CN116478570B - Gravure ink for forming organic photoactive layer, preparation method and application - Google Patents

Gravure ink for forming organic photoactive layer, preparation method and application Download PDF

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CN116478570B
CN116478570B CN202310528237.6A CN202310528237A CN116478570B CN 116478570 B CN116478570 B CN 116478570B CN 202310528237 A CN202310528237 A CN 202310528237A CN 116478570 B CN116478570 B CN 116478570B
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gravure printing
surfactant
printing ink
organic
ink
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CN116478570A (en
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潘雅琴
王振国
刘媛琪
韩云飞
骆群
马昌期
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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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
    • C09D11/03—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
    • 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
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • 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
    • H10K30/50—Photovoltaic [PV] devices
    • 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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Abstract

The invention discloses gravure printing ink for forming an organic photoactive layer, a preparation method and application thereof. The gravure ink comprises an organic active material, an organic solvent and a surfactant; the surfactant includes a nonionic surfactant, and the volume fraction of the surfactant in the intaglio printing ink is 0.5% or less. The gravure ink provided by the invention is used for preparing the flexible battery based on gravure printing, has the advantages of patternability, high precision, high-speed printing, high printing durability, large-scale high-flux production and the like, and is beneficial to the industrialization and multi-scene application of the organic solar battery; the rheological property of the gravure ink is suitable for gravure printing, large-area high-quality film preparation can be realized, surface defects easily generated by the conventional gravure ink can be avoided, the influence on photoelectric properties is lower, and the prepared flexible solar cell has excellent large-area device performance.

Description

Gravure ink for forming organic photoactive layer, preparation method and application
Technical Field
The invention relates to the technical field of organic photoelectric devices, in particular to gravure ink for forming an organic photoactive layer, a preparation method and application.
Background
Organic solar cells (Organic solar cells, OSCs) have become a research hotspot in the field of solar cells due to their advantages of light weight, low cost, solution processibility, etc. In the past 20 years, organic solar cells have achieved a great breakthrough in energy conversion efficiency (Power conversion efficiency, PCE) and the efficiency of small area devices has broken through 19% thanks to the development of active layer donor/acceptor materials, interfacial layer materials, device structures and fabrication processes in organic solar cells.
As is well known, most of the reported high efficiency OSCs are prepared using spin-coating methods, and the main advantage of this technique is the suitability for depositing high quality organic films of well-defined thickness of various compositions. However, this approach wastes more than 90% of the solution and generally has limitations on substrate size, which is incompatible with high throughput yields of flat-pressed sheet (S2S) and roll-to-roll (R2R). Thus, commercialization of OSCs requires the use of malleable S2S or R2R fabrication techniques such as doctor blade coating, slot coating, gravure printing, inkjet printing, screen printing, and the like. However, the research of large-area devices has been far lagged, and the main disadvantage of these methods for preparing OSCs in large areas is that it is difficult to control the uniformity, thickness, crystallization and morphology of the organic thin film. Compared with small-area devices, large-area devices have higher requirements on the solubility of active layer materials, the processing mode of the devices and the like, and how to prepare efficient and stable flexible large-area devices remains a challenge. Therefore, the key basic problems in the organic photovoltaic large-area device are studied in depth, the large-area printing preparation method is developed, the method has important significance for promoting the industrial application of the organic solar cell, and the method is a hot spot and a difficult direction of the development of the organic solar cell in the future.
In particular, the existing flexible large-area organic solar cells mostly use coating technology, but solution processing technology such as doctor blade coating, slit coating and the like has limited ink supply, so that large-scale high-flux production of the organic solar cells is blocked, patterning cannot be realized, and the application situation is limited to a certain extent. Gravure printing is taken as a very promising solution method processing technology, has the advantages of patternability, high precision, high-speed printing, high printing endurance, large-scale high-flux (R2R) production and the like, and can meet the actual production requirements of various printed electronic products.
The intaglio printing process consists of three parts, namely: the ink is filled in the net hole by the doctor blade, the excessive ink is scraped off, the ink is transferred from the net hole to the printing stock after the pressure combination, and the ink drops are dried horizontally to form a film. During the ink transfer process, the print quality of the film is mainly determined by three competing relationships, namely the adhesion between the ink and the mesh, the adhesion between the ink and the substrate, and the cohesion of the ink itself (for example, see literature ：Nguyen Ho Anh Duc,Lee Changwoo,Shin Kee-Hyun,et al.An Investigation of the Ink-Transfer Mechanism During the Printing Phase of High-Resolution Roll-to-Roll Gravure Printing[J].IEEE Transactions on Components,Packaging and Manufacturing Technology,2015,5(10)：1516-1524.).
The strength of the interaction between the ink and the substrate during gravure printing determines its wet adhesion properties, which can be generally improved by treating the substrate, regulating the rheology of the ink. Oxygen plasma treatment of substrates to increase substrate surface energy, improve wettability and adhesion of inks on substrates is mostly used in the prior art (e.g. reference ：Thomas Michael,Herrmann Annika,Dohse Antje,et al.Printing ofμm structures with nano inks using a novel combination of high-resolution plasma printing and subsequent rotogravure printing[J].Plasma Processes and Polymers,2019,16(9).). furthermore, the wettability and adhesion properties between inks and substrates can also be adjusted by incorporating surfactants in the printing inks (e.g. reference.) ：Voigt Monika M.,Mackenzie Roderick C.I.,King Simon P.,et al.Gravure printing inverted organic solar cells：The influence of ink properties on film quality and device performance[J].Solar Energy Materials and Solar Cells,2012,105：77.).
However, when the surfactant used in the prior art is added to the organic photoactive layer ink, the morphology of the film and the photoelectric performance of the film are affected. In addition, surfactants often foam easily in the ink, creating holes in the printed film. Quality problems often occur during large-area batch preparation, and the application of the gravure printing technology in preparing large-area organic photoactive layers is affected.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide gravure printing ink for forming an organic photoactive layer, a preparation method and application.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
In a first aspect, the present invention provides an intaglio printing ink for forming an organic photoactive layer comprising an organic active material, an organic solvent, and a surfactant; the surfactant includes a nonionic surfactant, and the volume fraction of the surfactant in the intaglio printing ink is 0.5% or less.
In a second aspect, the present invention also provides a method for preparing intaglio printing ink, comprising:
providing a surfactant solution comprising a nonionic surfactant and an organic solvent;
the organic active material is sufficiently dissolved in the surfactant solution to obtain the gravure ink.
In a third aspect, the invention also provides the use of the intaglio printing ink described above for the preparation of an organic photovoltaic device, in particular for the preparation of an organic solar cell.
In a fourth aspect, the present invention also provides an organic solar cell, including a first semiconductor layer, a photoactive layer, and a second semiconductor layer in ohmic contact in order, where the first semiconductor layer and the second semiconductor layer have opposite conductive properties; the photoactive layer is prepared from the intaglio printing ink through intaglio printing.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that:
The gravure ink provided by the invention is used for preparing flexible batteries based on gravure printing, has the advantages of patternability, high precision, high-speed printing, high printing resistance, large-scale high-flux (such as R2R) production and the like, and is beneficial to the industrialization and multi-scene application of organic solar batteries; the rheological property of the gravure ink is suitable for gravure printing, large-area high-quality film preparation can be realized, surface defects easily generated by the conventional gravure ink can be avoided, the influence on photoelectric properties is lower, and the prepared flexible solar cell has excellent large-area device performance.
The above description is only an overview of the technical solutions of the present application, and in order to enable those skilled in the art to more clearly understand the technical means of the present application, the present application may be implemented according to the content of the specification, and the following description is given of the preferred embodiments of the present application with reference to the detailed drawings.
Drawings
FIG. 1 is an exemplary diagram of a macroscopic photograph of a gravure printed organic photoactive layer provided in accordance with an exemplary comparative example of the present invention;
fig. 2 is a schematic diagram of a macroscopic photograph of a gravure-printed organic photoactive layer according to an exemplary embodiment of the present invention.
Detailed Description
In view of the shortcomings in the prior art, the inventor of the present invention has long studied and practiced in a large number of ways to propose the technical scheme of the present invention. The technical scheme, the implementation process, the principle and the like are further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
In the prior art, the rheological property of the ink is regulated by adding a relatively larger amount of surfactant so as to improve the wettability of the ink to the substrate, but a large amount of surfactant can cause some film defects and photoelectric performance problems, so that the regulation of the interaction force between the printing ink and the substrate is realized by adding a very small amount of surfactant, thereby ensuring the quality of the printing film and ensuring the photoelectric performance of the film.
The invention aims to provide a printing electronic ink based on surfactant addition and a regulating method. The acting force between the printing ink and the substrate can be regulated and controlled by adding a very small amount of surfactant, so that a uniform film is obtained.
Based on the above object, the gravure ink for forming an organic photoactive layer provided by the embodiment of the invention comprises an organic active material, an organic solvent and a surfactant, wherein the surfactant comprises a nonionic surfactant, and the volume fraction of the surfactant in the gravure ink is below 0.5%.
The gravure printing mode provided by the invention utilizes the characteristic of the nonionic surfactant, and the nonionic surfactant can adjust the interaction strength between ink and a substrate during gravure printing, so that the wet film stability and the film uniformity are improved, and on the basis of ensuring the macroscopic uniformity regulating effect, the addition amount of the nonionic surfactant can be very low, so that the influence on the photoelectric performance is avoided, and meanwhile, the surfactant can enhance the molecular accumulation to a certain extent and inhibit the excessive aggregation of molecules.
The prior art discloses some technical schemes for improving the film forming performance of water-based ink by adding polyoxyethylene or polyol surfactant into the water-based ink system, but the invention is different from the prior art, and is an organic system based on the difference of the ink system, so that the action principle is essentially different, the introduction of the surfactant does not change the rheological properties of the organic ink such as viscosity, surface tension and the like, but acts as a binder, and stronger intermolecular interaction force is formed between the surfactant and a printing substrate, so that the stability of a wet film on the substrate is improved, and the uniformity of the film is ensured; in the above aqueous ink system, the action of the surfactant is mainly performed by changing the rheological properties such as viscosity and surface tension of the aqueous ink.
In some embodiments, the organic solvent comprises any one or a combination of two or more of chlorobenzene, dichlorobenzene, toluene, xylene, trimethylbenzene.
In some embodiments, the intaglio printing ink further comprises a liquid additive that can adjust the micro-nano morphology of the organic photoactive layer, improve the crystallinity and molecular packing of organic molecules, and affect the dynamic process of the active layer solution to the thin film, thereby improving device performance.
In some embodiments, the volume fraction of liquid additive in the intaglio printing ink is between 0.2 and 1%.
In some embodiments, the liquid additive comprises any one or a combination of two or more of 1-chloronaphthalene, 1, 8-diiodooctane, diphenyl ether, N-methylpyrrolidone.
According to the technical scheme, the composition of the ink is continuously optimized, the liquid additives are added into the ink, the liquid additives have the characteristic of adjusting the phase separation morphology of the active layer and can be fully compatible with other components, so that when gravure printing is carried out, the liquid additives can act synergistically with the nonionic surfactant, the ordered accumulation and the molecular crystallinity of molecules in the organic photoactive layer are improved together, the excessive aggregation behavior of the molecules in the drying process is inhibited, and the efficient preparation of the organic solar cell is realized.
In some embodiments, the nonionic surfactant comprises any one or a combination of two or more of a polyoxyethylene type surfactant, a polyol type surfactant, an alkyl alcohol amide type surfactant, an acetylenic diol ethoxylate.
In some embodiments, the volume fraction of the nonionic surfactant in the intaglio printing ink is from 0.01 to 0.5%, preferably from 0.05 to 0.1%.
In some embodiments, the organic active material includes a donor material and a acceptor material.
In some embodiments, the donor material comprises any one or a combination of two or more of P3HT, PTB7-Th, PBDB-T, PBDB-TF, PBDB-T-2Cl, PBDB-T-2F.
In some embodiments, the acceptor material includes a fullerene acceptor and/or a non-fullerene acceptor.
In some embodiments, the fullerene receptor comprises any one or a combination of two of PC 71BM、PC61 BM.
In some embodiments, the non-fullerene receptor comprises any one or a combination of two or more of ITIC, IT-4F, Y, BTP-BO-4Cl, L8-BO.
In some embodiments, the mass ratio of donor material to acceptor material in the organic active material is from 1:0.6 to 1:1.5, and may further preferably be from 1:0.8 to 1:1.2.
In some embodiments, the concentration of the organic active material in the intaglio printing ink is between 16 and 160mg/mL, further may preferably be between 17.6 and 50mg/mL.
As some typical application examples of the technical scheme, the organic photoactive layer material is dissolved in the surfactant solution, the total solid content is 16-160mg/mL, the dissolution temperature is 50-100 ℃, and the dissolution time is 2-12h. Further, the preferable solid content is 17.6-50mg/mL, the preferable dissolution temperature is 80℃and the preferable dissolution time is 4-8 hours.
In addition, the second aspect of the embodiment of the invention also provides a preparation method of the gravure ink, which comprises the following steps:
A surfactant solution is provided that includes a nonionic surfactant and an organic solvent.
The organic active material is sufficiently dissolved in the surfactant solution to obtain the gravure ink.
As some typical examples of application of the above technical scheme, a surfactant solution selected from materials such as polyoxyethylene type, polyol type, alkyl alcohol amide type, alkynediol ethoxy compound and the like of nonionic surfactant may be used, which is dissolved in a small proportion in an organic solvent including but not limited to chlorobenzene, dichlorobenzene, toluene, xylene, trimethylbenzene and the like
The organic active layer material system may include, for example, two-component combinations of the above donor materials, and a donor multiple acceptor or a multiple blend system of a acceptor and multiple donors, and the like.
In some embodiments, the organic active material has a dissolution temperature of 50-100 ℃ for a period of 2-12 hours.
As a further extension of the above technical solution, the third aspect of the embodiment of the present invention further provides an application of the gravure ink provided by any one of the above embodiments in preparing an organic optoelectronic device.
In some embodiments, the organic photovoltaic device is selected from an organic solar cell.
In a specific application, the fourth aspect of the embodiment of the invention further provides an organic solar cell, which comprises a first semiconductor layer, a photoactive layer and a second semiconductor layer which are in ohmic contact in sequence, wherein the conductive characteristics of the first semiconductor layer and the second semiconductor layer are opposite; the photoactive layer is prepared by gravure printing of the gravure printing ink provided by any embodiment.
As a very typical exemplary structure of the above organic solar cell, the organic solar cell is characterized in that:
1. The flexible organic solar cell may alternatively be in an inverted or a positive configuration. Wherein the device of the inverted device structure is a substrate/a metal electrode/an electron transport layer/a photoactive layer/a hole transport layer/a metal electrode. The structure of the positive device is prepared as a substrate, a metal electrode, a hole transport layer, a photoactive layer, an electron transport layer and a metal electrode.
2. The substrate can be a plastic substrate such as PET, PEN, PI, but is not limited thereto, and the plastic substrate is mainly used for preparing the flexible battery, but other non-flexible substrates can be replaced to achieve the same technical effect.
3. The electron transport layer may be, for example, a metal oxide such as zinc oxide, titanium oxide, tin oxide, or the like. The thickness of the electron transport layer is preferably 30 to 200nm, but is not limited thereto.
4. The photoactive layer is an organic blend heterojunction film or an organic-inorganic perovskite film, and is prepared from the gravure printing ink through gravure printing, and the thickness of the photoactive layer can be 100-10000nm.
5. The hole transport layer may be, for example, molybdenum oxide, nickel oxide, PEDOT: PSS, etc. The thickness of the hole layer may be 30-100nm.
6. The preparation of the flexible large-area organic solar cell can be realized based on the gravure printing technology, wherein the ink characteristics of the metal electrode, the electron transport layer and the photoactive layer can be suitable for gravure printing.
The technical scheme of the invention is further described in detail below through a plurality of embodiments and with reference to the accompanying drawings. However, the examples are chosen to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
The preparation of gravure ink and the preparation process of the thin film solar cell are illustrated in the embodiment, and specifically the following steps are shown:
1. Ink formulation
Polyoxyethylene type surfactant 2,4,7, 9-tetramethyl-5-deca-4, 7-diol polyoxyethylene ether and 1, 8-diiodooctane are dissolved in dichlorobenzene as organic solvent to form surfactant solution with 0.5% of surfactant volume fraction and 0.5% of liquid additive volume fraction.
And dissolving an organic active material in the surfactant solution at 50 ℃ for 2 hours to form gravure printing ink, wherein the organic active material is PBDB-T donor material and ITIC acceptor material in a mass ratio of 1:1, and the total concentration of the donor material and the acceptor material in the ink is 20mg/mL.
2. Preparation of solar cells
And depositing a silver nanowire film electrode on the PI substrate through gravure printing, forming a zinc oxide electron transport layer with the thickness of 30nm through gravure printing, forming a photoactive layer with the thickness of 130nm through gravure printing ink prepared through the steps, forming a molybdenum oxide hole transport layer with the thickness of 20nm through gravure printing, and finally depositing an aluminum film electrode to finally form the large-size thin film solar cell.
The photoactive layer of the formed thin film solar cell is shown in fig. 2, and it can be seen that the surface of the thin film solar cell has no obvious defects such as holes, bubbles and the like, and the appearance of the thin film solar cell is uniform; and the photoelectric conversion efficiency of the battery was 6.42% through the battery performance test.
Example 2
This example is substantially the same as example 1, except that the liquid additive is omitted when the ink is formulated.
The uniformity of the finally prepared photoactive layer remained consistent with example 1, but the device performance was reduced with a photoelectric conversion efficiency of 5.45%.
Comparative example 1
This comparative example is substantially the same as example 1, with the main difference that:
No surfactant was added when formulating the ink.
The macro morphology of the prepared photoactive layer is shown in figure 1, a large number of wrinkles, pits and cell defects appear in the photoactive layer, the surface smoothness is poor, and the photoelectric conversion efficiency is only 1.21% after test.
Comparative example 2
This comparative example is substantially the same as example 1, with the main difference that:
In the preparation of the ink, the surfactant is replaced by other types of surfactants, namely sodium dodecyl benzene sulfonate, and the addition amount of the sodium dodecyl benzene sulfonate is kept unchanged.
The surface of the prepared film of the photoactive layer has a small quantity of ripple defects, and the photoelectric conversion efficiency is only 3.08 percent through test.
Comparative example 3
This comparative example is substantially the same as example 1, with the main difference that:
when the ink is prepared, the surfactant is replaced by other types of surfactants, namely sodium dodecyl benzene sulfonate, and the addition amount of the surfactant is increased to 1vol% so as to ensure the regulation and control effect of the stability of the wet film.
The corrugated defect on the surface of the prepared film of the photoactive layer is eliminated, a large number of needle holes exist on the surface of the film, and the photoelectric conversion efficiency is only 1.21 percent through test.
Comparative example 4
This comparative example is substantially the same as example 1, with the main difference that:
When the ink is prepared, the surfactant is not replaced, and is still polyoxyethylene surfactant, but the addition amount is increased to 1.5% and is out of the proper range.
Pinholes and ghosts appear on the surface of the prepared photoactive layer, and the photoelectric conversion efficiency is only 4.20% after testing.
Example 3
The preparation of gravure ink and the preparation process of the thin film solar cell are illustrated in the embodiment, and specifically the following steps are shown:
1. Ink formulation
The polyol type surfactant monoglyceride and 1-chloronaphthalene are dissolved in the chlorobenzene organic solvent to form a surfactant solution with the volume fraction of 0.1% and the volume fraction of 0.2% of the liquid additive.
And dissolving an organic active material in the surfactant solution at 80 ℃ for 6 hours to form gravure ink, wherein the organic active material is PTB7-Th donor material and PC 71 BM acceptor material with the mass ratio of 1:1.5, and the total concentration of the acceptor material in the ink is 17.5mg/mL.
2. Preparation of solar cells
And depositing a nano silver wire film electrode on the PET substrate through gravure printing, forming a titanium oxide electron transport layer with the thickness of 30nm through gravure printing, forming a photoactive layer with the thickness of 130nm through gravure printing ink prepared through the steps, forming a PEDOT/PSS hole transport layer with the thickness of 20nm through gravure printing, and finally depositing an aluminum film electrode to finally form the large-size thin film solar cell.
The film of the photoactive layer of the formed thin film solar cell is similar to that of the embodiment 1, the surface of the photoactive layer has no obvious defects such as holes, bubbles and the like, and the appearance of the film is uniform; and the photoelectric conversion efficiency of the battery was 7.51% through the battery performance test.
Example 4
The preparation of gravure ink and the preparation process of the thin film solar cell are illustrated in the embodiment, and specifically the following steps are shown:
1. Ink formulation
The alkyl alcohol amide type surfactant N, N-dihydroxyethyl dodecyl amide and diphenyl ether are dissolved in the organic solvent trimethylbenzene to form a surfactant solution with the volume fraction of the surfactant of 0.05% and the volume fraction of the liquid additive of 1%.
Dissolving an organic active material in the surfactant solution at 80 ℃ for 12 hours to form gravure ink, wherein the mass ratio of the organic active material is 1:0.6 of PBDB-T-2F donor material and BTP-BO-4Cl acceptor material, the total concentration of donor acceptor material in the ink being 25.6mg/mL.
2. Preparation of solar cells
And depositing a nano silver wire film electrode on the PEN substrate through gravure printing, forming a tin oxide electron transport layer with the thickness of 30nm through gravure printing, forming a photoactive layer with the thickness of 130nm through gravure printing ink prepared through the steps, forming a nickel oxide hole transport layer with the thickness of 20nm through gravure printing, and finally depositing an aluminum film electrode to finally form the large-size thin film solar cell.
The film of the photoactive layer of the formed thin film solar cell is similar to that of the embodiment 1, the surface of the photoactive layer has no obvious defects such as holes, bubbles and the like, and the appearance of the film is uniform; and the photoelectric conversion efficiency of the battery was 11.87% through the battery performance test.
The invention also adopts various raw material combinations to prepare the organic solar cell, and similar results are obtained, the main technical means of the invention is how to realize the regulation and control of the rheological property of the ink and avoid influencing the photoelectric property of the photoactive layer through the addition of the surfactant, the film forming process of the ink is not influenced by adopting other semiconductor layers and device structures in various forms, and the equivalent or similar replacement is considered to be within the protection scope of the invention.
Based on the above examples and comparative examples, it can be seen that the gravure ink provided by the embodiment of the invention is used for preparing a flexible battery based on gravure printing, has the advantages of patternability, high precision, high-speed printing, high endurance, large-scale high-throughput (R2R) production and the like, and is beneficial to industrialization and multi-scene application of an organic solar battery; the rheological property of the gravure ink is suitable for gravure printing, large-area high-quality film preparation can be realized, surface defects easily generated by the conventional gravure ink can be avoided, the influence on photoelectric properties is lower, and the prepared flexible solar cell has excellent large-area device performance.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.

Claims (11)

1.一种用于形成有机光活性层的凹版印刷墨水，包括有机活性材料、有机溶剂以及表面活性剂，其特征在于：所述表面活性剂选自非离子型表面活性剂，且所述凹版印刷墨水中表面活性剂的体积分数为0.01-0.5%；1. A gravure printing ink for forming an organic photoactive layer, comprising an organic active material, an organic solvent and a surfactant, wherein the surfactant is selected from a non-ionic surfactant, and the volume fraction of the surfactant in the gravure printing ink is 0.01-0.5%; 所述非离子型表面活性剂包括聚氧乙烯型表面活性剂、多元醇型表面活性剂、烷基醇酰胺型表面活性剂、炔二醇乙氧基化合物中的任意一种或两种以上的组合，所述有机溶剂包括氯苯、二氯苯、甲苯、二甲苯、三甲苯中的任意一种或两种以上的组合。The nonionic surfactant includes any one or a combination of two or more of a polyoxyethylene surfactant, a polyol surfactant, an alkyl alcohol amide surfactant, and an acetylene glycol ethoxylate; and the organic solvent includes any one or a combination of two or more of chlorobenzene, dichlorobenzene, toluene, xylene, and trimethylbenzene. 2.根据权利要求1所述的凹版印刷墨水，其特征在于，所述凹版印刷墨水还包括液态添加剂以调节相分离形貌；2. The gravure printing ink according to claim 1, characterized in that the gravure printing ink further comprises a liquid additive to adjust the phase separation morphology; 所述凹版印刷墨水中液态添加剂的体积分数为0.2-1%；The volume fraction of the liquid additive in the gravure printing ink is 0.2-1%; 所述液态添加剂包括1-氯萘、1,8-二碘辛烷、二苯醚、N-甲基吡咯烷酮中的任意一种或两种以上的组合。The liquid additive includes any one of 1-chloronaphthalene, 1,8-diiodooctane, diphenyl ether, and N-methylpyrrolidone, or a combination of two or more thereof. 3.根据权利要求1所述的凹版印刷墨水，其特征在于，所述凹版印刷墨水中所述非离子型表面活性剂的体积分数为0.05-0.1%。3. The gravure printing ink according to claim 1, characterized in that the volume fraction of the non-ionic surfactant in the gravure printing ink is 0.05-0.1%. 4.根据权利要求1所述的凹版印刷墨水，其特征在于，所述有机活性材料包括给体材料和受体材料；4. The gravure printing ink according to claim 1, wherein the organic active material comprises a donor material and an acceptor material; 所述给体材料包括P3HT、PTB7、PTB7-Th、PBDB-T、PBDB-TF、PBDB-T-2Cl、PBDB-T-2F中的任意一种或两种以上的组合；The donor material includes any one or a combination of two or more of P3HT, PTB7, PTB7-Th, PBDB-T, PBDB-TF, PBDB-T-2Cl, and PBDB-T-2F; 所述受体材料包括富勒烯受体和/或非富勒烯受体。The acceptor material includes a fullerene acceptor and/or a non-fullerene acceptor. 5.根据权利要求4所述的凹版印刷墨水，其特征在于，所述富勒烯受体包括PC71BM、PC61BM中的任意一种或两种的组合；5. The gravure printing ink according to claim 4, characterized in that the fullerene acceptor comprises any one of PC 71 BM and PC 61 BM or a combination of both; 所述非富勒烯受体包括ITIC、IT-4F、Y6、BTP-BO-4Cl、L8-BO中的任意一种或两种以上的组合。The non-fullerene acceptor includes any one of ITIC, IT-4F, Y6, BTP-BO-4Cl, and L8-BO, or a combination of two or more thereof. 6.根据权利要求4所述的凹版印刷墨水，其特征在于，所述有机活性材料中给体材料与受体材料的质量比为1:0.6-1:1.3；6. The gravure printing ink according to claim 4, characterized in that the mass ratio of the donor material to the acceptor material in the organic active material is 1:0.6-1:1.3; 所述凹版印刷墨水中有机活性材料的浓度为16-160 mg/mL。The concentration of the organic active material in the gravure printing ink is 16-160 mg/mL. 7.根据权利要求6所述的凹版印刷墨水，其特征在于，所述有机活性材料中给体材料与受体材料的质量比为1:0.8-1:1.2；7. The gravure printing ink according to claim 6, characterized in that the mass ratio of the donor material to the acceptor material in the organic active material is 1:0.8-1:1.2; 所述凹版印刷墨水中有机活性材料的浓度为17.6-50 mg/mL。The concentration of the organic active material in the gravure printing ink is 17.6-50 mg/mL. 8.根据权利要求1所述的凹版印刷墨水，其特征在于，所述凹版印刷墨水的配制方法包括：8. The gravure printing ink according to claim 1, characterized in that the preparation method of the gravure printing ink comprises: 提供表面活性剂溶液，所述表面活性剂溶液包括非离子型表面活性剂以及有机溶剂；Providing a surfactant solution, wherein the surfactant solution comprises a nonionic surfactant and an organic solvent; 使有机活性材料充分溶解在所述表面活性剂溶液中，获得凹版印刷墨水。The organic active material is fully dissolved in the surfactant solution to obtain a gravure printing ink. 9.根据权利要求8所述的凹版印刷墨水，其特征在于，所述有机活性材料的溶解温度为50-100 ℃，时间为2-12 h。9. The gravure printing ink according to claim 8, characterized in that the dissolution temperature of the organic active material is 50-100°C and the dissolution time is 2-12 hours. 10.权利要求1-9中任意一项所述的凹版印刷墨水在制备有机光电器件中的应用。10. Use of the gravure printing ink according to any one of claims 1 to 9 in the preparation of an organic optoelectronic device. 11.根据权利要求10所述的应用，其特征在于，所述有机光电器件为有机太阳能电池。11 . The use according to claim 10 , wherein the organic photoelectric device is an organic solar cell.
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