CN107502064A - Ink of cushion and preparation method thereof - Google Patents

Ink of cushion and preparation method thereof Download PDF

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Publication number
CN107502064A
CN107502064A CN201710674556.2A CN201710674556A CN107502064A CN 107502064 A CN107502064 A CN 107502064A CN 201710674556 A CN201710674556 A CN 201710674556A CN 107502064 A CN107502064 A CN 107502064A
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China
Prior art keywords
ink
buffer layer
zinc oxide
organic solvent
nano zinc
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CN201710674556.2A
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Chinese (zh)
Inventor
李胜夏
蓝河
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Shanghai Power Fang Electronic Technology Co Ltd
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Shanghai Power Fang Electronic Technology Co Ltd
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Priority to CN201710674556.2A priority Critical patent/CN107502064A/en
Publication of CN107502064A publication Critical patent/CN107502064A/en
Priority to CN201810182607.4A priority patent/CN108314927A/en
Withdrawn legal-status Critical Current

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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
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • 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
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D11/30—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
    • C09D11/30—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
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • 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
    • 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
    • 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
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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

Abstract

This disclosure relates to which a kind of be used to make ink of flexible organic photovoltaic thin-film device cushion and preparation method thereof and application and cushion, the ink for making flexible organic photovoltaic thin-film device cushion includes：Epoxy resin 150AB glue, nano zine oxide and organic solvent；Wherein, 150A concentration is 5 25mg/mL in the ink, and the concentration of the 150B is 2 12mg/mL, and the nano oxidized zinc concentration is 10 50mg/mL.The cushion that the disclosure provides has an electron transport property, and the active layer that the solvent of ink used will not be destroyed in photovoltaic device, film itself can be crosslinked, and the ink sprayed afterwards will not be permeated, and cushion will not be also dissolved even if upper strata heating.

Description

Buffer layer ink and preparation method thereof
Technical Field
The disclosure relates to the technical field of organic photovoltaic devices, in particular to ink for manufacturing a buffer layer of a flexible organic photovoltaic thin film device, a preparation method and application of the ink, and the buffer layer prepared by the preparation method of the ink.
Background
Compared with inorganic solar cells, Organic Photovoltaic (OPV) devices have the advantages of low cost, thin thickness, light weight, simple manufacturing process, capability of being made into large-area flexible devices and the like, have wide development and application prospects, and become one of the most vigorous and vital research fronts in the fields of new materials and new energy sources at present.
In terms of preparation process, the preparation process of inorganic photovoltaic devices which are applied more in industry at present mostly adopts a vacuum evaporation method, the vacuum evaporation method has more rigorous requirements on equipment and process, the evaporation method has requirements on heat resistance and cohesiveness of a base material, and only a single component can be evaporated in the same time period in the evaporation process. In the preparation process of the organic photovoltaic device, the organic material can be dissolved in a proper solvent, and the solution can be coated at a low temperature, and the like, compared with the traditional evaporation method, the method has the advantages of high speed, energy conservation, high material utilization rate and the like, so that the continuous large-scale production of the organic photovoltaic device by the solution method including screen printing, inkjet deposition, blade coating and the like is one of the main current improvement directions.
One of the major problems encountered in the solution method for manufacturing a multilayer device is that after the functional material is formed into a film, the functional material can be dissolved in a solvent used in the process of manufacturing the next film, thereby causing interpenetration between adjacent films, which makes it impossible to manufacture the multilayer device or makes the performance of the manufactured multilayer device poor. Crosslinking is one of the common approaches to this problem. The cross-linking refers to the process of cross-linking the surface or the whole of the film under a certain condition to form a reticular high polymer material, and when the film is cross-linked, the film is not dissolved in a solvent orthogonal to the film, so that the problem of mutual permeation among multiple layers of films is solved.
Organic photovoltaic devices generally have a multilayer structure including at least two electrodes and an organic semiconductor layer sandwiched between the two electrodes, the organic semiconductor layer being an active layer that converts light energy into electric energy. In order to reduce the energy level difference between the electrode and the active layer, improve the transmission efficiency of electrons and holes between the active layer and the electrode, reduce the recombination probability of electrons and holes, and improve the photo-generated current, thereby improving the conversion efficiency of the cell, in the organic photovoltaic device structure, a buffer layer is usually added between the electrode and the active layer. At present, the active layer and the buffer layer in the organic photovoltaic device are mainly made of high polymer materials, or organic small molecules or high polymer materials doped with inorganic materials can be adopted.
The crosslinkable buffer layer material includes a crosslinking agent and a charge transport material. Although theoretically, substances which can be dissolved in common solvents and realize the crosslinking function can be used as the crosslinking agent of the buffer layer, in reality, the film prepared by the solution method is mostly made of metal oxides and sulfides, and is limited by the requirement of charge transmission performance in application, and the preparation of a subsequent solution (ink) electrode cannot be realized. And another class of polymer materials widely studied at present often has no good crosslinking characteristics, cannot block the permeation of solution (ink) electrodes, and has little effect.
Therefore, finding a suitable combination of charge transport material and crosslinker is key to preparing a crosslinkable buffer layer. In recent years, it has been reported that, in the process of preparing an OLED element by a solution method, the material engineering college of south china university adopts PFNR2 and ELC2500 type epoxy resin to prepare a crosslinkable buffer layer, which has a significantly better effect than a non-crosslinkable buffer layer. However, although this buffer layer is crosslinkable, it has a limited blocking effect, and a small amount of solvent still permeates to affect the performance of the whole device, and the preparation of this buffer layer requires uv treatment, which, in addition to increasing the cost, has an uncertain effect on the electrical performance of the electrical device.
Therefore, in the process of preparing the electric element by the current solution method, a novel buffer layer solution with good crosslinking performance, good blocking effect and simple post-treatment is urgently needed, and for the process of preparing the electric element by ink-jet printing, the solution also needs to meet the viscosity requirement of printer ink.
Disclosure of Invention
The purpose of the present disclosure is: the first aspect provides ink for manufacturing a buffer layer of a flexible organic photovoltaic thin film device, the second aspect provides a preparation method of the ink for manufacturing the buffer layer of the flexible organic photovoltaic thin film device, the third aspect provides a method for manufacturing the buffer layer of the flexible organic photovoltaic thin film device by adopting the ink provided by the first aspect of the disclosure, and the fourth aspect provides a buffer layer of the flexible organic photovoltaic thin film device manufactured by the method for manufacturing the buffer layer of the flexible organic photovoltaic thin film device 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 photovoltaic thin film device.
To achieve the above object, a first aspect of the present disclosure: an ink for making a buffer layer of a flexible organic photovoltaic thin film device is provided, comprising: epoxy resin 150AB glue, nano zinc oxide and an organic solvent; wherein the concentration of 150A in the ink is 5-25mg/mL, the concentration of 150B is 2-12mg/mL, and the concentration of the nano zinc oxide is 10-50 mg/mL.
Optionally, the organic solvent is at least one selected from ethanol, isopropanol, propylene glycol monomethyl ether acetate and dibutyl carbonate.
Optionally, the organic solvent is isopropanol and/or propylene glycol methyl ether acetate.
Optionally, the ink further comprises 1-5 wt% of an additive, wherein the additive is at least one selected from ethylene glycol and glycerol.
Optionally, the particle size of the nano zinc oxide is less than 10 nm.
In a second aspect of the present disclosure: the preparation method of the ink for manufacturing the buffer layer of the flexible organic photovoltaic thin film device comprises the following steps: mixing epoxy resin 150AB glue and nano zinc oxide with an organic solvent to obtain ink; wherein the concentration of 150A in the ink is 5-25mg/mL, the concentration of 150B is 2-12mg/mL, and the concentration of the nano zinc oxide is 10-50 mg/mL.
Optionally, the organic solvent is at least one selected from ethanol, isopropanol, propylene glycol monomethyl ether acetate and dibutyl carbonate.
Optionally, the organic solvent is isopropanol and/or propylene glycol methyl ether acetate.
Optionally, the ink further comprises 1-5 wt% of an additive, wherein the additive is at least one selected from ethylene glycol and glycerol.
Optionally, the particle size of the nano zinc oxide is less than 10 nm.
Optionally, the step of mixing 150A, 150B and nano zinc oxide with an organic solvent to obtain the ink includes: mixing epoxy resin 150AB glue with a part of organic solvent to obtain a first mixed solution; dispersing the nano zinc oxide in the other part of the organic solvent to obtain a second mixed solution; mixing the first mixed solution and the second mixed solution to obtain ink; wherein the volume ratio of the first mixed solution to the second mixed solution is 1: 10.
optionally, the method further includes: mixing epoxy resin 150AB glue and nano zinc oxide with an organic solvent, and then sequentially carrying out ultrasonic treatment and filtration to obtain the ink.
A third aspect of the disclosure: there is provided a method of fabricating a buffer layer of a flexible organic photovoltaic thin film device using an ink provided in the first aspect of the present disclosure, 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; the resulting ink film is thermally crosslinked.
Optionally, the ink film is made by inkjet printing and/or screen printing.
Optionally, the temperature of the thermal crosslinking is 80-100 ℃, and the time is 40-60 min.
A fourth aspect of the present disclosure provides a flexible organic thin film device buffer layer made by the method of making a flexible organic thin film device buffer layer provided by the third aspect of the present disclosure.
According to the preparation method, the ink for manufacturing the buffer layer of the flexible organic photovoltaic thin film device is provided by adjusting the composition of the ink, the buffer layer is printed between the light emitting layer and the cathode, and the prepared buffer layer can be used for blocking the permeation of the silver ink and transmitting electrons, so that the ink-jet printing of the cathode is realized, and the free patterned light emission is realized under the condition without a mask plate.
In addition, the buffer layer film formed by inkjet provided by the present disclosure can be crosslinked by itself, post-sprayed ink does not penetrate, the buffer layer is not dissolved even if the upper layer is heated, and a solvent used in the buffer layer does not damage an active layer in the organic photovoltaic device. The organic photovoltaic device has good electron transmission effect, solves the problem of mutual permeation between an active layer and a buffer layer and between the buffer layer and electrode ink in the preparation of the organic photovoltaic device by ink-jet printing, and improves the performance of the organic photovoltaic device.
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.
The first aspect of the disclosure: an ink for making a buffer layer of a flexible organic photovoltaic thin film device is provided, comprising: epoxy resin 150AB glue, nano zinc oxide and an organic solvent; wherein, epoxy resin 150AB glue and nano zinc oxide are mixed with an organic solvent to obtain ink; wherein the concentration of 150A in the ink is 5-25mg/mL, the concentration of 150B is 2-12mg/mL, and the concentration of the nano zinc oxide is 10-50 mg/mL; preferably, the concentration of 150A in the ink is 4-8mg/mL, the concentration of 150B in the ink is 2-4mg/mL, and the concentration of the nano zinc oxide is 20-40 mg/mL.
According to the first aspect of the present disclosure, in order to realize the all solution preparation, even the ink-jet printing preparation, of the OPV device, the present disclosure prepares an organic buffer layer ink orthogonal to the solvent of the active layer, the ink is mainly composed of a semiconductor oxide and a thermally crosslinkable polymer, and in addition, the ink can isolate the permeation of the upper layer solution after film formation by adding other additives, and simultaneously has certain electron transport characteristics, and in use, the film can be well formed no matter by spin coating, doctor blading, screen printing, ink-jet printing and the like.
According to the first aspect of the present disclosure, the organic solvent is well known to those skilled in the art, and is used for dissolving poly (4-vinylphenol), poly (melamine formaldehyde) and dispersing nano zinc oxide, and an organic solvent having a boiling point below 200 ℃ is generally used, and may be, for example, at least one selected from ethanol, isopropanol, Propylene Glycol Methyl Ether Acetate (PGMEA), and dibutyl carbonate, preferably isopropanol and/or Propylene Glycol methyl ether acetate.
According to the first aspect of the disclosure, the epoxy resin 150AB is a common pouring sealant, and is very soluble in alcohol reagents, and the mixed solution can prepare a film capable of self-crosslinking, so that the permeation of the electrode ink can be effectively blocked, and the mass ratio of 150A to 150B is preferably 2: 1.
According to the first aspect of the present disclosure, the ink may further contain 1 to 5% by weight of an additive, which may be at least one selected from the group consisting of ethylene glycol and glycerin, for increasing the viscosity and surface tension of the ink, facilitating the ink to form a film, and also having a moisturizing effect.
According to the first aspect of the present disclosure, zinc oxide (ZnO) is a semiconductor material having an electron output capability, and can be used as an electron transport layer between an active layer and an electrode, and the particle size of the nano zinc oxide is preferably less than 10nm in order to obtain a better dispersion effect.
According to the first aspect of the present disclosure, the viscosity of the ink of the present disclosure is preferably in the range of 2 to 30 Centipoise (CPS), more preferably 3 to 10 CPS, and the surface tension is preferably 15 to 50 dynes/cm2(dynes/cm2) And more preferably 25 to 40 dynes/cm2。
In a second aspect of the present disclosure: the preparation method of the ink for manufacturing the buffer layer of the flexible organic photovoltaic thin film device comprises the following steps: epoxy resin 150AB glue, nano zinc oxide and an organic solvent; wherein, epoxy resin 150AB glue and nano zinc oxide are mixed with an organic solvent to obtain ink; wherein the concentration of 150A in the ink is 5-25mg/mL, the concentration of 150B is 2-12mg/mL, and the concentration of the nano zinc oxide is 10-50 mg/mL; preferably, the concentration of 150A in the ink is 4-8mg/mL, the concentration of 150B in the ink is 2-4mg/mL, and the concentration of the nano zinc oxide is 20-40 mg/mL.
According to the second aspect of the present disclosure, the organic solvent is well known to those skilled in the art, and is generally used for dissolving the epoxy resin 150AB glue and dispersing the nano zinc oxide, and the organic solvent having a boiling point below 200 ℃ is used, and may be at least one selected from ethanol, isopropanol, Propylene Glycol Methyl Ether Acetate (PGMEA), and dibutyl carbonate, for example, and is preferably isopropanol and/or propylene glycol methyl ether acetate.
According to the first aspect of the disclosure, the epoxy resin 150AB is a common pouring sealant, and is very soluble in alcohol reagents, and the film prepared from the mixed solution can be self-crosslinked, so that the permeation of the electrode ink can be effectively blocked, and the mass ratio of 150A to 150B is preferably 2: 1.
According to the second aspect of the present disclosure, the ink may further contain 1 to 5% by weight of an additive, which may be at least one selected from the group consisting of ethylene glycol and glycerin, for increasing the viscosity and surface tension of the ink, facilitating the ink to form a film, and also having a moisturizing effect.
According to the second aspect of the present disclosure, zinc oxide (ZnO) is a semiconductor material having an electron output capability, and can be used as an electron transport layer between an active layer and an electrode, and the particle size of the nano zinc oxide is preferably less than 10nm in order to obtain a better dispersion effect.
According to the second aspect of the present disclosure, the step of mixing the epoxy resin 150AB and the nano zinc oxide with the organic solvent to obtain the ink may include: mixing epoxy resin 150AB with a part of organic solvent to obtain a first mixed solution; dispersing the nano zinc oxide in the other part of the organic solvent to obtain a second mixed solution; mixing the first mixed solution and the second mixed solution to obtain ink; wherein the volume ratio of the first mixed solution to the second mixed solution is 1: (2-10). The first mixed solution and the second mixed solution are prepared respectively by adopting the mode, and the first mixed solution and the second mixed solution can be placed for a long time and can be prepared according to the needs when in use.
According to the second aspect of the present disclosure, the method may further include: and mixing the epoxy resin 150AB, the nano zinc oxide and the organic solvent, and then sequentially carrying out ultrasonic treatment and filtration to obtain the ink. Sonication and filtration are well known to those skilled in the art, and are used to disperse the components of the ink and reduce sedimentation, and may be at a frequency of 20 to 40kHz for a period of 5 to 10 minutes; the filtering process is used to filter a precipitated portion in the ink, prevent the head of the printer from being clogged, and improve the printing effect, and the filtering accuracy thereof may be 0.1 to 0.5 μm.
A third aspect of the disclosure: there is provided a method of fabricating a buffer layer of a flexible organic photovoltaic thin film device using an ink provided in the first aspect of the present disclosure, 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; the resulting ink film is thermally crosslinked.
According to the third aspect of the present disclosure, the buffer layer refers to the layer or layers between the active layer and the electrode in the thin film electronic device, and can be divided into an anode buffer layer and a cathode buffer layer, and the buffer layer mainly functions to transport electrons or holes.
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 100nm to 2 μm; if the ink film is manufactured by spin coating, the ink film with the thickness of 50-300 nm 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 may be prepared using the ink of the present disclosure in various ways, and the thickness of the thin film may be different according to the method. In order to realize the free patterning preparation of the buffer layer under the condition of no mask plate, the mode of manufacturing the ink 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 film is generally 300nm-1 μm.
According to a third aspect of the present disclosure, thermal crosslinking is well known to those skilled in the art, and the present disclosure is preferably carried out at a lower temperature, for example, at a temperature of 80-100 ℃ for a time of 40-60 min. According to the method, after the solvent is removed by heating, a good crosslinking effect can be achieved by heating for a short time, redundant solvent does not need to be removed in special requirements such as a vacuum drying oven and a nitrogen glove box, post-treatment is not needed under light source conditions such as an infrared lamp, an ultraviolet lamp and laser, and the post-treatment process is simplified.
A fourth aspect of the present disclosure: there is provided a flexible organic photovoltaic thin film device buffer layer made by the method of making a flexible organic photovoltaic thin film device buffer layer provided by 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 active layer prepared by the existing spin coating and doctor blade coating methods.
In addition to preparing the buffer layer, the inks of the present disclosure can also be applied as an overcoat crosslinker in a render coating, and can also be used to prepare crosslinkable semiconductor 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.
Example 1
Epoxy resin 60mg150A and 30mg 150B were weighed and transferred to 5mL reagent bottle A, and 1mL of isopropyl alcohol was added to the reagent bottle A and dissolved with stirring. Weighing 30mg ZnO (particle size less than 10nm) and placing in a reagent bottle, weighing 1mL isopropanol and adding in a reagent bottle B, and performing ultrasonic dispersion for 10min under the condition of 40 kHz. Mixing the solutions in the reagent bottles A and B according to a volume ratio of 1:10, performing ultrasonic treatment for 5min, and filtering by using a filter head with the diameter of 0.22 μm to obtain ink, wherein the specific composition is shown in Table 1.
The ink is filled into an ink box, an ink film can be stably ejected by an ink-jet printer, a compact cross-linked film can be formed after heating and cross-linking at 120 ℃, the effect of blocking the permeation of the ink on the upper layer can be achieved, the specific ink-jet performance is shown in table 2, and a buffer layer made of the ink can reach the use standard, can block the permeation of the silver ink and can transmit electrons.
Examples 2 to 7
The preparation steps of the examples 2-7 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 2-7 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 ink composition Table
TABLE 2 ink viscosity and surface tension table
Examples Viscosity, centipoise Surface tension, dyne/cm2
Example 1 4.22 23.8
Example 2 4.08 24.2
Example 3 6.66 25.5
Example 4 5.12 23.7
Example 5 7.85 24.6
Example 6 11.02 24.5
Example 7 3.86 25.3

Claims (16)

1. An ink for making a buffer layer of a flexible organic photovoltaic thin film device, comprising:
epoxy resin 150AB glue, nano zinc oxide and an organic solvent; wherein,
the concentration of 150A in the ink is 5-25mg/mL, the concentration of 150B is 2-12mg/mL, and the concentration of the nano zinc oxide is 10-50 mg/mL.
2. The ink according to claim 1, wherein the organic solvent is at least one selected from the group consisting of ethanol, isopropanol, propylene glycol methyl ether acetate, and dibutyl carbonate.
3. Ink according to claim 1 or 2, wherein the organic solvent is isopropanol and/or propylene glycol methyl ether acetate.
4. The ink according to claim 1, wherein the ink further contains 1 to 5% by weight of an additive, the additive being at least one selected from the group consisting of ethylene glycol and glycerin.
5. The ink of claim 1, wherein the nano zinc oxide has a particle size of less than 10 nm.
6. A preparation method of ink for manufacturing a buffer layer of a flexible organic photovoltaic thin film device comprises the following steps:
mixing epoxy resin 150AB glue and nano zinc oxide with an organic solvent to obtain ink;
wherein the concentration of 150A in the ink is 5-25mg/mL, the concentration of 150B is 2-12mg/mL, and the concentration of the nano zinc oxide is 10-50 mg/mL.
7. The production method according to claim 6, wherein the organic solvent is at least one selected from the group consisting of ethanol, isopropanol, propylene glycol monomethyl ether acetate, and dibutyl carbonate.
8. The production method according to claim 6 or 7, wherein the organic solvent is isopropyl alcohol and/or propylene glycol methyl ether acetate.
9. The production method according to claim 6, wherein the ink further contains 1 to 5% by weight of an additive which is at least one selected from the group consisting of ethylene glycol and glycerin.
10. The preparation method according to claim 6, wherein the nano zinc oxide has a particle size of less than 10 nm.
11. The method of claim 6, wherein the step of mixing the poly (4-vinylphenol), the poly (melamine formaldehyde) and the nano zinc oxide with an organic solvent to obtain the ink comprises:
mixing epoxy resin 150AB glue with a part of organic solvent to obtain a first mixed solution;
dispersing the nano zinc oxide in the other part of the organic solvent to obtain a second mixed solution;
mixing the first mixed solution and the second mixed solution to obtain ink; wherein the volume ratio of the first mixed solution to the second mixed solution is 1: 10.
12. the method of making according to claim 6, the method further comprising: mixing epoxy resin 150AB glue and nano zinc oxide with an organic solvent, and then sequentially carrying out ultrasonic treatment and filtration to obtain the ink.
13. A method of fabricating a buffer layer for a flexible organic photovoltaic thin film device using the ink of any one of claims 1-5, 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;
the resulting ink film is thermally crosslinked.
14. A method of fabricating a flexible organic photovoltaic thin film device buffer layer according to claim 13, wherein the manner of fabricating the ink thin film is inkjet printing and/or screen printing.
15. The method of fabricating a flexible organic photovoltaic thin film device buffer layer according to claim 13, wherein the thermal crosslinking is at a temperature of 80-100 ℃ for a time of 40-60 min.
16. A flexible organic thin film device buffer layer made according to the method of making a flexible organic thin film device buffer layer of claim 13, 14, or 15.
CN201710674556.2A 2017-08-09 2017-08-09 Ink of cushion and preparation method thereof Withdrawn CN107502064A (en)

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CN110499070A (en) * 2019-08-14 2019-11-26 深圳市华星光电半导体显示技术有限公司 Prepare the ink and its manufacturing method of cathode buffer layer

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KR100869163B1 (en) * 2007-05-18 2008-11-19 한국전기연구원 Fabrication method of transparent conductive films containing carbon nanotubes and polymer binders and the transparent conductive films
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CN106987172A (en) * 2017-04-19 2017-07-28 上海幂方电子科技有限公司 A kind of ink, preparation method and application for being used to make cushion

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CN108963102A (en) * 2017-12-29 2018-12-07 广东聚华印刷显示技术有限公司 The preparation method of OLED device
CN110499070A (en) * 2019-08-14 2019-11-26 深圳市华星光电半导体显示技术有限公司 Prepare the ink and its manufacturing method of cathode buffer layer

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