CN106987172A - A kind of ink, preparation method and application for being used to make cushion - Google Patents
A kind of ink, preparation method and application for being used to make cushion Download PDFInfo
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- CN106987172A CN106987172A CN201710258768.2A CN201710258768A CN106987172A CN 106987172 A CN106987172 A CN 106987172A CN 201710258768 A CN201710258768 A CN 201710258768A CN 106987172 A CN106987172 A CN 106987172A
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- cushion
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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
- C09D11/02—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
- C09D11/03—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
- C09D11/103—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds of aldehydes, e.g. phenol-formaldehyde resins
-
- 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
- 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
- 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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- 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
Abstract
This disclosure relates to which a kind of cushion for being used to make ink of flexible organic photovoltaic thin-film device cushion and preparation method and application and be prepared with this ink, the ink for making flexible organic photovoltaic thin-film device cushion includes：Poly- (4 vinylphenol), poly- (melamino-formaldehyde), nano zine oxide and organic solvent；Wherein, the concentration of (4 vinylphenol) poly- in the ink is 5 10mg/mL, and the concentration of poly- (melamino-formaldehyde) is 2 10mg/mL, and the nano oxidized zinc concentration is 10 70mg/mL.The cushion that the disclosure is provided has electron transport property, and the solvent of ink used will not destroy the luminescent layer of transient metal complex class, and film itself can be crosslinked, and the ink sprayed afterwards will not permeate, and cushion will not be also dissolved even if upper strata heating.
Description
Technical field
The disclosure relates to organic photovoltaic devices technical field, in particular it relates to which a kind of be used to make flexible organic photovoltaic film
Ink of device cushion and preparation method and application and the cushion prepared with this ink.
Background technology
Compared with inorganic solar cell, organic photovoltaic (Organic Photovoltaic, OPV) device has cost
Low, thickness is small, light weight, manufacturing process are simple, the advantages of can make large area flexible device, with wide development and application
Prospect, it has also become one of study frontier of current new material and the most rich vigour and vitality of new energy field.Used in OPV devices
Active layer can be made up of small molecule or the based semiconductor material of polymer two.Small molecular semiconductor device mainly passes through evaporation process
Prepare, and polymeric material device is mainly prepared by solwution method, such as spin coating, blade coating or volume to volume technique.
In recent years, having machine photovoltaic film device (OPV) for whole soln legal system has had more extensive research, with biography
The evaporation coating method of system is compared, and solwution method preparation technology is simple, it is possible to achieve prepared by quick large area flexible.But prior art
In, whole soln method prepares cushion and still not enough facilitated, strong to large scale equipment dependence, not good enough using flexibility.
The content of the invention
The purpose of the disclosure is：First aspect provides a kind of ink for being used to make flexible organic photovoltaic thin-film device cushion
Water, second aspect provides a kind of preparation method for being used to make the ink of flexible organic photovoltaic thin-film device cushion, third party
The method that face provides the flexible organic photovoltaic thin-film device cushion of ink making that a kind of use disclosure first aspect is provided,
Fourth aspect provides a kind of side of the flexible organic photovoltaic thin-film device cushion of making provided by the disclosure third aspect
Flexible organic photovoltaic thin-film device cushion made by method, the disclosure for making flexible organic photovoltaic thin-film device by delaying
The printing of cushion can be realized by rushing the ink of layer.
To achieve these goals, disclosure first aspect provides a kind of for making flexible organic photovoltaic thin-film device
The ink of cushion, including：Poly- (4-Vinyl phenol), poly- (melamino-formaldehyde), nano zine oxide and organic solvent；Its
In, the concentration of (4-Vinyl phenol) poly- in the ink is 5-10mg/mL, and the concentration of poly- (melamino-formaldehyde) is 2-
10mg/mL, the nano oxidized zinc concentration is 10-70mg/mL.
Optionally, the organic solvent is at least one in ethanol, propylene glycol methyl ether acetate or dibutyl carbonate
Kind.
Optionally, the organic solvent is ethanol and/or propylene glycol methyl ether acetate.
Optionally, additive of the ink also containing 1-5 weight %, the additive is selected from ethylene glycol, isopropanol
At least one of or glycerine.
Optionally, the particle diameter of the nano zine oxide is less than 10nm.
There is provided a kind of system for being used to make the ink of flexible organic photovoltaic thin-film device cushion for disclosure second aspect
Preparation Method, including：Poly- (4-Vinyl phenol), poly- (melamino-formaldehyde) and nano zine oxide are mixed with organic solvent, obtained
To ink；Wherein, the concentration of poly- (4-Vinyl phenol) is 5-10mg/mL, poly- (melamino-formaldehyde) in the ink
Concentration be 2-10mg/mL, the nano oxidized zinc concentration be 10-70mg/mL.
Optionally, the organic solvent is at least one in ethanol, propylene glycol methyl ether acetate or dibutyl carbonate
Kind.
Optionally, the organic solvent is ethanol and/or propylene glycol methyl ether acetate.
Optionally, additive of the ink also containing 1-5 weight %, the additive is selected from ethylene glycol, isopropanol
At least one of with glycerine.
Optionally, the particle diameter of the nano zine oxide is less than 10nm.
Optionally, it is described by poly- (4-Vinyl phenol), poly- (melamino-formaldehyde) and nano zine oxide and organic solvent
Mixing, the step of obtaining ink includes：By poly- (4-Vinyl phenol) and poly- (melamino-formaldehyde) and a part of organic solvent
Mixing, obtains the first mixed liquor；Nano zine oxide is dispersed in another part organic solvent, the second mixed liquor is obtained；By institute
The first mixed liquor and the mixing of the second mixed liquor are stated, ink is obtained；Wherein, the volume ratio of first mixed liquor and the second mixed liquor
For 1：(8-12).
Optionally, methods described also includes：By poly- (4-Vinyl phenol), poly- (melamino-formaldehyde) and nano zine oxide
Ultrasound and filtering are carried out after being mixed with organic solvent successively, the ink is obtained.
The disclosure third aspect makes flexible organic light there is provided the ink that a kind of use disclosure first aspect is provided
The method for lying prostrate thin-film device cushion, including：Make ink film；Wherein, the mode for making ink film is selected from spray
At least one of black printing, silk-screen printing, spin coating or blade coating；Heat cross-linking is carried out to gained ink film.
Optionally, the mode for making ink film is inkjet printing or silk-screen printing.
Optionally, the temperature of the heat cross-linking is 100-150 DEG C, and the time is 30-60min.
There is provided a kind of flexible organic photovoltaic of making provided by the disclosure third aspect is thin for disclosure fourth aspect
Flexible organic photovoltaic thin-film device cushion made by the method for membrane module cushion.
There is provided the ink for making flexible organic photovoltaic thin-film device cushion by allocating the composition of ink for the disclosure
Water, can not only obstruct the infiltration of silver inks water but also can transmit the buffering of electronics by printing one layer between luminescent layer and negative electrode
Layer, realizes the inkjet printable of negative electrode, so as to realize that free patterning is luminous in the case of without mask plate.
In addition, the cushion that the disclosure is provided has electron transport property, solvent used will not destroy transition metal and match somebody with somebody
The luminescent layer of compound class, the film itself that ink-jet is formed can be crosslinked, and the ink sprayed afterwards will not permeate, and be heated even if upper strata
Cushion will not be dissolved.
Other feature and advantage of the disclosure will be described in detail in subsequent embodiment part.
Embodiment
Embodiment of this disclosure is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explained the disclosure, is not limited to the disclosure.
The semi-conducting material with electronics fan-out capability is used alone in the prior art as between active layer and electrode
Electron transfer layer, electrode is typically prepared using the technique of evaporation, or is prepared using the higher silver paste of viscosity.Pass through inkjet printing
The report that the method for electrode prepares OPV devices is considerably less, because electrode ink can penetrate lower film, causes device power-on and power-off
Pole electric leakage is serious, and device can not work.Top electrode is mainly the method using vacuum evaporation, and equipment is expensive, and preparation time is very long,
And most of needs are operated in glove box.Other electrode evaporation is, it is necessary to the mask plate of various patterns, and patterns of high precision is covered
Diaphragm plate price is sufficiently expensive.
There is provided a kind of ink for being used to make flexible organic photovoltaic thin-film device cushion, bag for disclosure first aspect
Include：Poly- (4-Vinyl phenol), poly- (melamino-formaldehyde), nano zine oxide and organic solvent；Wherein, gather in the ink
The concentration of (4-Vinyl phenol) is 5-10mg/mL, and the concentration of poly- (melamino-formaldehyde) is 2-10mg/mL, described to receive
Rice oxidation zinc concentration is 10-70mg/mL；Preferably, the concentration of poly- (4-Vinyl phenol) is 6-7mg/mL in the ink,
The concentration of poly- (melamino-formaldehyde) is 2-8mg/mL, and the nano oxidized zinc concentration is 20-40mg/mL.
According to the disclosure in a first aspect, in order to realize OPV devices whole soln prepare, even inkjet printing prepare,
The disclosed invention people is prepared for a kind of organic buffer layer ink orthogonal with active layer by many experiments, and the ink is mainly
It is made up of the polymer of conductor oxidate and thermally cross-linkable, can makes ink in film forming by adding other additives in addition
The infiltration of upper solution can be completely cut off afterwards, while having certain Electronic Transport of Two Benzene, in use, pass through spin coating, blade coating, silk screen
Printing or inkjet printing can obtain good filming performance.
According to the disclosure in a first aspect, the organic solvent is used to dissolve poly- (4-Vinyl phenol), poly- (melamine
Formaldehyde) and scattered nano zine oxide.There is organic solvent suitable boiling point, viscosity and surface tension to be their ability to beat for ink-jet
The key of print, therefore simultaneously not all solvent can reach very good ink jet printing performance.Inventor sends out by many experiments
Existing, the boiling point of organic solvent is no more than 200 DEG C.Further, the organic solvent with good ink jet printing performance can be
Selected from ethanol, propylene glycol methyl ether acetate (Propylene Glycol Methyl Ether Acetate, PGMEA) or carbonic acid
At least one of dibutyl ester, preferably ethanol and/or propylene glycol methyl ether acetate.
According to the disclosure in a first aspect, the present inventor has found by many experiments, the polymer of thermally cross-linkable is used as
The concentration of poly- (4-Vinyl phenol) (poly (4-vinylphenol), PVP) is 5-10mg/mL, is used as poly- (the three of crosslinking agent
Melamine-formaldehyde) concentration of (Poly (melamine-formaldehyde), PMF) is 2-10mg/mL, and the two weight is than excellent
Elect as (1-7)：When 1, cushion of good performance can be just obtained.
According to the disclosure in a first aspect, the ink can also the additive containing 1-5 weight %, the additive can
Think selected from least one of ethylene glycol, isopropanol or glycerine, additive is used for the viscosity and surface tension for improving ink, has
Beneficial to ink formation film, and also there is moisture-keeping function.
According to the disclosure in a first aspect, zinc oxide (zinc oxide, ZnO) is the semiconductor with electronics fan-out capability
Material, can be as the electron transfer layer between active layer and electrode, for more preferably scattered, the particle diameter of the nano zine oxide
Preferably smaller than 10nm.
According to the disclosure in a first aspect, viscosity and surface tension are the important physical parameters of ink, ink is together decided on
The quality of ink-jet.If the viscosity of ink is excessive, ink can not spray, so as to block shower nozzle；If ink viscosity is too small, it can go out
Now drip ink or drop down the phenomenon of ink.If the surface tension of ink is excessive, ink can not similarly spray or ink-jet after ink
Water is not easy to infiltrate substrate, if the surface tension of ink is too small, and satellite ink droplet, drop ink or the phenomenon for dropping down ink occurs.This
Open inventor has found that the viscosity and surface tension of ink are within the scope of following, and ink jetting quality is more excellent through overtesting：Ink
Range of viscosities is preferably 2-20 centipoises (CPS), more preferably 5-10 centipoises, when the viscosity of ink is less than 2 centipoise, there is maximum probability
There is drop ink or drop down the phenomenon of ink, when ink viscosity is more than 20 centipoise, there is maximum probability the phenomenon for blocking shower nozzle occur.Separately
Outside, surface tension is preferably 20-40 dynes per centimeters (dynes/cm), more preferably 26-36 dynes per centimeters.When the surface of ink
Tension force be less than 20 dynes per centimeter when, there is maximum probability the phenomenon of satellite ink droplet occur, when ink surface tension be more than 40 dynes/
Centimetre when, have maximum probability occur can not ink-jet situation.
There is provided a kind of system for being used to make the ink of flexible organic photovoltaic thin-film device cushion for disclosure second aspect
Preparation Method, including：Poly- (4-Vinyl phenol), poly- (melamino-formaldehyde) and nano zine oxide are mixed with organic solvent, obtained
To ink；Wherein, the concentration of poly- (4-Vinyl phenol) is 5-10mg/mL, poly- (melamino-formaldehyde) in the ink
Concentration be 2-10mg/mL, the nano oxidized zinc concentration be 10-70mg/mL；Preferably, poly- (4- ethene in the ink
Base phenol) concentration be 6-7mg/mL, the concentration of poly- (melamino-formaldehyde) is 2-8mg/mL, the nano zine oxide
Concentration is 20-40mg/mL.
According to the second aspect of the disclosure, the organic solvent is used to dissolve poly- (4-Vinyl phenol), poly- (melamine
Formaldehyde) and scattered nano zine oxide, there is organic solvent suitable boiling point, viscosity and surface tension to be their ability to beat for ink-jet
The key of print, and simultaneously not all solvent can reach very good ink jet printing performance.Inventor has found by many experiments
The boiling point of organic solvent is no more than 200 DEG C.Further, the organic solvent with good result can be selected from ethanol, third
In glycol methyl ether acetate (Propylene Glycol Methyl Ether Acetate, PGMEA) or dibutyl carbonate extremely
Few one kind, preferably ethanol and/or propylene glycol methyl ether acetate.
According to the disclosure in a first aspect, the present inventor has found by many experiments, the polymer of thermally cross-linkable is used as
The concentration of poly- (4-Vinyl phenol) (poly (4-vinylphenol), PVP) is 5-10mg/mL, is used as poly- (the three of crosslinking agent
Melamine-formaldehyde) concentration of (Poly (melamine-formaldehyde), PMF) is 2-10mg/mL, and the two weight is than excellent
Elect as (1-7)：When 1, cushion of good performance can be just obtained.
According to the second aspect of the disclosure, the ink can also the additive containing 1-5 weight %, the additive can
Think selected from least one of ethylene glycol, isopropanol or glycerine, additive is used for the viscosity and surface tension for improving ink, has
Beneficial to ink formation film, and also there is moisture-keeping function.
According to the second aspect of the disclosure, zinc oxide (zinc oxide, ZnO) is the semiconductor with electronics fan-out capability
Material, can be as the electron transfer layer between active layer and electrode, for more preferably scattered, the particle diameter of the nano zine oxide
Preferably smaller than 10nm.
It is described by poly- (4-Vinyl phenol), poly- (melamino-formaldehyde) and nano oxygen according to the second aspect of the disclosure
Change zinc to mix with organic solvent, the step of obtaining ink can include：By poly- (4-Vinyl phenol) and poly- (melamine first
Aldehyde) mixed with a part of organic solvent, obtain the first mixed liquor；Nano zine oxide is dispersed in another part organic solvent,
Obtain the second mixed liquor；First mixed liquor and the second mixed liquor are mixed, ink is obtained；Wherein, first mixed liquor
Volume ratio with the second mixed liquor is 1：(2-10).First mixed liquor and the second mixed liquor are prepared using this kind of mode respectively, can
So that the first mixed liquor and the second mixed liquor place and allocated as needed when in use for a long time.
According to the second aspect of the disclosure, methods described can also include：By poly- (4-Vinyl phenol), poly- (melamine
Amine formaldehyde) and nano zine oxide mixed with organic solvent after successively carry out ultrasound and filtering, obtain the ink.It is ultrasonically treated and
Filtration treatment is technology well-known to those skilled in the art, ultrasonically treated to be used for each component in dispersible ink, reduces precipitation, its
Frequency can be 20-40kHz, and the time can be 5-10min；Filtration treatment is used to filter the sediment fraction in ink, prevents from beating
Print machine shower nozzle is blocked and improves printing effect, and its filtering accuracy can be 0.1-0.5 microns.
The disclosure third aspect：The ink that a kind of use disclosure first aspect provided is provided to carry out making flexible organic
The method of photovoltaic film device cushion, including：Make ink film；Wherein, it is described make ink film mode be selected from
At least one of inkjet printing, silk-screen printing, spin coating or blade coating；Heat cross-linking is carried out to gained ink film.
According to the third aspect of the disclosure, cushion refers to active layer in thin film electronic device (luminescent layer) between electrode
That layer or several layers of, anode buffer layer and cathode buffer layer can be divided into, main function is transmission electronics or hole.
According to the third aspect of the disclosure, if making ink film by scratching, change concentration and blade coating condition is (such as fast
Degree, baseplate temp, blade coating height etc.) it can obtain the ink film that thickness is 100nm-2 μm；If it is thin to make ink by spin coating
Film, changes concentration and spin coating rotating speed can obtain the ink film that thickness is 50-300nm.
According to the third aspect of the disclosure, it can adopt and cushion, method are prepared by the ink of the disclosure in various manners
Difference, the thickness of film is also different.In order to reach realized in the case of without mask plate cushion freely pattern prepare
Purpose, the mode of the making ink film is preferably inkjet printing or silk-screen printing, more preferably lasting inkjet printing, spray
Voltage when black is preferably more than 20V, sprays film thickness and is generally 300nm-1 μm.
According to the third aspect of the disclosure, heat cross-linking is well-known to those skilled in the art, and the disclosure is preferably relatively low
At a temperature of carry out, for example, the temperature of the heat cross-linking be 100-150 DEG C, the time is 30-60min.The disclosure only needs to heating
Remove after solvent, the heating short period can just reach good cross-linking effect, it is not necessary in vacuum drying chamber, nitrogen glove box
Etc. removing excess of solvent in particular/special requirement environment, it is not necessary to locate after being carried out under the light conditions such as infrared lamp, uviol lamp and laser
Reason.
There is provided a kind of flexible organic photovoltaic of making provided by the disclosure third aspect is thin for disclosure fourth aspect
Flexible organic photovoltaic thin-film device cushion made by the method for membrane module cushion.
According to the fourth aspect of the disclosure, the mode according to inkjet printing or silk-screen printing prepares cushion, the disclosure
The pattern for the cushion that fourth aspect is provided can with unrestricted choice, pattern accuracy and definition ratio in the prior art by spin coating or
Cushion prepared by knife coating procedure is more preferable.
In addition to preparing cushion, ink described in the disclosure can also make as coating outside cross-linking agent in paint coating
With can be also used for preparing the crosslinkable semiconductor material thin film in wearable device.
The disclosure will be further illustrated by embodiment below, but the disclosure is not therefore any way limited.
Unless otherwise specified, disclosure agents useful for same is commercially available, and commercial grades difference does not influence to use.In the embodiment of the present disclosure
Ink viscosity is tested by the portable viscosity apparatus of U.S. Rheosense microVISC, and surface tension is full-automatic using BZY-101
Surface tension instrument is tested by platinum plate method, and test temperature is 20 DEG C.
Embodiment 1
Weigh 70mg poly- (4-Vinyl phenol) and 50mg poly- (melamino-formaldehyde) and be transferred in 5mL reagent bottles A, measure
1mL ethanol is taken to add in reagent bottle A, stirring and dissolving.The ZnO (particle diameter is less than 10nm) for weighing 35mg is placed in reagent bottle, is measured
1mL ethanol is added in reagent bottle B, ultrasonic disperse 10min under the conditions of 40kHz.Solution in reagent bottle A and reagent bottle B is pressed into body
Product compares 1:10 are mixed, ultrasonic 5min, are then filtered using 0.22 μm of filtering head, are obtained ink, concrete composition is shown in Table 1.
Ink is fitted into print cartridge, can be stablized with ink-jet printer and spray ink film, (120 DEG C) can after heat cross-linking
To form fine and close crosslinked film, it can play a part of stopping upper strata ink bleed, the specific performance of ink is shown in Table 2, use
The cushion that the ink makes can reach the standard that uses, and can not only obstruct the infiltration of silver inks water but also can transmit electronics.
Embodiment 2-7
Embodiment 2-7 preparation process is substantially the same manner as Example 1, and concrete composition is shown in Table 1, and the specific performance of ink is shown in Table
2, the cushion that the ink prepared using embodiment 2-7 is made can reach the standard that uses, and can both obstruct the infiltration of silver inks water
Electronics can be transmitted again.
The preferred embodiment of the disclosure described in detail above, still, the disclosure are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the disclosure, a variety of simple variants can be carried out with technical scheme of this disclosure, this
A little simple variants belong to the protection domain of the disclosure.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the disclosure to it is various can
The combination of energy no longer separately illustrates.
In addition, can also be combined between a variety of embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought, it should equally be considered as disclosure disclosure of that.
Table 1
Table 2
| Embodiment | Viscosity, centipoise | Surface tension, dynes per centimeter | Ink-jet situation |
| Embodiment 1 | 4.08 | 23.6 | Well |
| Embodiment 2 | 8.99 | 24.3 | Well |
| Embodiment 3 | 12.64 | 25.5 | Well |
| Embodiment 4 | 9.72 | 23.5 | Well |
| Embodiment 5 | 5.63 | 23.6 | Well |
| Embodiment 6 | 13.02 | 24.4 | Well |
| Embodiment 7 | 11.46 | 25.3 | Well |
Claims (16)
1. a kind of ink for being used to make flexible organic photovoltaic thin-film device cushion, including：
Poly- (4-Vinyl phenol), poly- (melamino-formaldehyde), nano zine oxide and organic solvent；
Wherein, in the ink poly- (4-Vinyl phenol) concentration be 5-10mg/mL, poly- (melamino-formaldehyde) it is dense
Spend for 2-10mg/mL, the nano oxidized zinc concentration is 10-70mg/mL.
2. ink according to claim 1, wherein, the organic solvent be selected from ethanol, propylene glycol methyl ether acetate or
At least one of dibutyl carbonate.
3. ink according to claim 1 or 2, wherein, the organic solvent is ethanol and/or propylene glycol monomethyl ether acetic acid
Ester.
4. ink according to claim 1, wherein, additive of the ink also containing 1-5 weight %, the additive
For selected from least one of ethylene glycol, isopropanol or glycerine.
5. ink according to claim 1, wherein, the particle diameter of the nano zine oxide is less than 10nm.
6. a kind of preparation method for being used to make the ink of flexible organic photovoltaic thin-film device cushion, including：
Poly- (4-Vinyl phenol), poly- (melamino-formaldehyde) and nano zine oxide are mixed with organic solvent, ink is obtained；
Wherein, in the ink poly- (4-Vinyl phenol) concentration be 5-10mg/mL, poly- (melamino-formaldehyde) it is dense
Spend for 2-10mg/mL, the nano oxidized zinc concentration is 10-70mg/mL.
7. preparation method according to claim 6, wherein, the organic solvent is selected from ethanol, propylene glycol monomethyl ether acetic acid
At least one of ester or dibutyl carbonate.
8. the preparation method according to claim 6 or 7, wherein, the organic solvent is ethanol and/or propylene glycol monomethyl ether vinegar
Acid esters.
9. preparation method according to claim 6, wherein, additive of the ink also containing 1-5 weight % is described to add
Plus agent is selected from least one of ethylene glycol, isopropanol or glycerine.
10. preparation method according to claim 6, wherein, the particle diameter of the nano zine oxide is less than 10nm.
11. preparation method according to claim 6, wherein, it is described by poly- (4-Vinyl phenol), poly- (melamine first
Aldehyde) and nano zine oxide mixed with organic solvent, the step of obtaining ink includes：
Poly- (4-Vinyl phenol) and poly- (melamino-formaldehyde) is mixed with a part of organic solvent, the first mixed liquor is obtained；
Nano zine oxide is dispersed in another part organic solvent, the second mixed liquor is obtained；
First mixed liquor and the second mixed liquor are mixed, ink is obtained；Wherein, first mixed liquor and the second mixed liquor
Volume ratio be 1：(8-12).
12. preparation method according to claim 6, methods described also includes：By poly- (4-Vinyl phenol), poly- (trimerization
Cyanamide formaldehyde) and nano zine oxide mixed with organic solvent after successively carry out ultrasound and filtering, obtain the ink.
13. the ink in a kind of use claim 1-5 described in any one makes flexible organic photovoltaic thin-film device cushion
Method, including：
Make ink film；Wherein, the mode for making ink film is selected from inkjet printing, silk-screen printing, spin coating or scraped
At least one of apply；
Heat cross-linking is carried out to gained ink film.
14. the method according to claim 13 for making flexible organic photovoltaic thin-film device cushion, wherein, it is described to make
The mode of ink film is inkjet printing or silk-screen printing.
15. the method according to claim 13 for making flexible organic photovoltaic thin-film device cushion, wherein, the heat is handed over
The temperature of connection is 100-150 DEG C, and the time is 30-60min.
16. made by the method for the flexible organic photovoltaic thin-film device cushion of making according to claim 13,14 or 15
Flexible organic photovoltaic thin-film device cushion.
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