CN116478570A - 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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Publication number
CN116478570A
CN116478570A CN202310528237.6A CN202310528237A CN116478570A CN 116478570 A CN116478570 A CN 116478570A CN 202310528237 A CN202310528237 A CN 202310528237A CN 116478570 A CN116478570 A CN 116478570A
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organic
ink
surfactant
gravure
printing ink
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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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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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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Photovoltaic Devices (AREA)

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, and the like. In the past 20 years, organic solar cells have achieved a great breakthrough in energy conversion efficiency (Power conversion efficiency, PCE) thanks to the development of active layer donor/acceptor materials, interface layer materials, device structures and fabrication processes in organic solar cells, the efficiency of small area devices has broken through 19%.
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. The print quality of the film during ink transfer is determined by the competing relationship of the three forces, namely the adhesion between the ink and the ink well, the adhesion between the ink and the substrate, and the cohesion of the ink itself (see, for example, 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 treatments are mostly used in the prior art to increase the surface energy of the substrate and improve the wetting and adhesion of the ink to the substrate (for example, reference is made to Thomas Michael, hermmann anika, dohse Antje, et al printing of μm 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)). In addition, the wetting and adhesion characteristics between the ink and the substrate may also be adjusted by incorporating surfactants in the printing ink. (for example, reference may be made to 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 invention, and in order to enable those skilled in the art to more clearly understand the technical means of the present application, the present invention may be implemented according to the content of the specification, the following description is given of the preferred embodiments of the present invention with reference to the accompanying 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, however, 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 PC 71 BM、PC 61 Either or a combination of both BMs.
In some embodiments, the non-fullerene receptor comprises any one or a combination of two or more of ITIC, IT-4F, Y6, 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 flexible batteries, but other non-flexible substrates can be replaced to achieve the same technical effects.
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 a PBDB-T donor material and an 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.
Dissolving organic active material in the surfactant solution at 80deg.C for 6 hr to form gravure ink, wherein the organic active material is PTB7-Th donor material and PC with mass ratio of 1:1.5 71 BM acceptor material the total concentration of donor acceptor material in the ink was 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 percent and the volume fraction of the liquid additive of 1 percent.
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 the donor and acceptor materials in the ink was 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 (10)

1. An intaglio printing ink for forming an organic photoactive layer, comprising an organic active material, an organic solvent and a surfactant, characterized in that the surfactant comprises a nonionic surfactant, and the volume fraction of the surfactant in the intaglio printing ink is below 0.5%.
2. The intaglio printing ink according to claim 1, wherein said organic solvent comprises any one or a combination of two or more of chlorobenzene, dichlorobenzene, toluene, xylene, trimethylbenzene;
and/or the intaglio printing ink further comprises a liquid additive to adjust the phase separation morphology;
preferably, the volume fraction of the liquid additive in the gravure ink is 0.2-1%;
preferably, the liquid additive comprises any one or more than two of 1-chloronaphthalene, 1, 8-diiodooctane, diphenyl ether and N-methyl pyrrolidone.
3. The intaglio printing ink according to claim 1, wherein said nonionic surfactant comprises any one or a combination of two or more of polyoxyethylene type surfactants, polyhydric alcohol type surfactants, alkyl alcohol amide type surfactants, acetylenic diol ethoxylates.
4. Intaglio printing ink according to claim 1 characterized in that the volume fraction of said nonionic surfactant in said intaglio printing ink is comprised between 0.01 and 0.5%, preferably between 0.05 and 0.1%.
5. The intaglio printing ink according to claim 1, wherein said organic active material comprises a donor material and a acceptor material;
preferably, the donor material comprises any one or more than two of P3HT, PTB7-Th, PBDB-T, PBDB-TF, PBDB-T-2Cl and PBDB-T-2F;
the acceptor material comprises fullerene acceptors and/or non-fullerene acceptors;
preferably, the fullerene receptor comprises PC 71 BM、PC 61 Any one or the combination of two of BM;
preferably, the non-fullerene receptor comprises any one or more than two of ITIC, IT-4F, Y6, BTP-BO-4Cl and L8-BO.
6. Intaglio printing ink according to claim 5 characterized in that the mass ratio of donor material to acceptor material in said organic active material is 1:0.6-1:1.3, preferably 1:0.8-1:1.2;
and/or the concentration of the organic active material in the intaglio printing ink is 16-160mg/mL, preferably 17.6-50mg/mL.
7. A method of 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.
8. The method of claim 7, wherein the organic active material has a dissolution temperature of 50-100 ℃ for 2-12 hours.
9. Use of the intaglio printing ink according to any one of claims 1 to 6 for the preparation of an organic optoelectronic device;
preferably, the organic photoelectric device is an organic solar cell.
10. An organic solar cell comprises a first semiconductor layer, a photoactive layer and a second semiconductor layer which are in ohmic contact in sequence, wherein the first semiconductor layer and the second semiconductor layer are opposite in conductive property;
the photoactive layer is produced by gravure printing with the gravure ink of any one of claims 1-6.
CN202310528237.6A 2023-05-11 2023-05-11 Gravure ink for forming organic photoactive layer, preparation method and application Pending CN116478570A (en)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004006747A (en) * 2002-04-18 2004-01-08 Konica Minolta Holdings Inc Organic semiconductor material, organic transistor employing it, field-effect-transistor, and switching element
CN101622730A (en) * 2007-02-27 2010-01-06 拜尔技术服务有限责任公司 Hybrid organic solar cells with photoactive semiconductor nanoparticles enclosed in surface modifiers
US20120152357A1 (en) * 2010-12-15 2012-06-21 Plextronics, Inc. Fluoro monomers, oligomers, and polymers for inks and organic electronic devices
CN102903853A (en) * 2012-10-24 2013-01-30 中国科学院长春应用化学研究所 Ink-jet printing preparation method of organic solar battery optical active layer film
CN106611818A (en) * 2015-10-27 2017-05-03 中国科学院苏州纳米技术与纳米仿生研究所 Polymer-polyoxometalate composite material and preparation method and application thereof
KR20180000544A (en) * 2016-06-23 2018-01-03 코오롱인더스트리 주식회사 Composition for forming photoactive layer and organic photovoltaics comprising the same
CN108054278A (en) * 2017-11-23 2018-05-18 华中科技大学 A kind of high yield organic solar batteries and preparation method thereof
CN108550697A (en) * 2017-10-30 2018-09-18 上海幂方电子科技有限公司 Flexible organic solar batteries and its all print preparation method
CN110235263A (en) * 2017-02-23 2019-09-13 埃尼股份公司 Polymer photovoltaic cell and its preparation process with inverted structure
CN111211226A (en) * 2020-01-10 2020-05-29 长沙而道新能源科技有限公司 Method for improving photoelectric efficiency of organic polymer solar cell
CN111223996A (en) * 2019-12-09 2020-06-02 湖南理工学院 Ternary system organic solar cell with self-assembled nano spine-shaped active layer

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004006747A (en) * 2002-04-18 2004-01-08 Konica Minolta Holdings Inc Organic semiconductor material, organic transistor employing it, field-effect-transistor, and switching element
CN101622730A (en) * 2007-02-27 2010-01-06 拜尔技术服务有限责任公司 Hybrid organic solar cells with photoactive semiconductor nanoparticles enclosed in surface modifiers
US20120152357A1 (en) * 2010-12-15 2012-06-21 Plextronics, Inc. Fluoro monomers, oligomers, and polymers for inks and organic electronic devices
CN102903853A (en) * 2012-10-24 2013-01-30 中国科学院长春应用化学研究所 Ink-jet printing preparation method of organic solar battery optical active layer film
CN106611818A (en) * 2015-10-27 2017-05-03 中国科学院苏州纳米技术与纳米仿生研究所 Polymer-polyoxometalate composite material and preparation method and application thereof
KR20180000544A (en) * 2016-06-23 2018-01-03 코오롱인더스트리 주식회사 Composition for forming photoactive layer and organic photovoltaics comprising the same
CN110235263A (en) * 2017-02-23 2019-09-13 埃尼股份公司 Polymer photovoltaic cell and its preparation process with inverted structure
CN108550697A (en) * 2017-10-30 2018-09-18 上海幂方电子科技有限公司 Flexible organic solar batteries and its all print preparation method
CN108054278A (en) * 2017-11-23 2018-05-18 华中科技大学 A kind of high yield organic solar batteries and preparation method thereof
CN111223996A (en) * 2019-12-09 2020-06-02 湖南理工学院 Ternary system organic solar cell with self-assembled nano spine-shaped active layer
CN111211226A (en) * 2020-01-10 2020-05-29 长沙而道新能源科技有限公司 Method for improving photoelectric efficiency of organic polymer solar cell

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WANG, ZHENGUO ET AL.: "Manipulating the Macroscopic and Microscopic Morphology of Large-Area Gravure-Printed ZnO Films for High-Performance Flexible Organic Solar Cells", 《ENERGY & ENVIRONMENTAL MATERIALS》, pages 12592 *

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