CN108314927A - Buffer layer ink and preparation method thereof - Google Patents

Buffer layer ink and preparation method thereof Download PDF

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Publication number
CN108314927A
CN108314927A CN201810182607.4A CN201810182607A CN108314927A CN 108314927 A CN108314927 A CN 108314927A CN 201810182607 A CN201810182607 A CN 201810182607A CN 108314927 A CN108314927 A CN 108314927A
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Prior art keywords
ink
buffer layer
film
nano zine
zine oxide
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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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    • 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
    • C09D11/30—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
    • C09D11/03—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)
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  • 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 a kind of for making ink of flexible organic photovoltaic thin-film device buffer layer and preparation method thereof and application and buffer layer, the ink for making flexible organic photovoltaic thin-film device buffer layer includes epoxide-resin glue, nano zine oxide and organic solvent；There is the buffer layer that the disclosure provides electron transport property, the solvent of ink used will not destroy the active layer in photovoltaic device, and film can be crosslinked itself, and the ink sprayed afterwards will not permeate, and buffer layer will not be dissolved upper layer is heated.

Description

Buffer layer ink and preparation method thereof
Technical field
The disclosure relates to organic photovoltaic devices technical field, and in particular, to one kind is for making flexible organic photovoltaic film The ink and the preparation method and application thereof of device buffer layer, and the buffering that is prepared by the preparation method with the ink Layer.
Background technology
Compared with inorganic solar cell, organic photovoltaic (Organic Photovoltaic, OPV) device has cost It is low, thickness is thin, light weight, manufacturing process are simple, can make the advantages that large area flexible device, there is wide development and application Foreground, it has also become one of the study frontier of current new material and the most rich vigour and vitality of new energy field.
For preparation process, industrially vacuum steaming is mostly used using the preparation process of more inorganic photovoltaic device at present Plating method, vacuum vapour deposition has equipment, technique harsher requirement, and vapor deposition requires the heat resistance of base material with caking property, One-component can only be deposited during vapor deposition in the same period.And organic photovoltaic devices, in preparation process, organic material can To be dissolved in solvent appropriate, operations, this mode and traditional evaporation coating method phases such as solution may be implemented to be coated under low temperature Than, have many advantages, such as that quick, energy saving, stock utilization is high, therefore, by solwution method carry out include silk-screen printing, it is inkjet deposited, The modes such as knife coating are one of current main improvement directions come the serialization large-scale production for implementing organic photovoltaic devices.
Solwution method prepares the main problem that multilayer device faces, and can be still dissolved in after functional material film forming Implement in the solvent in the preparation process of next tunic, so as to cause interpenetrating between adjacent membranes, thus cannot achieve The preparation of multilayer device or the multilayer device performance prepared become very poor.Cross-linking method (cross linking) is to solve at present Certainly one of the common approach of this problem.Crosslinking refers to that film surface or entirety crosslink under certain condition, forms net The process of shape high molecular material is just no longer dissolve in orthogonal to that solvent after film crosslinks, to solve multilayer film Between interpenetrate problem.
Organic photovoltaic devices generally have multilayered structure, include at least two electrodes and folder between two electrodes organic Semiconductor layer, organic semiconductor layer are active layers, convert light energy into electric energy.In order to reduce the energy level between electrode and active layer Difference improves efficiency of transmission of the electrons and holes between active layer and electrode, while reducing electronics and the recombination probability in hole, carries High photogenerated current, to improve the conversion efficiency of battery, in organic photovoltaic devices structure, usually between electrode and active layer Buffer layer is added.Currently, active layer and cushioning layer material or may be used based on high molecular material in organic photovoltaic devices Machine small molecule, or adulterate the high molecular material of organic and/or inorganic materials.
Crosslinkable cushioning layer material includes crosslinking agent and charge transport materials.Although can theoretically be dissolved in common solvent And realize that the substance of crosslinked action all can serve as buffer layer crosslinking agent, but the film prepared with solution methods in reality is big Multiselect metal oxide and this kind of material of sulfide are limited to charge transport properties requirement, cannot achieve preparation in the application Subsequent solution (ink) electrode, in addition, this kind of solution has generally required high-temperature process in use, in addition it is also adjoint Toxic products.And the another kind of polymer material being widely studied at present does not often have preferable crosslinking feature, can not stop The firmly infiltration of solution (ink) electrode, has little effect.
Therefore, the combination for finding suitable charge transport materials and crosslinking agent is the key that prepare cross-linking buffer layer.Closely Nian Lai, it has been reported that, material engineering institute of South China Science ＆ Engineering University is during solwution method prepares OLED element, using PFNR2 It is mixed with cross-linking buffer layer with ELC2500 type epoxy resin, relative to non-crosslinkable buffer layer, is had apparent preferable Effect.However, this buffer layer is although cross-linking, but blocking effect is limited, a small amount of solvent penetration is still had, to entire The performance of element has an impact, and the preparation of this buffer layer needs to carry out ultraviolet processing, and this processing is in addition to increasing cost Outside, can also uncertain influence be generated on the electric property of electrical equipment.
Therefore, during current solwution method prepares electrical equipment, it is badly in need of that a kind of cross-linking properties is good, and blocking effect is good, Simple novel buffer layer solution is post-processed, for inkjet printing prepares electrical equipment technique, which, which also needs to meet, beats The viscosity requirement of print machine ink.
Invention content
The purpose of the disclosure is：First aspect provides a kind of ink for making flexible organic photovoltaic thin-film device buffer layer Water, second aspect provide a kind of preparation method for making the ink of flexible organic photovoltaic thin-film device buffer layer, third party Face provides a kind of method that the ink provided using disclosure first aspect makes flexible organic photovoltaic thin-film device buffer layer, Fourth aspect provides a kind of side of the flexible organic photovoltaic thin-film device buffer layer of the making provided by the disclosure third aspect Flexible organic photovoltaic thin-film device buffer layer made by method, the disclosure are slow by being used to make flexible organic photovoltaic thin-film device The printing of buffer layer may be implemented in the ink for rushing layer.
To achieve the goals above, disclosure first aspect：It provides a kind of for making flexible organic photovoltaic thin-film device The ink of buffer layer, including：Epoxide-resin glue, nano zine oxide and organic solvent；Wherein, the epoxide-resin glue is a concentration of 2-60mg/mL, a concentration of 5-75mg/mL of the nano zine oxide.
Optionally, the organic solvent is selected from methanol, ethyl alcohol, butanol, isopropanol, glycol methyl ether acetate, the third two At least one of alcohol methyl ether acetate and dibutyl carbonate.
Optionally, additive of the ink also containing 1-5 weight %, the additive be selected from ethylene glycol, propylene glycol, At least one of butanediol and glycerine.
Optionally, the grain size of the nano zine oxide is less than 10nm.
Disclosure second aspect：A kind of ink for making flexible organic photovoltaic thin-film device buffer layer is provided, including： Epoxide-resin glue, nano zine oxide and organic solvent；Wherein, a concentration of 2-60mg/mL of the epoxide-resin glue, the nanometer A concentration of 5-75mg/mL of zinc oxide.
Optionally, the organic solvent is selected from methanol, ethyl alcohol, butanol, isopropanol, glycol methyl ether acetate, the third two At least one of alcohol methyl ether acetate and dibutyl carbonate.
Optionally, additive of the ink also containing 1-5 weight %, the additive be selected from ethylene glycol, propylene glycol, At least one of butanediol and glycerine.
Optionally, the grain size of the nano zine oxide is less than 10nm.
Optionally, described the step of mixing epoxide-resin glue and nano zine oxide with organic solvent, obtaining ink, includes： Epoxide-resin glue is mixed with a part of organic solvent, obtains the first mixed liquor；Nano zine oxide, which is dispersed in another part, to be had In solvent, the second mixed liquor is obtained；First mixed liquor and the second mixed liquor are mixed, ink is obtained；Wherein, described The volume ratio of one mixed liquor and the second mixed liquor is 1：(0.1-20).
Optionally, the method further includes：After epoxide-resin glue and nano zine oxide are mixed with organic solvent successively into Row ultrasound and filtering, obtain the ink.
The disclosure third aspect：A kind of flexible organic photovoltaic of ink making provided using disclosure first aspect is provided The method of thin-film device buffer layer, including：Make ink film；Wherein, the mode for making ink film is selected from ink-jet At least one of printing, silk-screen printing, spin coating and blade coating；Make gained ink film that heat cross-linking occur.
Optionally, the mode for making ink film is inkjet printing and/or silk-screen printing.
Optionally, the temperature of the heat cross-linking is 60-120 DEG C, time 30-120min.
Disclosure fourth aspect provides a kind of making flexibility organic photovoltaic film provided by the disclosure third aspect Flexible organic photovoltaic thin-film device buffer layer made by the method for device buffer layer.
The disclosure provides the ink for making flexible organic photovoltaic thin-film device buffer layer by the composition of allotment ink Water, and between luminescent layer and cathode print one layer of buffer layer, prepared buffer layer can not only obstruct the infiltration of silver ink water but also Electronics can be transmitted, to realize the inkjet printable of cathode, realizes that free patterning shines in the case of no mask plate.
In addition, the buffer layer thin film itself formed by ink-jet that the disclosure provides can be crosslinked, the ink sprayed afterwards is not It can permeate, buffer layer will not be dissolved upper layer is heated, and solvent used in buffer layer will not destroy organic photovoltaic Active layer in device.While playing the role of good electron-transport, solves inkjet printing and prepare organic photovoltaic devices Present between active layer and buffer layer, between buffer layer and electrode ink the problem of interpenetrating, improve organic light Lie prostrate the performance of device.
Other feature and advantage of the disclosure will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the disclosure is described in detail below.It should be understood that described herein specific Embodiment is only used for describing and explaining the disclosure, is not limited to the disclosure.
Disclosure first aspect：A kind of ink for making flexible organic photovoltaic thin-film device buffer layer is provided, including： Epoxide-resin glue, nano zine oxide and organic solvent；Wherein, epoxide-resin glue and nano zine oxide are mixed with organic solvent, Obtain ink；Wherein, a concentration of 2-60mg/mL of the epoxide-resin glue, a concentration of 5-75mg/ of the nano zine oxide mL；Preferably, a concentration of 5-40mg/mL of the epoxide-resin glue, a concentration of 10-50mg/mL of the nano zine oxide.
According to the disclosure in a first aspect, in order to realize prepared by the whole soln of OPV devices, even prepared by inkjet printing, The disclosure is prepared for a kind of organic buffer layer ink orthogonal with active layer solvent, the ink mainly by conductor oxidate and Thermally cross-linkable polymer composition can make ink that can completely cut off upper layer after film forming molten by adding other additives in addition The infiltration of liquid, while there is certain electron transport property, in use, whether pass through spin coating, blade coating, silk-screen printing and ink-jet Printing etc. can good filming.
According to the disclosure in a first aspect, organic solvent is well-known to those skilled in the art, for dissolving poly- (4- second Alkenyl phenol), poly- (melamino-formaldehyde) and dispersion nano zine oxide, generally using boiling point in 200 DEG C of organic solvents below, Such as can be selected from methanol, ethyl alcohol, butanol, isopropanol, glycol methyl ether acetate, propylene glycol methyl ether acetate At least one of (Propylene Glycol Methyl Ether Acetate, PGMEA) and dibutyl carbonate.
According to the disclosure in a first aspect, epoxide-resin glue is a kind of common casting glue, very soluble in alcohol reagent In, film prepared by mixed solution can self-crosslinking, so as to the infiltration of effectively blocking electrode ink.
According to the disclosure in a first aspect, the ink can also be containing the additive of 1-5 weight %, the additive can Think that, selected from least one of ethylene glycol, propylene glycol, butanediol and glycerine, additive is used to improve viscosity and the surface of ink Tension is conducive to ink and forms film, and also has 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 described nano oxidized in order to obtain better dispersion effect as the electron transfer layer between active layer and electrode The grain size of zinc is preferably smaller than 10nm.
It is further excellent according to the disclosure in a first aspect, the range of viscosities of disclosure ink is preferably 2-30 centipoises (CPS) 3-20 centipoises are selected as, surface tension is preferably 10-60 dynes per centimeters2(dynes/cm2), further preferably 20-50 dynes/li Rice2。
Disclosure second aspect：A kind of preparation for making the ink of flexible organic photovoltaic thin-film device buffer layer is provided Method, including：Epoxide-resin glue, nano zine oxide and organic solvent；Wherein, by epoxide-resin glue and nano zine oxide with it is organic Solvent mixes, and obtains ink；Wherein, a concentration of 2-60mg/mL of the epoxide-resin glue, the nano zine oxide it is a concentration of 5-75mg/mL；Preferably, a concentration of 5-40mg/mL of the epoxide-resin glue, a concentration of 10- of the nano zine oxide 50mg/mL。
According to the second aspect of the disclosure, organic solvent is well-known to those skilled in the art, for dissolving asphalt mixtures modified by epoxy resin Fat glue and dispersion nano zine oxide generally using boiling point in 200 DEG C of organic solvents below, such as can be selected from methanol, second Alcohol, butanol, isopropanol, glycol methyl ether acetate, propylene glycol methyl ether acetate (Propylene Glycol Methyl At least one of Ether Acetate, PGMEA) and dibutyl carbonate.
According to the disclosure in a first aspect, epoxide-resin glue is a kind of common casting glue, it is easily dissolved into alcohol reagent In the middle, the film that prepared by mixed solution can self-crosslinking, so as to the infiltration of effectively blocking electrode ink.
According to the second aspect of the disclosure, the ink can also be containing the additive of 1-5 weight %, and the additive can Think that, selected from least one of ethylene glycol, propylene glycol, butanediol and glycerine, additive is used to improve viscosity and the surface of ink Tension is conducive to ink and forms film, and also has 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 described nano oxidized in order to obtain better dispersion effect as the electron transfer layer between active layer and electrode The grain size of zinc is preferably smaller than 10nm.
It is described to mix epoxide-resin glue and nano zine oxide with organic solvent according to the second aspect of the disclosure, it obtains The step of ink may include：Epoxide-resin glue is mixed with a part of organic solvent, obtains the first mixed liquor；It will be nano oxidized Zinc is dispersed in another part organic solvent, obtains the second mixed liquor；First mixed liquor and the second mixed liquor are mixed, obtained To ink；Wherein, the volume ratio of first mixed liquor and the second mixed liquor is 1：(0.1-20).Matched respectively using this kind of mode The first mixed liquor and the second mixed liquor are made, the first mixed liquor and the second mixed liquor can be carried out placing for a long time and when in use It is allocated as needed.
According to the second aspect of the disclosure, the method can also include：Epoxide-resin glue and nano zine oxide with it is organic Ultrasound and filtering are carried out successively after solvent mixing, obtain the ink.It is ultrasonically treated and filtration treatment is those skilled in the art It is known, it is ultrasonically treated for each component in dispersible ink, reduces precipitation, frequency can be 10-60kHz, and the time can be with For 5-30min；Filtration treatment is used to filter the sediment fraction in ink, prevents printer head to be blocked and improves printing effect Fruit, filtering accuracy can be 0.1-0.5 μm.
The disclosure third aspect：A kind of flexible organic photovoltaic of ink making provided using disclosure first aspect is provided The method of thin-film device buffer layer, including：Make ink film；Wherein, the mode for making ink film is selected from ink-jet At least one of printing, silk-screen printing, spin coating and blade coating；Make gained ink film that heat cross-linking occur.
According to the third aspect of the disclosure, buffer layer refers in thin film electronic device, that between active layer and electrode Layer is several layers of, can be divided into anode buffer layer and cathode buffer layer, and main function is transmission electronics or hole.
According to the third aspect of the disclosure, if by blade coating make ink film, change concentration and blade coating condition (such as speed Degree, baseplate temp, blade coating height etc.) ink film that thickness is 100nm-2 μm can be obtained；If it is thin to make ink by spin coating Film, changes concentration and the ink film that thickness is 50-300nm can be obtained in spin coating rotating speed.
According to the third aspect of the disclosure, various modes may be used and prepare buffer layer using the ink of the disclosure, according to Method is different, and the thickness of film is also different.Realize that buffer layer freely patterns system in the case of no mask plate to realize Standby, the mode for making ink film is preferably inkjet printing and/or silk-screen printing, more preferably lasting inkjet printing, Voltage when ink-jet is preferably more than 20V, and sprayed film thickness is generally 100nm-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 60-120 DEG C, time 30-120min.The disclosure only needs to heat After removing solvent, the heating short period can reach good cross-linking effect, need not be in vacuum drying chamber, nitrogen glove box Etc. remove excess of solvent in particular/special requirements environment, after need not being carried out under the light conditions such as infrared lamp, ultraviolet lamp and laser Reason, simplifies aftertreatment technology.
Disclosure fourth aspect：A kind of making flexibility organic photovoltaic thin-film device that the disclosure third aspect is provided is provided Flexible organic photovoltaic thin-film device buffer layer made by the method for buffer layer.
According to the fourth aspect of the disclosure, buffer layer is prepared according to the mode of inkjet printing or silk-screen printing, then this public affairs The pattern for opening the buffer layer of fourth aspect offer can be with unrestricted choice, pattern accuracy and the existing spin coating of clarity ratio and knife coating procedure The active layer of preparation is more preferable.
Other than preparing buffer layer, the ink of the disclosure can also be used as rustproof lacquer crosslinking agent application in paint coating, It can also be used to prepare crosslinkable semiconductor material thin film in wearable device.
It will further illustrate the disclosure 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.
Embodiment 1
Epoxide-resin glue 90mg is weighed, and is added in 5mL reagent bottles A, 1mL isopropanols is measured and is added in reagent bottle A, stir Mix dissolving.It weighs 30mg ZnO (grain size is less than 10nm) to be placed in reagent bottle, measures 1mL isopropanols and be added in reagent bottle B, Ultrasonic disperse 5-30min under the conditions of 10-60kHz.By the solution in reagent bottle A and reagent bottle B by volume 1:10 are mixed, Then ultrasonic 5min uses 0.22 μm of filtering head to filter, obtains ink, concrete composition is shown in Table 1.
Ink is fitted into print cartridge, ejection ink film can be stablized with ink-jet printer, at 120 DEG C after heat cross-linking Fine and close crosslinked film can be formed, can play the role of stopping that upper layer ink bleed, specific inkjet performance are shown in Table 2, use The buffer layer that the ink makes can reach the infiltration that can not only obstruct silver ink water using standard but also can transmit electronics.
Embodiment 2-8
The preparation process of embodiment 2-8 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 buffer layer that the ink prepared using embodiment 2-8 is made can reach using standard, can both obstruct the infiltration of silver ink water Electronics can be transmitted again.
The preferred embodiment of the disclosure described in detail above, still, the disclosure is not limited in the above embodiment Detail can carry out a variety of simple variants to the technical solution of the disclosure in the range of the technology design of the disclosure, this A little simple variants belong to the protection domain of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, 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, arbitrary combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally Disclosed thought equally should be considered as disclosure disclosure of that.
1 ink composition table of table
2 ink viscosity of table and surface tension table
Embodiment Viscosity, centipoise Surface tension, dynes per centimeter2
Embodiment 1 4.22 23.8
Embodiment 2 4.08 24.2
Embodiment 3 6.66 25.5
Embodiment 4 5.12 23.7
Embodiment 5 7.85 24.6
Embodiment 6 11.02 24.5
Embodiment 7 3.86 25.3
Embodiment 8 7.32 24.8

Claims (14)

1. a kind of ink for making flexible organic photovoltaic thin-film device buffer layer, including：
Epoxide-resin glue, nano zine oxide and organic solvent；Wherein,
A concentration of 2-60mg/mL of the ink epoxy resin glue, a concentration of 5-75mg/mL of the nano zine oxide.
2. ink according to claim 1, wherein the organic solvent is selected from methanol, ethyl alcohol, butanol, isopropanol, second At least one of glycol methyl ether acetate, propylene glycol methyl ether acetate and dibutyl carbonate.
3. ink according to claim 1, wherein additive of the ink also containing 1-5 weight %, the additive To be selected from least one of ethylene glycol, propylene glycol, butanediol and glycerine.
4. ink according to claim 1, wherein the grain size of the nano zine oxide is less than 10nm.
5. a kind of preparation method for making the ink of flexible organic photovoltaic thin-film device buffer layer, including：
Epoxide-resin glue and nano zine oxide are mixed with organic solvent, obtain ink；
Wherein, a concentration of 2-60mg/mL of the ink epoxy resin glue, a concentration of 5-75mg/ of the nano zine oxide mL。
6. preparation method according to claim 5, wherein the organic solvent is selected from methanol, ethyl alcohol, butanol, isopropyl At least one of alcohol, glycol methyl ether acetate, propylene glycol methyl ether acetate and dibutyl carbonate.
7. preparation method according to claim 5, wherein additive of the ink also containing 1-5 weight %, it is described to add It is selected from least one of ethylene glycol, propylene glycol, butanediol and glycerine to add agent.
8. preparation method according to claim 5, wherein the grain size of the nano zine oxide is less than 10nm.
9. preparation method according to claim 5, wherein described by poly- (4-Vinyl phenol), poly- (melamine first Aldehyde) and nano zine oxide the step of being mixed with organic solvent, obtaining ink include：
Epoxide-resin glue is mixed with a part of organic solvent, obtains the first mixed liquor；
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：(0.1-20).
10. preparation method according to claim 5, the method further include：By epoxide-resin glue and nano zine oxide with Ultrasound and filtering are carried out successively after organic solvent mixing, obtain the ink.
11. a kind of ink using described in any one of claim 1-4 makes flexible organic photovoltaic thin-film device buffer layer Method, including：
Make ink film；Wherein, the mode for making ink film is selected from inkjet printing, silk-screen printing, spin coating and to scrape At least one of apply；
Make gained ink film that heat cross-linking occur.
12. the method according to claim 11 for making flexible organic photovoltaic thin-film device buffer layer, wherein the making The mode of ink film is inkjet printing and/or silk-screen printing.
13. the method according to claim 11 for making flexible organic photovoltaic thin-film device buffer layer, wherein the heat is handed over The temperature of connection is 60-120 DEG C, time 30-120min.
14. the flexible organic photovoltaic thin-film device buffer layer of making according to any one of claim 11,12 or 13 Flexible organic photovoltaic thin-film device buffer layer made by method.
CN201810182607.4A 2017-08-09 2018-03-06 Buffer layer ink and preparation method thereof Withdrawn CN108314927A (en)

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