CN108550697A - Flexible organic solar batteries and its all print preparation method - Google Patents

Flexible organic solar batteries and its all print preparation method Download PDF

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Publication number
CN108550697A
CN108550697A CN201810182427.6A CN201810182427A CN108550697A CN 108550697 A CN108550697 A CN 108550697A CN 201810182427 A CN201810182427 A CN 201810182427A CN 108550697 A CN108550697 A CN 108550697A
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solution
layer
poly
organic solar
solar batteries
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李胜夏
王家林
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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    • 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
    • H10K30/451—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a metal-semiconductor-metal [m-s-m] structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0023—Digital printing methods characterised by the inks used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/36—Backcoats; Back layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Electromagnetism (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Photovoltaic Devices (AREA)
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Abstract

The present invention relates to area of solar cell, specifically, provide a kind of flexible organic solar batteries and its all print preparation method, pectination silver electrode is formed by printing silver conductive ink on a flexible substrate, and use the transport layer of high conductivity, the absorption loss water for reducing light reduces dependence of the battery device to ITO electrode；Dispensing or printing conducting polymer blend solution on active layer, form the top electrode layer of hole transport and electrode blending, or print silver conductive ink in the second transport layer and form pectination silver electrode, destruction of the solvent to active layer film is reduced, the yield rate of flexible organic solar batteries is improved.

Description

Flexible organic solar batteries and its all print preparation method
Technical field
The present invention relates to area of solar cell, and in particular to it is a kind of flexibility organic solar batteries and its all print prepare Method.
Background technology
Organic solar batteries are mainly the material using the organic matter with photo-sensitive characteristic as semiconductor, with photovoltaic effect And generate voltage and form electric current, realize the effect of solar power generation.Organic solar batteries can be divided into list according to device architecture Matter junction structure, heterojunction structure etc..The photoelectric conversion process of organic solar batteries is usually after battery absorbs light, in donor or Generate exciton in receptor, exciton diffusion to give, acceptor interface layer, exciton splits into free carrier in boundary layer, i.e., electronics and Hole, then electrons and holes be mutually transmitted to corresponding electrode through respective main body respectively and form photoelectric current.
Organic solar batteries are formed generally by preparations such as vacuum evaporation technology, inkjet printing technologies.Wherein, vacuum Evaporation coating technique is that substance to be filmed is placed in vacuum to be evaporated or distil, and is allowed to the mistake being precipitated in workpiece or substrate surface Journey.Inkjet printing is moved on processed support after drawing probe reagent from microwell plate using nozzle, by temperature-sensitive or Drop is ejected into support surface by the power of the forms injector such as acoustic control.
When preparing organic solar batteries, vacuum evaporation technology, inkjet printing technology all have some disadvantages.Its In, vacuum evaporation technology needs expensive equipment, and preparation time is long.And inkjet printing usually needs to ensure ink-jet effect Some such as naphthanes, ethylene glycol high boiling solvent are added, these solvents can be in printing and last handling process to active layer Film, which generates, greatly to be destroyed, and the yield rate of organic solar batteries is reduced.It is prepared by vacuum evaporation technology and inkjet printing technology Top electrode it is opaque, in order to ensure the effective absorption of donor and receptor to light, organic solar batteries are to indium tin oxide transparent The dependence of hearth electrode is very big, and the patterned process of flexible substrates such as PET/ITO is complicated, is unfavorable for the connection in series-parallel of electronic device It uses, it is industrially prepared to be also unfavorable for large area.
Invention content
In view of this, a kind of flexible organic solar batteries of present invention offer and its all print preparation method, can reduce Organic solar batteries reduce the destruction to active layer film to the dependence of ITO electrode, improve organic solar batteries at Product rate.
The disclosure in a first aspect, provide a kind of all print preparation method of flexible organic solar batteries, including：
The first transmission layer material is printed or scratched in the flexible substrates with hearth electrode, forms the first transport layer；
Conjugated polymer blend solution is scratched on the surface of first transport layer, forms active layer；
Form top electrode layer；
Wherein, the formation top electrode layer includes：
Surface dispensing in the active layer or printing conducting polymer/metal nano dispersion liquid composite solution, form top Electrode layer；
Alternatively,
The all print preparation method further includes：
On the surface of the active layer, the second transmission of blade coating layer material, forms the second transport layer；
Wherein, the formation top electrode layer includes：
Top electrode layer is formed in the printout surface silver conductive ink of second transport layer.
Preferably, the flexible substrates with hearth electrode are polyethylene terephthalate-tin indium oxide (Polyethylene terephthalate-ITO, PET-ITO), polyethylene naphthalate-tin indium oxide (Polyethylene naphthalate-ITO, PEN-ITO) or polyimides-tin indium oxide (Polyimide-ITO, PI- ITO) one kind in flexible substrates.
Preferably, the flexible substrates with hearth electrode include：
Silver-colored dielectric layer conductive ink is printed on a flexible substrate forms pectination hearth electrode.
Preferably, the conducting polymer blend solution includes electrode material and third transmission layer material；
Wherein, the electrode material is the blend of silver powder, nano silver wire solution or silver powder and nano silver wire, the third Transmission layer material is poly- 3,4-ethylene dioxythiophene：Poly styrene sulfonate (Poly (3,4- ethylenedioxythiophene):Poly (styrenesulfonate), PEDOT:PSS) solution.
Preferably, the electrode material is silver powder, silver powder 5-20mg, PEDOT:PSS solution is 1-2mL；Alternatively,
The electrode material is nano silver wire solution, and nano silver wire solution is 0.1-0.5mL, PEDOT:PSS solution is 1- 2mL；Alternatively,
The electrode material is the blend of silver powder and nano silver wire, and the blend of silver powder and nano silver wire is 5-20mg, PEDOT:PSS solution is 1-2mL, wherein the mass ratio of the silver powder and nano silver wire is 1:1-4:1.
Preferably, described second layer material is transmitted as electron transfer layer solution, including nano zine oxide (ZnO) dispersion liquid, Polyethoxy aziridine (Polyethylenimine ethoxylated, PEIE) solution, polyetherimide (Polyetherimide, PEI) solution, PFN solution, ZnO-PEIE composite solutions, ZnO-PEI composite solutions.
Preferably, a concentration of 10-20mg/mL of the nano zinc oxide fluid dispersion.It PEIE, PEI and PFN and its is compounding A concentration of 0.02-0.20mg/mL in solution.The solvent or dispersant of different solutions are methanol, ethyl alcohol, isopropanol, butanol, third Ketone.Solution stabilizer or additive are chloroform, toluene, formic acid, percent by volume 0.5-5%.
Preferably, forming top electrode layer in the printout surface silver dielectric layer conductive ink of second transport layer includes：
Pectination top electrode layer is formed in the printout surface silver dielectric layer conductive ink of second transport layer.
Preferably, the conjugated polymer blend solution is made of donor, receptor and solvent.
Preferably, donor be PffBT4T-2OD (PCE11), P3HT, PTB7, PTB7-Th, DPP-DTT, PDPP4T, PBDB-T (PCE12), PBDTT-DPP, PDPP4T-2F, PBDTTPD, PBDTTTPD, PJ61, PJ71, TQ1 or PBDD4T-2F are total It is one or more in conjugated polymer.
Preferably, one kind of receptor PC60BM, PC70BM, bis-PCBM, ICBA, C60-N, ITIC, N2200 polymer Or it is a variety of.
Preferably, solvent is chloroform, chlorobenzene, toluene, dichloro-benzenes, dimethylbenzene, trimethylbenzene, methyl phenyl ethers anisole, diphenyl ether, tetrahydrochysene furan It mutters, one kind in naphthane or its arbitrary blend solvent.
Preferably, donor is 1 with the mass ratio that is blended of receptor:0.5-1:4.0, a concentration of 8-30mg/mL of blend solution.
Preferably, the first transmission layer material is nano zine oxide (ZnO) dispersion liquid, polyethoxy aziridine (Polyethylenimine ethoxylated, PEIE) solution, polyetherimide (Polyetherimide, PEI) solution, PFN solution, ZnO-PEIE composite solutions, ZnO-PEI composite solutions or poly- 3,4-ethylene dioxythiophene：Poly styrene sulfonate (Poly(3,4-ethylenedioxy thioph-ene):Poly (styrene sulfonate), PEDOT:PSS it) is blended molten Liquid.
Preferably, a concentration of 10-20mg/mL of the nano zinc oxide fluid dispersion.It PEIE, PEI and PFN and its is compounding A concentration of 0.02-0.20mg/mL in solution.The solvent or dispersant of different solutions are methanol, ethyl alcohol, isopropanol, butanol, third Ketone.Solution stabilizer or additive are chloroform, toluene, formic acid, percent by volume 0.2-5%.
Second aspect provides a kind of flexible organic solar batteries, including：
Flexible substrates；
First transport layer is set in the flexible substrates, is formed by printing or scratching the first transmission layer material；
Active layer is set in first transport layer, is formed by scratching conjugated polymer blend solution；
Top electrode layer is set on the active layer, multiple by dispensing or printing conducting polymer/metal nano dispersion liquid Solution is closed to be formed；
Wherein, the conducting polymer/metal nano dispersion liquid composite solution includes electrode material and third transport layer material Material, wherein the electrode material is the blend of silver powder, nano silver wire solution or silver powder and nano silver wire, the third transmission Layer material is poly- 3,4-ethylene dioxythiophene：Poly styrene sulfonate (Poly (3,4-ethylenedioxythiophene): Poly (styrenesulfonate), PEDOT:PSS) solution.
Preferably, the flexible substrates are polyethylene terephthalate-tin indium oxide (Polyethylene Terephthalate-ITO, PET-ITO) flexible substrates.
Preferably, the flexible substrates include pectination hearth electrode, are formed by printing silver conductive ink.
Preferably, the first transmission layer material is nano zine oxide (ZnO) dispersion liquid, polyethoxy aziridine (Polyethylenimine ethoxylated, PEIE) solution, polyetherimide (Polyetherimide, PEI) solution, PFN solution, ZnO-PEIE composite solutions, ZnO-PEI composite solutions or poly- 3,4-ethylene dioxythiophene：Poly styrene sulfonate (Poly(3,4-ethylenedioxy thioph-ene):Poly (styrene sulfonate), PEDOT:PSS it) is blended molten Liquid.
Preferably, a concentration of 10-20mg/mL of the nano zinc oxide fluid dispersion.It PEIE, PEI and PFN and its is compounding A concentration of 0.02-0.20mg/mL in solution.The solvent or dispersant of different solutions are methanol, ethyl alcohol, isopropanol, butanol, third Ketone.Solution stabilizer or additive are chloroform, toluene, formic acid, percent by volume 0.2-5%.
Preferably, the conjugated polymer blend solution is made of donor, receptor and solvent.
Preferably, donor be PffBT4T-2OD (PCE11), P3HT, PTB7, PTB7-Th, DPP-DTT, PDPP4T, PBDB-T (PCE12), PBDTT-DPP, PDPP4T-2F, PBDTTPD, PBDTTTPD, PJ61, PJ71, TQ1, PBDD4T-2F are total Conjugated polymer it is one or more.
Preferably, one kind of receptor PC60BM, PC70BM, bis-PCBM, ICBA, C60-N, ITIC, N2200 polymer Or it is a variety of.
Preferably, solvent is chloroform, chlorobenzene, toluene, dichloro-benzenes, dimethylbenzene, trimethylbenzene, methyl phenyl ethers anisole, diphenyl ether, tetrahydrochysene furan It mutters, one kind in naphthane or its arbitrary blend solvent.
Preferably, donor is 1 with the mass ratio that is blended of receptor:0.5-1:4.0, a concentration of 8-30mg/mL of blend solution.
The third aspect provides a kind of flexible organic solar batteries, including：
Flexible substrates；
First transport layer is set in the flexible substrates, is formed by blade coating the first transmission layer material；
Active layer is set in first transport layer, is formed by scratching conjugated polymer blend solution；
Second transport layer is set on the active layer, is formed by blade coating the second transmission layer material；
Top electrode layer is set in second transport layer, and scheduled pattern is formed by printing silver conductive ink.
Preferably, the flexible substrates are PET, PEN, PI flexible substrates.
Preferably, the flexible substrates include pectination hearth electrode, are formed by printing silver conductive ink.
Preferably, the first transmission layer material is poly- 3,4-ethylene dioxythiophene：Poly styrene sulfonate (Poly (3, 4-ethylenedioxythioph-ene):Poly (styrene sulfonate), PEDOT:PSS) blend solution.
Preferably, the conjugated polymer blend solution is made of donor, receptor and solvent.
Preferably, donor be PffBT4T-2OD (PCE11), P3HT, PTB7, PTB7-Th, DPP-DTT, PDPP4T, PBDB-T (PCE12), PBDTT-DPP, PDPP4T-2F, PBDTTPD, PBDTTTPD, PJ61, PJ71, TQ1, PBDD4T-2F are total Conjugated polymer it is one or more.
Preferably, one kind of receptor PC60BM, PC70BM, bis-PCBM, ICBA, C60-N, ITIC, N2200 polymer Or it is a variety of.
Preferably, solvent is chloroform, chlorobenzene, toluene, dichloro-benzenes, dimethylbenzene, trimethylbenzene, methyl phenyl ethers anisole, diphenyl ether, tetrahydrochysene furan It mutters, one kind in naphthane or its arbitrary blend solvent.
Preferably, donor is 1 with the mass ratio that is blended of receptor:0.5-1:4.0, a concentration of 8-30mg/mL of blend solution.
Preferably, the second transmission layer material is nano zine oxide (ZnO) dispersion liquid, polyethoxy aziridine (Polyethylenimine ethoxylated, PEIE) solution, polyetherimide (Polyetherimide, PEI) solution, PFN solution, ZnO-PEIE composite solutions, ZnO-PEI composite solutions or poly- 3,4-ethylene dioxythiophene：Poly styrene sulfonate (Poly(3,4-ethylenedioxy thioph-ene):Poly (styrene sulfonate), PEDOT:PSS it) is blended molten Liquid.
Preferably, a concentration of 10-20mg/mL of the nano zinc oxide fluid dispersion.It PEIE, PEI and PFN and its is compounding A concentration of 0.02-0.20mg/mL in solution.The solvent or dispersant of different solutions are methanol, ethyl alcohol, isopropanol, butanol, third Ketone.Solution stabilizer or additive are chloroform, toluene, formic acid, percent by volume 0.2-5%.
The disclosure forms pectination silver electrode by printing silver conductive ink on a flexible substrate, and uses the biography of high conductivity Defeated layer reduces the absorption loss water of light, reduces dependence of the battery device to ITO electrode；Dispensing or printing on active layer Conducting polymer blend solution forms the top electrode layer of hole transport and electrode blending, or prints silver in the second transport layer and lead Electric ink forms pectination silver electrode, reduces destruction of the solvent to active layer film, improve flexible organic solar batteries at Product rate.
Description of the drawings
By referring to the drawings to the description of the embodiment of the present invention, the above and other purposes of the present invention, feature and Advantage will be apparent from, in the accompanying drawings：
Fig. 1 is the structural schematic diagram of the flexible organic solar batteries of first embodiment of the invention；
Fig. 2 is all print preparation method flow chart of the flexible organic solar batteries of first embodiment of the invention；
Fig. 3 is density of photocurrent-voltage curve of the flexible organic solar batteries of first embodiment of the invention；
Fig. 4 is the structural schematic diagram of the flexible organic solar batteries of second embodiment of the invention；
Fig. 5 is all print preparation method flow chart of the flexible organic solar batteries of second embodiment of the invention；
Fig. 6 is density of photocurrent-voltage curve of the flexible organic solar batteries of second embodiment of the invention；
Fig. 7 is the structural schematic diagram of the flexible organic solar batteries of third embodiment of the invention；
Fig. 8 is all print preparation method flow chart of the flexible organic solar batteries of third embodiment of the invention；
Fig. 9 is density of photocurrent-voltage curve one of the flexible organic solar batteries of third embodiment of the invention；
Figure 10 is density of photocurrent-voltage curve two of the flexible organic solar batteries of third embodiment of the invention；
Figure 11 is the structural schematic diagram of the flexible organic solar batteries of fourth embodiment of the invention；
Figure 12 is all print preparation method flow chart of the flexible organic solar batteries of fourth embodiment of the invention；
Figure 13 is density of photocurrent-voltage curve of the flexible organic solar batteries of fourth embodiment of the invention；
Figure 14 is the structural schematic diagram of the flexible organic solar batteries of fifth embodiment of the invention；
Figure 15 is all print preparation method flow chart of the flexible organic solar batteries of fifth embodiment of the invention；
Figure 16 is density of photocurrent-voltage curve of the flexible organic solar batteries of fifth embodiment of the invention.
Specific implementation mode
Below based on embodiment, present invention is described, but the present invention is not restricted to these embodiments.Under Text to the present invention datail description in, it is detailed to describe some specific detail sections.Do not have for a person skilled in the art The description of these detail sections can also understand the present invention completely.In order to avoid obscuring the essence of the present invention, well known method, mistake There is no narrations in detail for journey, flow, element and circuit.
In addition, it should be understood by one skilled in the art that provided herein attached drawing be provided to explanation purpose, and What attached drawing was not necessarily drawn to scale.
Unless the context clearly requires otherwise, "include", "comprise" otherwise throughout the specification and claims etc. are similar Word should be construed as the meaning for including rather than exclusive or exhaustive meaning；That is, being containing for " including but not limited to " Justice.
In the description of the present invention, it is to be understood that, term " first ", " second " etc. are used for description purposes only, without It can be interpreted as indicating or implying relative importance.In addition, in the description of the present invention, unless otherwise indicated, the meaning of " multiple " It is two or more.
Unless otherwise clearly defined and limited, the terms such as term " installation ", " connected ", " connection ", " fixation " should be done extensively Reason and good sense solution may be a detachable connection for example, it may be being fixedly connected, or integral；Can be mechanical connection, it can also It is electrical connection；Can be directly connected, can also indirectly connected through an intermediary, can be connection inside two elements or The interaction relationship of two elements, unless otherwise restricted clearly.For the ordinary skill in the art, Ke Yigen Understand the concrete meaning of above-mentioned term in the present invention according to concrete condition.
Embodiment one：
Fig. 1 is the structural schematic diagram of the flexible organic solar batteries of first embodiment of the invention.As shown in Figure 1, flexible Organic solar batteries include polyethylene terephthalate-tin indium oxide (Polyethylene terephthalate- ITO, PET-ITO) flexible substrates electrode 1, the first transport layer 2, active layer 3 and top electrode layer 4.Organic solar batteries absorb light Afterwards, light penetrates the first transport layer 2, and absorbing light by the material in active layer 3 generates exciton (electron-hole pair), and then exciton expands It is scattered in active layer material and splits into free carrier, i.e. electrons and holes on the interface of donor material and acceptor material.Then, Electrons and holes pass in respective main body phase (the donor phase of donor material and the receptor phase of acceptor material) through transport layer respectively Electrode is transported to, i.e. electronics is received through the first transport layer 2 by flexible substrates electrode 1, and hole is received by top electrode layer 4, most end form At photoelectric current.
PET-ITO flexible substrates electrode 1 is PET-ITO conductive membrane layers.PET-ITO refers to using magnetron sputtering technique, High-tech transparent indium tin oxide (ITO) conductive film coating and obtained through the high temperature anneal is sputtered on PET base material Product.The thickness of ito film layer is different, and the electric conductivity and light transmission of film are also different.In general, in identical process conditions In the case of PET base material identical with performance, ito film layer is thicker, and the sheet resistance of PET-ITO films is smaller, light transmission rate Also corresponding smaller.The resistance of the present embodiment PET-ITO substrates is 5-40 Ω/cm2, it is purchased from the limited public affairs of Shenzhen south China Xiang Cheng science and technology Department.Polyethylene terephthalate (PET) has good mechanical property, and impact strength is 3-5 times of other films, corrosion resistant The advantages that erosion, transparency is high.Tin indium oxide (ITO) is a kind of N-type oxide semiconductor, and ito thin film, that is, indium tin oxide is partly led Body transparent conductive film has good electric conductivity and the transparency.
First transport layer 2 is mainly used for transmitting electronics.First transport layer 2 on PET-ITO flexible substrates electrode 1 by beating Print or blade coating nano zinc oxide fluid dispersion, then anneal 10-30 minutes at 60-150 DEG C and are formed.Wherein, nano zine oxide point Dispersant in dispersion liquid is isopropanol and a small amount of stabilizer, a concentration of 10-20mg/mL.
Active layer 3 is set to the surface of the first transport layer 2, by scratching PTB7-Th on the surface of the first transport layer 2: ITIC blend solutions are formed.Active layer 3 can absorb sunlight.Scratch the PTB7-Th formed:ITIC blend solution layers need 80-130 DEG C is annealed 10-30 minutes.
Top electrode layer 4 is arranged on active layer 3, is formed by dispensing or printing conducting polymer blend solution.Conduction is poly- It includes electrode material and third transmission layer material to close object blend solution.Electrode material is silver powder or nano silver wire solution.Third passes Defeated layer material is poly- 3,4-ethylene dioxythiophene：Poly styrene sulfonate (Poly (3,4-ethylenedioxythiophene): Poly (styre nesulfonate), PEDOT:PSS) solution.When electrode material is silver powder, conducting polymer blend solution By the silver powder of 5-20mg, the PEDOT of 1-2mL:PSS solution is made；When electrode material is nano silver wire solution, conducting polymer Blend solution is by the nano silver wire solution of 0.1-0.5mL, the PEDOT of 1-2mL:PSS solution is made.PEDOT:PSS solution has It is highly conductive forthright.By dispensing or the above-mentioned conducting polymer blend solution of printing on active layer 3, anneal 30- at 70-130 DEG C 60 minutes, obtain the top electrode layer 4 that there is hole transport and electrode to be blended.Top electrode layer 4 can avoid being prepared separately hole transport Layer and electrode layer destroy the generation of active layer film twice.
The all print preparation method of the flexible organic solar batteries of the present embodiment is as shown in Fig. 2, prepared by all print Method includes：
Step S110, nano zinc oxide fluid dispersion is printed or scratched in PET-ITO flexible substrates, forms the first transmission Layer.
Step S120, PTB7-Th is scratched in first transport layer:ITIC blend solutions form active layer.
Step S130, on the active layer, dispensing or printing conducting polymer blend solution, form top electrode layer.
Conducting polymer blend solution includes electrode material and third transmission layer material.Wherein, electrode material 5-20mg Silver powder or 0.1-0.5mL nano silver wire solution.Third transmits the PEDOT that layer material is 1-2mL:PSS solution.By silver powder or PEDOT is added in nano silver wire solution:It is sufficiently stirred in PSS solution and PEDOT is made:PSS-Ag (powder) top electrode layers or PEDOT: PSS-Ag (nano wire) top electrode layer.
The flexible organic solar batteries completed will be prepared to be tested for the property, flexible organic solar batteries can be obtained Density of photocurrent-voltage (J-V) curve graph.Density of photocurrent-voltage of flexible organic solar batteries according to Fig.3, Curve can obtain being based on PEDOT:The open-circuit voltage of PSS-Ag (powder) top electrode layer is 0.48V, and short-circuit current density is 1.58mA/cm2, fill factor 27.9%, photoelectric conversion efficiency 0.21%；Based on PEDOT:The tops PSS-Ag (nano wire) electricity The open-circuit voltage of pole layer is 0.55V, short-circuit current density 3.79mA/cm2, fill factor 28.1%, photoelectric conversion efficiency It is 0.58%.
By the way that the third transmission layer material of flexible organic solar batteries is blended to obtain conducting polymer with electrode material Blend solution, and dispensing or printing conducting polymer blend solution on active layer, form the top of hole transport and electrode blending Electrode layer, avoid be prepared separately hole transmission layer and electrode layer to active layer film generation destroy twice.
Embodiment two：
Fig. 4 is the structural schematic diagram of the flexible organic solar batteries of second embodiment of the invention.As shown in figure 4, flexible Organic solar batteries include polyethylene terephthalate-tin indium oxide (Polyethylene terephthalate- ITO, PET-ITO) flexible substrates electrode 1, the first transport layer 2, active layer 3 and top electrode layer 4.Organic solar batteries absorb light Afterwards, light penetrates the first transport layer 2, and absorbing light by the material in active layer 3 generates exciton (electron-hole pair), and then exciton expands It is scattered in active layer material and splits into free carrier, i.e. electrons and holes on the interface of donor material and acceptor material.Then, Electrons and holes pass in respective main body phase (the donor phase of donor material and the receptor phase of acceptor material) through transport layer respectively Electrode is transported to, i.e. electronics is received through the first transport layer 2 by flexible substrates electrode 1, and hole is received by top electrode layer 4, most end form At photoelectric current.
PET-ITO flexible substrates electrode 1 is PET-ITO conductive membrane layers.PET-ITO refers to using magnetron sputtering technique, High-tech transparent indium tin oxide (ITO) conductive film coating and obtained through the high temperature anneal is sputtered on PET base material Product.The thickness of ito film layer is different, and the electric conductivity and light transmission of film are also different.In general, in identical process conditions In the case of PET base material identical with performance, ito film layer is thicker, and the sheet resistance of PET-ITO films is smaller, light transmission rate Also corresponding smaller.The resistance of the present embodiment PET-ITO substrates is 5-40 Ω/cm2, it is purchased from the limited public affairs of Shenzhen south China Xiang Cheng science and technology Department.Polyethylene terephthalate (PET) has good mechanical property, and impact strength is 3-5 times of other films, corrosion resistant The advantages that erosion, transparency is high.Tin indium oxide (ITO) is a kind of N-type oxide semiconductor, and ito thin film, that is, indium tin oxide is partly led Body transparent conductive film has good electric conductivity and the transparency.
First transport layer 2 is mainly used for transmitting electronics.First transport layer 2 on PET-ITO flexible substrates electrode 1 by scraping Polyethoxy aziridine (Polyethylenimine ethoxylated, PEIE) solution is applied to be formed.Wherein, by PEIE solution Then the first transport layer 2 formed is moved back by scratching PEIE solution on PET-ITO flexible substrates electrode 1 at 60-120 DEG C It is formed after 5-30 minutes fiery.Wherein, a concentration of 0.2-5wt% of PEIE solution, solvent are isopropanol.
Active layer 3 is set to the surface of the first transport layer 2, by scratching PTB7-Th on the surface of the first transport layer 2: ITIC blend solutions are formed.Active layer 3 can absorb sunlight, improve the photoelectric conversion efficiency of flexible organic solar batteries. Scratch the PTB7-Th formed:ITIC blend solution layers needs are annealed 10-30 minutes at 80-130 DEG C.PTB7-Th:ITIC is blended Solution is using PTB7-Th and ITIC as solute, is the mixed solution that solvent is formed with toluene, dimethylbenzene, trimethylbenzene etc..Wherein, The mass ratio of PTB7-Th and ITIC is 1:0.8-1:1.5, PTB7-Th:A concentration of 10-25mg/mL of ITIC blend solutions.
Top electrode layer 4 is arranged on active layer 3, is formed by dispensing or printing conducting polymer blend solution.Conduction is poly- It includes electrode material and third transmission layer material to close object blend solution, and electrode material is added in third transmission layer material, and is stirred It mixes 0.5-2 hours and is formed.Electrode material is silver powder.It is poly- 3,4-ethylene dioxythiophene that third, which transmits layer material,：Polystyrene sulphur Hydrochlorate (Poly (3,4-ethylenedioxy thiophene):Poly (styrenesulfonate), PEDOT:PSS) solution. The conducting polymer blend solution of the present embodiment is by the silver powder of 5-20mg, the PEDOT of 1-2mL:PSS solution is made.Wherein, PEDOT:PSS solution has highly conductive forthright.By dispensing or the above-mentioned conducting polymer blend solution of printing on active layer 3, It anneals 30-60 minutes at 70-130 DEG C, obtains the top electrode layer 4 that there is hole transport and electrode to be blended.Top electrode layer 4 can avoid Hole transmission layer and electrode layer is prepared separately to destroy the generation of active layer film twice.
The all print preparation method of the flexible organic solar batteries of the present embodiment is as shown in figure 5, prepared by all print Method includes：
Step S210, PEIE solution is scratched in PET-ITO flexible substrates, forms the first transport layer.
Step S220, PTB7-Th is scratched in first transport layer:ITIC blend solutions form active layer.
Step S230, on the active layer, dispensing or printing conducting polymer blend solution, form top electrode layer.
Conducting polymer blend solution is by the silver powder of 5-20mg and the PEDOT of 1-2mL:The stirring of PSS solution is made.
The flexible organic solar batteries completed will be prepared to be tested for the property, flexible organic solar batteries can be obtained Density of photocurrent-voltage (J-V) curve graph.Density of photocurrent-voltage of flexible organic solar batteries according to figure 6 Curve can obtain being based on PEDOT:The open-circuit voltage of PSS-Ag (powder) top electrode layer is 0.48V, and short-circuit current density is 3.78mA/cm2, fill factor 30.9%, photoelectric conversion efficiency 0.56%.
By the way that the third transmission layer material of flexible organic solar batteries is blended to obtain conducting polymer with electrode material Blend solution, and dispensing or printing conducting polymer blend solution on active layer, form the top of hole transport and electrode blending Electrode layer, avoid be prepared separately hole transmission layer and electrode layer to active layer film generation destroy twice.
Embodiment three：
Fig. 7 is the structural schematic diagram of the flexible organic solar batteries of third embodiment of the invention.As shown in fig. 7, flexible Organic solar batteries include flexible substrates 1, hearth electrode 2, the first transmitting layer 3, active layer 4 and top electrode layer 5.Organic solar After battery absorbs light, light penetrates flexible substrates 1 and the first transmitting layer 3, and absorbing light by the material in active layer 4 generates exciton (electron-hole pair) then splits into freedom in exciton diffusion to active layer material on the interface of donor material and acceptor material Carrier, i.e. electrons and holes.Then, electrons and holes are respectively in respective main body phase (the donor phase and receptor of donor material The receptor phase of material) in through transport layer be transmitted to electrode, i.e. electronics is received through the first transmitting layer 3 by hearth electrode 2, and hole is by top electricity Pole layer 5 is received, and photoelectric current is ultimately formed.
The material of flexible substrates 1 is polyethylene naphthalate (PEN) plastic film, has electrical insulation capability.Poly- naphthalene Naphthalate (PEN) has excellent barrier properties for gases, ultraviolet radiation preventing performance and heat resistance, and PEN exists The various aspects of performance such as toughness, wrinkle resistance and temperature tolerance are relatively more balanced, can heatproof be up to 150 DEG C.
Hearth electrode 2 is formed in flexible substrates 1.Hearth electrode 2 forms comb by printing silver conductive ink in flexible substrates 1 Shape silver electrode need to anneal 10-30 minutes after printing at 60-150 DEG C.Hearth electrode 2 is printed as pectinate texture, it is possible to reduce light Absorption loss water, ensure that active layer can effectively absorb light, reduce dependence of the battery device to ITO electrode.
First transmitting layer 3 is mainly used for transmitting electronics.First transmitting layer 3 on hearth electrode 2 by scratching polyethoxy second Alkene imines (Polyethylenimine ethoxylated, PEIE) solution is formed.Wherein, the first biography formed by PEIE solution Defeated layer 3 is formed by scratching PEIE solution on hearth electrode 2 after then annealing 5-30 minutes at 60-120 DEG C.Wherein, A concentration of 0.2-5wt% of PEIE solution, solvent are isopropanol.
Active layer 4 is set to the surface of the first transmitting layer 3, by scratching PTB7-Th on the surface of the first transmitting layer 3: ITIC blend solutions are formed.Active layer 4 can absorb sunlight, improve the photoelectric conversion efficiency of flexible organic solar batteries. Scratch the PTB7-Th formed:ITIC blend solution layers needs are annealed 10-30 minutes at 80-130 DEG C.PTB7-Th:ITIC is blended Solution is using PTB7-Th and ITIC as solute, is the mixed solution that solvent is formed with toluene, dimethylbenzene, trimethylbenzene etc..Wherein, The mass ratio of PTB7-Th and ITIC is 1:0.8-1:1.5, PTB7-Th:A concentration of 10-25mg/mL of ITIC blend solutions.
Top electrode layer 5 is arranged on active layer 4, is formed by dispensing or printing conducting polymer blend solution.Conduction is poly- It includes electrode material and third transmission layer material to close object blend solution, and electrode material is added in third transmission layer material, and is stirred It mixes 0.5-2 hours and is formed.Electrode material is the blend of silver powder or silver powder and nano silver wire.It is poly- 3,4- that third, which transmits layer material, Ethylenedioxy thiophene：Poly styrene sulfonate (Poly (3,4-ethylenedioxy thiophene):poly (styrenesulfonate), PEDOT:PSS) solution.When electrode material is silver powder, the conducting polymer of the present embodiment is blended Solution is added to the PEDOT of 1-2mL by the silver powder of 5-20mg:PSS solution is made.When electrode material is silver powder and nano silver wire When blend, the conducting polymer blend solution of the present embodiment is 4 by the mass ratio of 5-20mg:1-1:1 silver powder and silver nanoparticle The blend of line is added to the PEDOT of 1-2mL:PSS solution is made.Wherein, PEDOT:PSS solution has highly conductive forthright. By dispensing or the above-mentioned conducting polymer blend solution of printing on active layer 4, anneals 30-60 minutes, had at 70-130 DEG C There is the top electrode layer 5 that hole transport and electrode are blended.Top electrode layer 5 can avoid being prepared separately hole transmission layer and electrode layer to work Property layer film generation destroy twice.
The all print preparation method of the flexible organic solar batteries of the present embodiment is as shown in figure 8, prepared by all print Method includes：
Step S310, silver conductive ink is printed in PEN flexible substrates, forms pectination hearth electrode.
Step S320, PEIE solution is scratched on the hearth electrode, forms the first transport layer.
Step S330, PTB7-Th is scratched in first transport layer:ITIC blend solutions form active layer.
Step S340, on the active layer, dispensing or printing conducting polymer blend solution, form top electrode layer.
The conducting polymer blend solution of the present embodiment is divided into two kinds：One is the silver powder and 1-2mL by 5-20mg PEDOT:The stirring of PSS solution is made；It is 4 that another kind, which is by the mass ratio of 5-20mg,:1-1:1 silver powder and nano silver wire blend It is added to the PEDOT of 1-2mL:The stirring of PSS solution is made.
The flexible organic solar batteries completed will be prepared to be tested for the property, flexible organic solar batteries can be obtained Density of photocurrent-voltage (J-V) curve graph.Density of photocurrent-voltage of flexible organic solar batteries according to Fig.9, Curve can obtain being based on PEDOT:The open-circuit voltage of PSS-Ag (powder) top electrode layer is 0.46V, short-circuit current density 1.6mA/ cm2, fill factor 31.1%, photoelectric conversion efficiency 0.24%.Flexible organic solar batteries according to Fig.10, Density of photocurrent-voltage curve can obtain being based on PEDOT:PSS-Ag (silver powder and nano silver wire blend) top electrode layer is opened Road voltage is 0.42V, short-circuit current density 1.61mA/cm2, fill factor 36.4%, photoelectric conversion efficiency 0.25%.
The disclosure prints on a flexible substrate forms pectination silver electrode, while by the transmission material of flexible organic solar batteries Material is blended to obtain conducting polymer blend solution with electrode material, and dispensing or printing conducting polymer blending are molten on active layer Liquid forms the top electrode layer of hole transport and electrode blending, on the one hand reduces the absorption loss water of light, reduce battery device pair The dependence of ITO electrode, on the other hand avoid be prepared separately hole transmission layer and electrode layer to active layer film generate twice It destroys.
Example IV：
Figure 11 is the structural schematic diagram of the flexible organic solar batteries of fourth embodiment of the invention.As shown in figure 11, soft Property organic solar batteries include polyethylene terephthalate-tin indium oxide (Polyethylene terephthalate- ITO, PET-ITO) flexible substrates electrode 1, the first transport layer 2, active layer 3, the second transport layer 4 and top electrode layer 5.Organic sun For energy battery under the irradiation of light, light penetrates flexible substrates electrode 1 and the first transport layer 2, is absorbed by the light absorbent in active layer 3 Exciton is generated, exciton is diffused into donor material again and the coblended interface of acceptor material carries out splitting into electrons and holes, then empty The first transport layer of cave 2 is captured by flexible substrates electrode 1, and electronics is captured through the second transport layer 4 by top electrode 5, to be formed Photoelectric current.
PET-ITO flexible substrates electrode 1 is PET-ITO conductive membrane layers.PET-ITO refers to using magnetron sputtering technique, High-tech transparent indium tin oxide (ITO) conductive film coating and obtained through the high temperature anneal is sputtered on PET base material Product.The thickness of ito film layer is different, and the electric conductivity and light transmission of film are also different.In general, in identical process conditions In the case of PET base material identical with performance, ito film layer is thicker, and the sheet resistance of PET-ITO films is smaller, light transmission rate Also corresponding smaller.The resistance of the present embodiment PET-ITO substrates is 5-40 Ω/cm2.Polyethylene terephthalate (PET) has There is the advantages that good mechanical property, impact strength is 3-5 times of other films, corrosion-resistant, and transparency is high.Tin indium oxide (ITO) it is a kind of N-type oxide semiconductor, ito thin film, that is, indium tin oxide transparent conductive semiconductor film, with good conduction Property and the transparency.
First transport layer 2 is mainly used for transporting holes.First transport layer 2 on PET-ITO flexible substrates electrode 1 by scraping Apply PEDOT:PSS solution forms hole transmission layer.First transport layer 2 on PET-ITO flexible substrates electrode 1 by scratching PEDOT:PSS solution is formed after then annealing 5-30 minutes at 60-120 DEG C.
Active layer 3 is set to the surface of the first transport layer 2, by scratching PTB7-Th on the surface of the first transport layer 2: ITIC blend solutions are formed.Active layer 3 can absorb sunlight, improve the photoelectric conversion efficiency of flexible organic solar batteries. Scratch the PTB7-Th formed:ITIC blend solution layers needs are annealed 10-30 minutes at 80-130 DEG C.PTB7-Th:ITIC is blended Solution is using PTB7-Th and ITIC as solute, is the mixed solution that solvent is formed with toluene, dimethylbenzene, trimethylbenzene etc..Wherein, The mass ratio of PTB7-Th and ITIC is 1:0.8-1:1.5, PTB7-Th:A concentration of 10-25mg/mL of ITIC blend solutions.
Second transport layer 4 is set to the surface of active layer 3, by scratching nano zine oxide dispersion on the surface of active layer 3 Liquid is formed.Second transport layer 4 can transmit electronics.The second transport layer 4 that blade coating is formed needs to anneal at 80-130 DEG C 10-30 points Clock.Wherein, a concentration of 10-20mg/mL in nano zinc oxide fluid dispersion, dispersant are isopropanol and a small amount of stabilizer.
Top electrode layer 5 is formed by printing silver conductive ink in the second transport layer 4.It is needed in 100- after the completion of printing It anneals 10-30 minutes at 150 DEG C.Top electrode layer 5 is printed as pectinate texture, solvent and lower layer in silver conductive ink can be reduced The contact area of film, to reduce destructiveness of the solvent to active layer film.
The all print preparation method of the flexible organic solar batteries of the present embodiment is as shown in figure 12, prepared by all print Method includes：
Step S410, PEDOT is scratched in PET-ITO flexible substrates:PSS solution forms the first transport layer.
Step S420, PTB7-Th is scratched in first transport layer:ITIC blend solutions form active layer.
Step S430, nano zinc oxide fluid dispersion is scratched on the active layer, forms the second transport layer.
Step S440, silver conductive ink is printed in second transport layer, forms top electrode layer.
The flexible organic solar batteries completed will be prepared to be tested for the property, flexible organic solar batteries can be obtained Density of photocurrent-voltage (J-V) curve graph.According to density of photocurrent-electricity of flexible organic solar batteries shown in Figure 13 It buckles line, the open-circuit voltage that flexible organic solar batteries can be obtained is 0.62V, short-circuit current density 6.70mA/cm2, fill out It is 33.2% to fill the factor, photoelectric conversion efficiency 1.38%.
Pectination silver electrode is formed by printing silver conductive ink in the second transport layer, can be reduced molten in silver conductive ink The contact area of agent and lower film, to reduce destructiveness of the solvent to active layer film.
Embodiment five：
Figure 14 is the structural schematic diagram of the flexible organic solar batteries of fifth embodiment of the invention.As shown in figure 14, soft Property organic solar batteries include flexible substrates 1, hearth electrode 2, the first transmitting layer 3, active layer 4, the second transport layer 5 and top electrode Layer 6.For organic solar batteries under the irradiation of light, light penetrates the first transport layer, is absorbed and generates by the light absorbent in active layer 4 Exciton, exciton is diffused into donor material again and the coblended interface of acceptor material carries out splitting into electrons and holes, and then hole passes through First transmitting layer 3 is captured by hearth electrode 2, and electronics is captured through the second transport layer 5 by top electrode 6, to form photoelectric current.
The material of flexible substrates 1 is polyethylene terephthalate (PET) plastic film, has electrical insulation capability.Poly- pair Polyethylene terephthalate (PET) has excellent barrier properties for gases, ultraviolet radiation preventing performance and transparency height, oil resistant, resistance to fat Fat, resistance to olefin(e) acid, diluted alkaline, resistance to most of solvents.Also there is excellent high- and low-temperature resistance performance simultaneously, it can be in 120 DEG C of temperature ranges It is used for a long time, short-period used is resistant to 150 DEG C of high temperature, is resistant to -70 DEG C of low temperature, and influence very little to its mechanical performance when high and low temperature.
Hearth electrode 2 is formed in flexible substrates 1.Hearth electrode 2 forms comb by printing silver conductive ink in flexible substrates 1 Shape silver electrode need to be annealed 10-30 minutes after printing at 100-150 DEG C.Hearth electrode 2 is printed as pectinate texture, it is ensured that living Property layer can effectively absorb light, reduce dependence of the battery device to ITO electrode.
First transmitting layer 3 is mainly used for transporting holes.First transmitting layer 3 on hearth electrode 2 by scratching PEDOT:PSS is molten Liquid is formed.Wherein, PEDOT:PSS solution has highly conductive forthright.First transmitting layer 3 on hearth electrode 2 by scratching PEDOT: PSS solution is formed after then annealing 5-30 minutes at 60-120 DEG C.
Active layer 4 is set to the surface of the first transmitting layer 3, by scratching PTB7-Th on the surface of the first transmitting layer 3: ITIC blend solutions are formed.Active layer 4 can fully absorb sunlight, improve the opto-electronic conversion effect of flexible organic solar batteries Rate.Scratch the PTB7-Th formed:ITIC blend solution layers needs are annealed 10-30 minutes at 80-130 DEG C.PTB7-Th:ITIC is total Miscible fluid is using PTB7-Th and ITIC as solute, is the mixed solution that solvent is formed with toluene, dimethylbenzene, trimethylbenzene etc..Its In, the mass ratio of PTB7-Th and ITIC are 1:0.8-1:1.5, PTB7-Th:A concentration of 10-25mg/mL of ITIC blend solutions.
Second transport layer 5 is set to the surface of active layer 4, by scratching nano zine oxide dispersion on the surface of active layer 4 Liquid is formed, and is mainly used for transmitting electronics.The second transport layer 5 needs that blade coating is formed are annealed 10-30 minutes at 80-130 DEG C.Its In, a concentration of 10-20mg/mL in nano zinc oxide fluid dispersion, dispersant is isopropanol and a small amount of stabilizer.
Top electrode layer 6 is formed by printing silver conductive ink in the second transport layer 5.It is needed in 100- after the completion of printing It anneals 10-30 minutes at 150 DEG C.The shape of top electrode layer 6 is pectinate texture, and top electrode layer 6 is printed as pectinate texture, can be with The contact area for reducing solvent and lower film in silver conductive ink, to reduce destructiveness of the solvent to active layer film.
The all print preparation method of the flexible organic solar batteries of the present embodiment is as shown in figure 15, prepared by all print Method includes：
Step S510, silver conductive ink is printed in PET flexible substrates, forms hearth electrode.
Step S520, PEDOT is scratched on the hearth electrode:PSS solution forms the first transport layer.
Step S530, PTB7-Th is scratched in first transport layer:ITIC blend solutions form active layer.
Step S540, nano zinc oxide fluid dispersion is scratched on the active layer, forms the second transport layer.
Step S550, silver conductive ink is printed in second transport layer, forms top electrode layer.
The flexible organic solar batteries completed will be prepared to be tested for the property, flexible organic solar batteries can be obtained Density of photocurrent-voltage (J-V) curve graph.According to density of photocurrent-electricity of flexible organic solar batteries shown in Figure 16 It buckles line, the open-circuit voltage that battery can be obtained is 0.48V, short-circuit current density 3.77mA/cm2, fill factor 31.2%, Photoelectric conversion efficiency is 0.56%.
The disclosure prints silver conductive ink and forms pectination silver electrode on a flexible substrate, and uses high conductivity material conduct Hole transmission layer is effectively guaranteed the electric conductivity of electrode and the absorbing properties of active layer film, reduces battery device To the dependence of ITO electrode.And pectination silver electrode is printed in the second transport layer, reduce silver conductive ink solvent and lower layer The contact area of film, to reduce destructiveness of the solvent to active layer film.
The foregoing is merely the preferred embodiment of the present invention, are not intended to restrict the invention, for those skilled in the art For, the present invention can have various modifications and changes.It is all within spirit and principles of the present invention made by any modification, equivalent Replace, improve etc., it should all be included in the protection scope of the present invention.

Claims (37)

1. a kind of all print preparation method of flexibility organic solar batteries, including：
The first transmission layer material is printed or scratched in the flexible substrates with hearth electrode, forms the first transport layer；
Conjugated polymer solution is scratched on the surface of first transport layer, forms active layer；
Form top electrode layer；
Wherein, the formation top electrode layer includes：
Surface dispensing in the active layer or printing conducting polymer blend solution, form top electrode layer；
Alternatively,
The all print preparation method further includes：
On the surface of the active layer, the second transmission of blade coating layer material, forms the second transport layer；
Wherein, the formation top electrode layer includes：
Top electrode layer is formed in the printout surface silver conductive ink of second transport layer.
2. all print preparation method according to claim 1, which is characterized in that the flexible substrates with hearth electrode are Polyethylene terephthalate-tin indium oxide (Polyethylene terephthalate-ITO, PET-ITO), poly- naphthalene two Formic acid glycol ester-tin indium oxide (Polyethylene naphthalate-ITO, PEN-ITO) or polyimides-indium oxide One kind in tin (Polyimide-ITO, PI-ITO) flexible substrates.
3. all print preparation method according to claim 1, which is characterized in that the flexible substrates packet with hearth electrode It includes：
Printing silver conductive ink forms pectination hearth electrode on a flexible substrate.
4. all print preparation method according to claim 1, which is characterized in that the conducting polymer blend solution includes Electrode material and third transmit layer material；
Wherein, the electrode material is the blend of nano-silver powder, nano silver wire solution or silver powder and nano silver wire, the third Transmission layer material is poly- 3,4-ethylene dioxythiophene：Poly styrene sulfonate (Poly (3,4- ethylenedioxythiophene):Poly (styrenesulfonate), PEDOT:PSS) blend solution.
5. all print preparation method according to claim 4, which is characterized in that the electrode material is silver powder, nano silver Powder is 5-20mg, PEDOT:PSS solution is 1-2mL；Alternatively,
The electrode material is nano silver wire solution, and nano silver wire solution is 0.1-0.5mL, PEDOT:PSS solution is 1-2mL； Alternatively,
The electrode material is the blend of silver powder and nano silver wire, and the blend of silver powder and nano silver wire is 5-20mg, PEDOT:PSS solution is 1-2mL, wherein the mass ratio of the silver powder and nano silver wire is 1:20-20:1.
6. all print preparation method according to claim 1, which is characterized in that the second transmission layer material is nano oxygen Change zinc (ZnO) dispersion liquid, polyethoxy aziridine (Polyethylenimine ethoxylated, PEIE) solution or polyethers This kind of or its arbitrary two or more of combination solution in acid imide (Polyetherimide, PEI) solution.
7. all print preparation method according to claim 6, which is characterized in that the concentration of the nano zinc oxide fluid dispersion Mass fraction for 6-20mg/mL, PEIE and PEI is 0.02%-1%.
8. all print preparation method according to claim 1, which is characterized in that in the printout surface of second transport layer Silver conductive ink forms top electrode layer：
Pectination top electrode layer is formed in the printout surface silver conductive ink of second transport layer.
9. all print preparation method according to claim 1, which is characterized in that the conjugated polymer solution is polymer The blend solution of donor and receptor.
10. all print preparation method according to claim 9, which is characterized in that the polymeric donor is PffBT4T- 2OD(PCE11)、P3HT、PTB7、PTB7-Th、DPP-DTT、PDPP4T、PBDB-T(PCE12)、PBDTT-DPP、PDPP4T- 2F, PBDTTPD, PBDTTTPD, PJ61, PJ71, TQ1 or PBDD4T-2F conjugated polymer it is one or more.
11. all print preparation method according to claim 9, which is characterized in that the polymeric acceptor be PC60BM, PC70BM, bis-PCBM, ICBA, C60-N, ITIC or N2200 polymer it is one or more.
12. all print preparation method according to claim 9, which is characterized in that the conjugated polymer solution be chloroform, One kind in chlorobenzene, toluene, dichloro-benzenes, dimethylbenzene, trimethylbenzene, methyl phenyl ethers anisole, diphenyl ether, tetrahydrofuran, naphthane or it is arbitrary Blend solvent.
13. all print preparation method according to claim 9, which is characterized in that donor in the conjugated polymer solution The mass ratio that is blended with receptor is 1:0.5-1:4.0.
14. all print preparation method according to claim 9, which is characterized in that the conjugated polymer solution concentration is 8-30mg/mL。
15. all print preparation method according to claim 1, which is characterized in that the first transmission layer material is nanometer Zinc oxide fluid dispersion, polyethoxy aziridine (Polyethylenimine ethoxylated, PEIE) solution, polyetherimide The combination solution or poly- 3,4- enedioxies thiophene of amine (Polyetherimide, PEI) solution and ZnO/PEIE and ZnO/PEI Pheno：Poly styrene sulfonate (Poly (3,4-ethylenedioxythioph-ene):Poly (styrene sulfonate), PEDOT:PSS) blend solution.
16. all print preparation method according to claim 15, which is characterized in that the nano zinc oxide fluid dispersion it is dense Degree is that the mass fraction of 6-20mg/mL, PEIE and PEI are 0.02%-1%.
17. according to flexible organic solar batteries prepared by any one of claim 1-16 the methods, including：
Flexible substrates；
First transport layer is set in the flexible substrates, is formed by printing or scratching the first transmission layer material；
Active layer is set in first transport layer, is formed by scratching conjugated polymer solution；
Top electrode layer is set on the active layer, is formed by dispensing or printing conducting polymer blend solution；
Wherein, the conducting polymer blend solution includes electrode material and third transmission layer material, wherein the electrode material For silver powder, the blend of nano silver wire solution or silver powder and nano silver wire, the third transmission layer material is poly- 3,4- ethylenes two Oxygen thiophene：Poly styrene sulfonate (Poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate), PEDOT:PSS) solution.
18. flexibility organic solar batteries according to claim 17, which is characterized in that the flexible substrates are poly- to benzene Naphthalate-tin indium oxide (Polyethylene terephthalate-ITO, PET-ITO), poly- naphthalenedicarboxylic acid second Diol ester-tin indium oxide (Polyethylene naphthalate-ITO, PEN-ITO), polyimides (Polyimide-ITO, PI-ITO) flexible substrates.
19. flexibility organic solar batteries according to claim 17, which is characterized in that the flexible substrates include pectination Hearth electrode is formed by printing silver conductive ink.
20. flexibility organic solar batteries according to claim 17, which is characterized in that described first, which transmits layer material, is Nano zinc oxide fluid dispersion, polyethoxy aziridine (Polyethylenimine ethoxylated, PEIE) solution, polyethers The combination solution of acid imide (Polyetherimide, PEI) solution and ZnO/PEIE and ZnO/PEI.
21. all print preparation method according to claim 17, which is characterized in that the conjugated polymer solution is polymerization The blend solution of object donor and receptor.
22. flexibility organic solar batteries according to claim 17, which is characterized in that the polymeric donor is PffBT4T-2OD(PCE11)、P3HT、PTB7、PTB7-Th、DPP-DTT、PDPP4T、PBDB-T(PCE12)、PBDTT-DPP、 PDPP4T-2F, PBDTTPD, PBDTTTPD, PJ61, PJ71, TQ1, PBDD4T-2F conjugated polymer it is one or more.
23. flexibility organic solar batteries according to claim 17, which is characterized in that the polymeric acceptor is PC60BM, PC70BM, bis-PCBM, ICBA, C60-N, ITIC, N2200 polymer it is one or more.
24. flexibility organic solar batteries according to claim 17, which is characterized in that the conjugated polymer solution is Chloroform, chlorobenzene, toluene, dichloro-benzenes, dimethylbenzene, trimethylbenzene, methyl phenyl ethers anisole, diphenyl ether, tetrahydrofuran, naphthane etc. single or altogether Miscible agent.
25. flexibility organic solar batteries according to claim 17, which is characterized in that in the conjugated polymer solution Donor is 1 with the mass ratio that is blended of receptor:0.5-1:4.0.
26. flexibility organic solar batteries according to claim 17, which is characterized in that the conjugated polymer solution is dense Degree is 8-30mg/mL.
27. according to flexible organic solar batteries prepared by any one of claim 1-16 the methods, including：
Flexible substrates；
First transport layer is set in the flexible substrates, is formed by blade coating the first transmission layer material；
Active layer is set in first transport layer, is formed by scratching conjugated polymer solution；
Second transport layer is set on the active layer, is formed by blade coating the second transmission layer material；
Top electrode layer is set in second transport layer, and scheduled pattern is formed by printing silver conductive ink.
28. flexibility organic solar batteries according to claim 27, which is characterized in that the flexible substrates are poly- to benzene Naphthalate (Polyethylene terephthalate, PET), polyethylene naphthalate (Polyethylene naphthalate, PEN), polyimides (Polyimide, PI) flexible substrates.
29. flexibility organic solar batteries according to claim 27, which is characterized in that the flexible substrates include pectination Hearth electrode is formed by printing silver conductive ink.
30. flexibility organic solar batteries according to claim 27, which is characterized in that described first, which transmits layer material, is Poly- 3,4-ethylene dioxythiophene：Poly styrene sulfonate (Poly (3,4-ethylenedioxythioph-ene):poly (styrene sulfonate), PEDOT:PSS) blend solution.
31. all print preparation method according to claim 27, which is characterized in that the conjugated polymer solution is polymerization The blend solution of object donor and receptor.
32. all print preparation method according to claim 27, which is characterized in that the polymeric donor is PffBT4T- 2OD(PCE11)、P3HT、PTB7、PTB7-Th、DPP-DTT、PDPP4T、PBDB-T(PCE12)、PBDTT-DPP、PDPP4T- It is one or more in 2F, PBDTTPD, PBDTTTPD, PJ61, PJ71, TQ1 or PBDD4T-2F conjugated polymer.
33. all print preparation method according to claim 27, which is characterized in that the polymeric acceptor be PC60BM, It is one or more in PC70BM, bis-PCBM, ICBA, C60-N, ITIC or N2200 polymer.
34. all print preparation method according to claim 27, which is characterized in that the conjugated polymer solution is chlorine The single or blending of imitative, chlorobenzene, toluene, dichloro-benzenes, dimethylbenzene, trimethylbenzene, methyl phenyl ethers anisole, diphenyl ether, tetrahydrofuran, naphthane etc. Solvent.
35. all print preparation method according to claim 27, which is characterized in that donor in the conjugated polymer solution The mass ratio that is blended with receptor is 1:0.5-1:4.0.
36. all print preparation method according to claim 27, which is characterized in that the conjugated polymer solution concentration is 8-30mg/mL。
37. flexibility organic solar batteries according to claim 27, which is characterized in that described second, which transmits layer material, is Nano zinc oxide fluid dispersion, polyethoxy aziridine (Polyethylenimine ethoxylated, PEIE) solution or poly- One kind in etherimide (Polyetherimide, PEI) solution or its arbitrary two or more of combination solution.
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