embodiment disclosed by the invention, the viscosity of the ink is tested by an American Rheosense microVISC portable viscometer, the surface tension is tested by a BZY-101 full-automatic surface tension meter by a platinum plate method, and the test temperature is 20 ℃.
Example 1
20mg of poly (vinyl cinnamate) and 2mg of poly (9, 9-dioctylfluorene) were weighed and transferred to a reagent bottle, 1mL of toluene was added, 2 wt% of polystyrene based on the weight of the ink was added, after magnetic stirring for 1 hour, ultrasound was performed at 40kHz for 5min, and then filtration was performed using a 0.22 μm filter head to obtain an ink, the specific composition of which is shown in Table 1.
The ink is filled into the ink box, the ink film can be stably ejected by an ink-jet printer, a compact cross-linked film can be formed after UV cross-linking, the effect of blocking the permeation of the ink on the upper layer can be achieved, the specific performance of the ink is shown in table 2, and a buffer layer made of the ink can reach the use standard, so that the permeation of the silver ink can be blocked, and electrons can be transmitted.
Examples 2 to 6
The preparation steps of the examples 2-6 are basically the same as that of the example 1, the specific composition is shown in table 1, the specific performance of the ink is shown in table 2, and the buffer layer prepared by the ink prepared in the examples 2-6 can reach the use standard, not only can block the permeation of the silver ink, but also can transmit electrons.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
TABLE 1
Figure BDA0001274159800000101
TABLE 2
Examples Viscosity, centipoise Surface tension, dyne/cm Ink jetting situation
Example 1 2.3 30.1 Good effect
Example 2 2.1 28.9 Good effect
Example 3 3.5 27.2 Good effect
Example 4 4.1 30.5 Good effect
Example 5 4.5 35.0 Good effect
Example 6 4.6 35.1 Good effect

Claims (9)

1. An ink for making a buffer layer of a flexible organic light-emitting electrochemical cell, comprising:
poly (vinyl cinnamate), poly (9, 9-dioctylfluorene), polymer additives, and organic solvents;
wherein the concentration of poly (vinyl cinnamate) in the ink is 5-40mg/mL, the concentration of poly (9, 9-dioctyl fluorene) is 0.5-5mg/mL, the weight ratio of the polymer additive in the ink is 1-10 wt%, and the weight average molecular weight of the polymer additive is 10000-50000;
the organic solvent is toluene and/or anisole; the polymer additive is polystyrene and/or polymethyl methacrylate.
2. The ink of claim 1, wherein the weight ratio of poly (vinyl cinnamate) to poly (9, 9-dioctylfluorene) is (5-20): 1.
3. a method of making an ink for making a buffer layer of a flexible organic light-emitting electrochemical cell, comprising:
mixing poly (vinyl cinnamate), poly (9, 9-dioctyl fluorene) and a polymer additive with an organic solvent to obtain ink;
wherein the concentration of poly (vinyl cinnamate) in the ink is 5-40mg/mL, the concentration of poly (9, 9-dioctyl fluorene) is 0.5-5mg/mL, the weight ratio of the polymer additive in the ink is 1-10 wt%, and the weight average molecular weight of the polymer additive is 10000-50000;
the organic solvent is toluene and/or anisole; the polymer additive is polystyrene and/or polymethyl methacrylate.
4. The production method according to claim 3, wherein the weight ratio of poly (vinyl cinnamate) to poly (9, 9-dioctylfluorene) is (5-20): 1.
5. the method of making according to claim 3, the method further comprising: mixing poly (vinyl cinnamate), poly (9, 9-dioctyl fluorene) and polymer additive with organic solvent, and stirring, ultrasonic treating and filtering in sequence.
6. The preparation method according to claim 5, wherein the stirring time is 0.5 to 1 hour, the ultrasonic time is 1 to 10min, the ultrasonic frequency is 20 to 40kHz, and the filtration precision is 0.1 to 0.5 μm.
7. A method of fabricating a buffer layer for a flexible organic light-emitting electrochemical cell using the ink of claim 1 or 2, comprising:
manufacturing an ink film; wherein, the mode of making the ink film is at least one selected from ink-jet printing, screen printing, spin coating and blade coating;
and placing the obtained ink film under ultraviolet light to enable the inside of the ink film to generate a crosslinking reaction.
8. The method of fabricating a buffer layer for a flexible organic light-emitting electrochemical cell according to claim 7, wherein the ink thin film is formed by inkjet printing and/or screen printing.
9. A flexible organic light-emitting electrochemical cell buffer layer made according to the method of making a flexible organic light-emitting electrochemical cell buffer layer of claim 7 or 8.
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