CN108054278B - High-yield organic solar cell and preparation method thereof - Google Patents

High-yield organic solar cell and preparation method thereof Download PDF

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CN108054278B
CN108054278B CN201711189613.4A CN201711189613A CN108054278B CN 108054278 B CN108054278 B CN 108054278B CN 201711189613 A CN201711189613 A CN 201711189613A CN 108054278 B CN108054278 B CN 108054278B
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insulating layer
layer
brush
thickness
solar cell
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CN108054278A (en
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周印华
毛霖
孙露露
罗邦武
熊思醒
蒋友宇
蒋方圆
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Huazhong University of Science and Technology
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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a high-yield organic solar cell and a preparation method thereof, belonging to the field of preparation of photovoltaic devices, wherein the high yield indicates that the number of prepared devices with the efficiency reaching the standard efficiency is more than 95%. Preparing a bottom electrode on a substrate, and preparing a light active layer on the bottom electrode; coating an insulating layer solution on the surface of the defect of the optical active layer to obtain an insulating layer; and preparing a top electrode on the insulating layer and the photoactive layer to obtain the organic solar cell. Before the top electrode of the thin film solar cell is prepared, the insulating layer solution is coated at the defect position of the optical active layer to obtain the insulating layer, and the insulating layer is insulated, so that the short circuit at the defect position is avoided. The method is simple and effective, can greatly improve the yield of the organic solar cell, and has important guiding and practical significance for the field of industrial manufacturing of the thin-film solar cell.

Description

High-yield organic solar cell and preparation method thereof
Technical Field
The invention belongs to the field of photovoltaic device preparation, and particularly relates to a high-yield organic solar cell and a preparation method thereof.
Background
Solar energy is clean, environment-friendly and inexhaustible, and is expected to become the best choice for replacing fossil energy under the large background of energy crisis. Organic solar cells are emerging cells, and through researches on material synthesis and device physics in the last two decades, the photoelectric conversion efficiency of laboratory-prepared organic solar cells exceeds 13%. The organic solar cell has the advantages of solution preparation, flexibility, light weight, low cost, colorful and beautiful appearance and the like, and is widely concerned by academia and industry
The organic solar cell has the greatest advantage that the organic solar cell can be manufactured by a mild low-energy-consumption liquid phase method and adopting the nano-thickness controllable thin film coating technologies such as spin coating, scraper coating and the like. One of the major drawbacks of the liquid phase method for preparing the thin film is that the thin film is easily affected by solid insoluble substances in the solution and pollutants such as dust and fibers in the external environment during the film forming process, or has low wettability caused by the difference between the surface energy of the substrate and the surface energy of the solution, thereby generating the defects of the thin film. In addition, the thickness of the photoactive layer of the thin film battery is only a few hundred nanometers, and the solution scratches due to misoperation and other reasons during the preparation process, so that the thin film defects are generated. The complete cell structure has a layer of photoactive layer (semiconductor), so the volt-ampere curve has obvious diode effect; however, the defect of the defective cell partially lacks the photoactive layer, which results in the reduction of the resistance at the defect, and the large leakage current causes short-circuit leakage, greatly damaging the cell performance and reducing the cell yield, especially the yield of large-area cells suitable for industrial production in the future.
Therefore, the technical problems that the film defect is easily generated, the resistance of the defect part is reduced, the short circuit leakage is caused due to large leakage current, the performance of the battery is greatly damaged, and the yield of the battery is reduced exist in the prior art.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides the organic solar cell with high yield and the preparation method thereof, so that the technical problems that the film defect is easy to generate, the resistance of the defect is reduced, the short circuit leakage is caused by large leakage current, the performance of the cell is greatly damaged, and the yield of the cell is reduced in the prior art are solved.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for manufacturing a high yield organic solar cell, including:
(1) preparing a bottom electrode on a substrate, and preparing a light active layer on the bottom electrode;
(2) coating an insulating layer solution on the surface of the defect of the optical active layer to obtain an insulating layer;
(3) and preparing a top electrode on the insulating layer and the photoactive layer to obtain the organic solar cell. The insulating layer is insulated, so that the short circuit at the defect part of the optical active layer is avoided, and the organic solar cell has high yield.
Further, the thickness of the substrate is 100 mu m-1 mm, and the substrate is one or more of glass, stainless steel, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone and polyimide. The bottom electrode and the top electrode are ITO and PEDOT: PSS, silver nanowires, carbon nanotubes, gold, silver, copper, aluminum, nickel, calcium and chromium, wherein the visible light reflectivity of the bottom electrode and the top electrode is more than 80%, and the thickness of the bottom electrode and the top electrode is 50 nm-1000 nm. The thickness of the optical active layer is 50 nm-500 nm. The thickness of the insulating layer is 100 nm-100 mu m, the solute of the insulating layer solution is polyetherimide, polyethenoxy ethylene imine, 9-dioctyl fluorene-9, 9-bis (N, N-dimethyl amine propyl) fluorene, polyvinyl alcohol, polyethylene oxide, polydimethylsiloxane or polymethyl methacrylate, and the solvent of the insulating layer solution is water, methanol, ethanol, isopropanol or methoxy ethanol. The organic solar cell prepared by the thickness and the material has good performance and high yield.
Further, the specific implementation manner of the step (2) is as follows:
dipping the insulating layer solution by a brush, coating the insulating layer solution on the surface of the defect of the optical active layer, and drying to obtain the insulating layer. The brush is used for dipping the insulating layer solution to repair the defects of the organic solar cell, and the method is simple, effective, economical and practical.
Further, the hairbrush is animal hair, plant fiber or synthetic fiber with the diameter of 80-200 mu m, and the length of the hairbrush is 5-8 cm. The pen touch is a flexible medium, the pen touch can easily move on the surface with undulation, the requirement on the flatness of a substrate material is reduced, the uneven surface can be coated, and the production cost is indirectly reduced; meanwhile, the method is easier to directly operate on special surfaces, such as clothes, buildings and the like, is economical and efficient, omits an intermediate medium, and is a brand-new conceptual application for the solar cell.
Furthermore, the density of the bristles on the brush is 2000/cm210000 roots/cm2The number of the brush hairs of the brush is 500-500000. The coating speed is 1 mm/s-200 mm/s, and the pressure applied during coating is 10 Pa-10000 Pa. The brush with different thicknesses is adopted, the thickness of the pen brush can be controlled by controlling the contact area with the coating medium with different forces, and the method is suitable for performing patterning into a film so as to repair key defects and reduce the influence on non-defects as far as possible. The defects of the active layer are repaired without obviously influencing the performance of the whole device.
In order to achieve the above objects, according to another aspect of the present invention, there is provided a high yield organic solar cell including a substrate, a bottom electrode, a photoactive layer, an insulating layer on a surface of a defect of the photoactive layer, and a top electrode, the top electrode being a cathode when the bottom electrode is an anode; when the bottom electrode is a cathode, the top electrode is an anode; an electron blocking layer is arranged between the anode and the photoactive layer, and a hole blocking layer is arranged between the photoactive layer and the cathode.
Further, the thickness of the substrate is 100 mu m-1 mm, and the substrate is one or more of glass, stainless steel, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone and polyimide; the bottom electrode and the top electrode are ITO and PEDOT: PSS, silver nanowires, carbon nanotubes, gold, silver, copper, aluminum, nickel, calcium and chromium, wherein the visible light reflectivity of the bottom electrode and the top electrode is more than 80%, and the thicknesses of the bottom electrode and the top electrode are 50 nm-1000 nm; the thickness of the optical activity layer is 50 nm-500 nm, the thickness of the insulating layer is 100 nm-100 mu m, the solute of the insulating layer solution is polyetherimide, polyethenoxy ethylene imine, 9-dioctyl fluorene-9, 9-bis (N, N-dimethyl amine propyl) fluorene, polyvinyl alcohol, polyethylene oxide, polydimethylsiloxane or polymethyl methacrylate, the solvent of the insulating layer solution is water, methanol, ethanol, isopropanol or methoxy ethanol, the thickness of the hole blocking layer is 1 nm-50 nm, and the thickness of the electronic blocking layer is 5 nm-30 nm.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following advantages:
1. according to the invention, the insulating layer solution is coated on the surface of the defect of the photoactive layer to obtain the insulating layer, so that the defect of the solar cell is repaired, expensive professional equipment is not required, and the threshold of the process is reduced. The method is simple and effective, can greatly improve the yield of the organic solar cell and the performance of the cell, and has important guiding and practical significance for the field of industrial manufacturing of the thin-film solar cell. The organic solar cell prepared by the invention has high yield, and the high yield indicates that the number of the prepared devices with the efficiency reaching the standard efficiency is more than 95%.
2. The invention adopts the brush for coating, the raw material solution is stored between the hair cavity structures of the brush hair and is uniformly coated on the surface of the next insulating layer along with the brush touch, the solution consumption process can be controlled, the required raw material solution is less, and the production cost is reduced.
3. The brush adopts animal hair, plant fiber or synthetic fiber with the diameter of 80-200 mu m, the length of the brush is 5-8 cm, the brush belongs to a flexible medium, the brush can easily move on the surface with fluctuant height, the requirement on the flatness of a substrate material is reduced, the uneven surface can be coated, and the production cost is indirectly reduced; meanwhile, the method is easier to directly operate on special surfaces, such as clothes, buildings and the like, is economical and efficient, omits an intermediate medium, and is a brand-new conceptual application for the solar cell.
4. The diameter of the bristles on the brush is 80-200 mu m, the length of the brush is 5-8 cm, and the density of the bristles on the brush is 2000 pieces/cm210000 roots/cm2The number of the brush hairs of the brush is 500-500000. The coating speed is 1 mm/s-200 mm/s, and the pressure applied during coating is 10 Pa-10000 Pa. The brush with different thicknesses is adopted, the thickness of the pen brush can be controlled by controlling the contact area with the coating medium with different forces, and the method is suitable for performing patterning into a film so as to repair key defects and reduce the influence on non-defects as far as possible. The defects of the active layer are repaired without obviously influencing the performance of the whole device.
Drawings
Fig. 1 is a schematic diagram illustrating a method for manufacturing a high-yield organic solar cell according to an embodiment of the present invention;
fig. 2 is a current-voltage curve of a solar cell provided in example 1 of the present invention;
fig. 3 is a current-voltage curve of a solar cell provided in example 2 of the present invention;
fig. 4 is a current-voltage curve of a solar cell provided in example 3 of the present invention;
FIG. 5 is a current-voltage curve of a solar cell provided in example 4 of the present invention;
fig. 6 is a current-voltage curve of a solar cell provided in example 5 of the present invention;
fig. 7 is a current-voltage graph of a solar cell provided in example 6 of the present invention;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The solar cell of the invention comprises a substrate (substrate), a bottom electrode (cathode), a cathode layer (hole blocking layer), a photoactive layer, an anode layer (electron blocking layer) and a top electrode (anode) from bottom to top. The battery structure can be inverted, namely, the anode is a bottom electrode, and the anode is sequentially from bottom to top: a substrate, a bottom electrode (anode), an electron blocking layer, a photoactive layer, a hole blocking layer, and a top electrode (cathode). The electron blocking layer and the hole blocking layer play a role in modifying the interface between the corresponding electrode (respectively corresponding to the anode and the cathode) and the optical activity layer, and if the work function of the selected electrode material reaches enough high (anode) or enough low (cathode), the electron blocking layer or the hole blocking layer is unnecessary.
As shown in fig. 1, a method for manufacturing a high yield organic solar cell includes:
(1) preparing a bottom electrode on a substrate, and preparing a light active layer on the bottom electrode; the thickness of the substrate is 100 mu m-1 mm, and the substrate is one or more of glass, stainless steel, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone and polyimide.
(2) Dipping the insulating layer solution by using a brush, coating the insulating layer solution on the surface of the defect of the optical active layer, and drying to obtain an insulating layer; the thickness of the optical active layer is 50 nm-500 nm. The thickness of the insulating layer is 100 nm-100 mu m, the solute of the insulating layer solution is polyetherimide, polyethenoxy ethylene imine, 9-dioctyl fluorene-9, 9-bis (N, N-dimethyl amine propyl) fluorene, polyvinyl alcohol, polyethylene oxide, polydimethylsiloxane or polymethyl methacrylate, and the solvent of the insulating layer solution is water, methanol, ethanol, isopropanol or methoxy ethanol. The hair brush is animal hair, plant fiber or synthetic fiber with the diameter of 80-200 mu m, and the length of the hair brush is 5-8 cm. The density of the bristles on the brush is 2000 bristles/cm210000 roots/cm2The number of the brush hairs of the brush is 500-500000. The coating speed is 1 mm/s-20 mm/s, and the pressure applied during coating is 10 Pa-10000 Pa.
(3) And preparing a top electrode on the insulating layer and the photoactive layer to obtain the organic solar cell. The bottom electrode and the top electrode are ITO and PEDOT: PSS, silver nanowires, carbon nanotubes, gold, silver, copper, aluminum, nickel, calcium and chromium, wherein the visible light reflectivity of the bottom electrode and the top electrode is more than 80%, and the thickness of the bottom electrode and the top electrode is 50 nm-1000 nm.
Preferably, in the embodiment of the present invention, the battery device is, from bottom to top: the bottom electrode (anode or cathode), the modification layer 1 (electron blocking layer or hole blocking layer), the photoactive layer, the modification layer 2 (hole blocking layer or electron blocking layer), and the top electrode (cathode or anode) briefly describe the preparation method;
if the bottom electrode and the top electrode are made of oxides such as ITO, AZO, MgZO and the like, the materials are prepared by vacuum magnetron sputtering or Atomic Layer Deposition (ALD); if the product is PEDOT: the PSS, silver nanowires or carbon nanotubes are prepared by a solution method as follows: preparing by spin coating, scraper coating, screen printing, ink-jet printing, slit printing and the like; if the material is gold, silver, copper, aluminum, nickel, calcium, chromium and other metal materials, the material is prepared by chemical plating or vacuum thermal evaporation deposition. The bottom electrode and the top electrode can be made of one or more of the above materials, so that various preparation processes can be involved;
if the material of the modification layer is polyetherimide, polyethenoxy ethylene imine, 9-dioctyl fluorene-9, 9-bis (N, N-dimethyl amine propyl) fluorene and other polymers, the modification layer is prepared by a solution method such as rotary coating, scraper coating, screen printing, ink-jet printing, slit printing and the like; if it is alkali metal oxide or carbonate, zinc oxide, titanium oxide or acetylacetone base salt, and lithium fluoride. The molybdenum oxide, the fullerene or the fullerene derivative can be deposited by atomic layer deposition and vacuum thermal evaporation deposition, and can also be prepared by a solution method;
and if the material of the light activity layer is poly-3 hexylthiophene, poly {4, 8-bis [ (2-ethylhexyl) oxy ] -benzo [1, 2-b: 4, 5-b '] dithiophene-2, 6-diyl ] [ 3-fluoro-2- [ (2-ethylhexyl) carbonyl ] thieno [3, 4-b ] thiophene-4, 6-diyl ] }, poly [ [9- (1-octylnonyl) -9H-carbazole-2, 7-diyl ] -2, 5-thiophenediyl-2, 1, 3-benzothiadiazole-4, 7-diyl-2, 5-thiophenediyl ], poly (p-phenylene vinylene), poly [ (2, 6- (4, 8-bis (5- (2-ethylhexyl) thiophene-2-substituted) -benzo [1, 2-b: 4, 5-b' ] dithiophene)) -alt- (5, 5- (1 ', 3 ' -di-2-thienyl-5 ', 7 ' -di (2-ethylhexyl) benzo [1 ', 2 ' -c: 4 ', 5 ' -c ' ] dithiophene-4, 8-dione)) ] and fullerene derivatives, 3, 9-bis (2-methylene- (3- (1, 1-dicyanomethylene) -indanone)) -5, 5, 11, 11-tetrakis (4-hexylphenyl) -bithiophene [2, 3-d: 2 ', 3 ' -d ' ] -s-indacene [1, 2-b: 5, 6-b' ] dithiophene), indene or a donor-acceptor heterojunction combination of C60 bis-adducts are prepared using solution processes such as spin coating, doctor blade coating, screen printing, inkjet printing, slit printing, and the like; if the small molecule donor/acceptor is used, the preparation can also be carried out by vacuum thermal evaporation deposition.
The insulating layer, which is a core portion of the present invention, has a thickness of 100nm to 100 μm. The usable materials are wide, and in principle, the materials are only insulated and have certain film-forming property, namely, the prepared solution has certain wettability on the surface of the active layer with high surface energy, and finally a compact insulating protective layer can be formed. Thus, different solvents (which need to be selective and not dissolve the photoactive layer) need to be chosen relative to different materials, and surfactants need to be added as necessary to reduce surface tension to enhance film formation of the insulating layer at the photoactive layer defects.
The bristles of the brush are animal hair or plant fiber with the diameter of 80-200 mu m; the length of the brush hair is 5mm to 8cm, and the density of the brush hair on the brush hair is 2000 pieces/cm210000 roots/cm2When the insulating layer is prepared manually or the area of the insulating layer to be prepared is small, the number of the brush hairs can be increased to about 500000;
the thicker the bristles are, the smaller the density of the bristles is, the thicker the correspondingly prepared insulating layer is, and otherwise, the thinner the insulating layer is; the brush handle of the brush can be made of materials such as bamboo, plastic, alloy and the like.
The speed of brushing by a brush is 1 mm/s-200 mm/s, and the pressure applied during brushing is 10 pa-10000 pa; the lower the brushing speed is, the lower the applied pressure is, the thicker the correspondingly prepared insulating layer is, and the thinner the correspondingly prepared insulating layer is otherwise; meanwhile, the speed of preparing the corresponding insulating layer is positively correlated with the area of the brush and the writing speed. If the thickness of the prepared corresponding insulating layer does not meet the preset requirement, the writing can be performed for many times so as to increase the thickness of the insulating layer.
The brushing mode can be manual, and can also be assisted by a mechanical device to control the brushing pressure and speed, so that the insulating layer with more accurate thickness can be prepared.
To further illustrate the above embodiments, reference is made to the accompanying drawings, which are illustrated in the accompanying drawings and scale, and in which is shown by way of illustration, in order to avoid obscuring the invention in unnecessary detailThe present invention is made clear by the accompanying drawings, which show only the structures and/or process steps that are germane to the solution according to the present invention, and which omit other details that are not germane to the present invention. In the examples and comparative examples, each english abbreviation represents the chinese meaning as follows: ITO-indium tin oxide, P3 HT-poly-3-hexylthiophene, ICBA-indene bis adduct with C60, PEDOT: PSS-poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate, PEI-polyetherimide, PTB 7-Th-poly {4, 8-bis [ (2-ethylhexyl) oxy group]-benzo [1, 2-b: 4, 5-b']Dithiophene-2, 6-diyl][ 3-fluoro-2- [ (2-ethylhexyl) carbonyl group]Thieno [3, 4-b]Thiophene-4, 6-diyl]}，PC71BM-[6，6]-phenyl-C71-methyl butyrate), PVA-polyvinyl alcohol, PEO-polyethylene oxide, PMMA-polymethyl methacrylate, PDMS-polydimethylsiloxane, PBDB-T-poly [ (2, 6- (4, 8-bis (5- (2-ethylhexyl) thiophene-2-substituted) -benzo [1, 2-b: 4, 5-b']Bithiophene)) -alt- (5, 5- (1 ', 3' -di-2-thienyl-5 ', 7' -di (2-ethylhexyl) benzo [1 ', 2' -c: 4 ', 5 ' -c ']Dithiophene-4, 8-dione))]ITIC-3, 9-bis (2-methylene- (3- (1, 1-dicyanomethylene) -indanone)) -5, 5, 11, 11-tetrakis (4-hexylphenyl) -bithiophene [2, 3-d: 2 ', 3 ' -d ']-s-indacene [1, 2-b: 5, 6-b']Bithiophene).
Example 1
The solar cell of example 1 comprises, in order from bottom to top, 2mm of glass as a rigid substrate, 300nm of ITO as a cathode, 5nm of PEI as a hole blocking layer, 180nm of a photoactive layer (comprising P3HT and ICBA in a mass ratio of 1: 1), and 120nm of a transparent anode, the area of the solar cell being about 1cm2. The preparation method specifically comprises the following steps:
s1, taking glass/ITO with the thickness of 2mm as a substrate/cathode, spinning and coating a layer of PEI/isopropanol solution with the mass fraction of 0.1% on the ITO, and heating at 80 ℃ for 2min to obtain a hole blocking layer with the thickness of 5 nm.
S2, dissolving P3HT serving as an active layer donor material and ICBA serving as an active layer acceptor material in a chlorobenzene solution according to the mass ratio of 1: 1 to prepare an optical active layer solution of 40 mg/ml. Then the prepared P3HT/ICBA chlorobenzene solution is rotated at the rotating speed of 600 revolutions per minuteSpin coating on the hole blocking layer in step S1 and annealing at 150 c for 10min to obtain a photoactive layer having a thickness of about 180 nm. At P3 HT: scraping a round ICBA film surface by using forceps, wherein the area of the round ICBA film surface is about 2mm2The defect of (2);
s3, carrying out surface hydrophilic treatment on the photoactive layer, coating a layer of PEI/isopropanol solution with the mass fraction of 10% at the defect position of the photoactive layer, and drying the solution completely. The material of the brush bristles of the brush used for coating is wolf hair, the diameter of the brush bristles is 120 mu m, the length of the brush bristles is 200mm, the density is about 5000 threads per square centimeter, the number of the brush bristles is about 3000, the pressure applied during coating is about 5000pa, the coating speed is 20mm/s, and the coating of the insulating layer can be completed within 1 second. Then coating a layer of PEDOT: PSS solution (PEDOT, namely Heraeus-Clevios PH1000 of PSS solution, PEDOT, namely 5-6% of PSS solid content, and 0.1% of surfactant PEG-TmDD and TOYNOLV R Superwet-340 in mass fraction are added into the solution); the material of the bristles of the brush used for coating is goat hair, the diameter of the bristles is 100 μm, the length of the bristles is 120mm, the density is about 4000 per square centimeter, the number of the bristles is about 800, the pressure applied during coating is about 2000pa, the coating speed is 20mm/s, therefore, the coating of the anode layer of the solar cell can be completed within 1 second, the anode layer is dried for 5min at 120 ℃, and the PEDOT of 120nm is obtained: PSS is used as an anode layer to obtain the solar cell.
Comparative example 1
Example 1 was repeated with the same procedure, except that in said step S3 PEDOT was applied directly: PSS, no insulating layer was applied.
Example 2
The solar cell of example 2 comprises, in order from the bottom to the top, 2mm thick glass as a hard substrate, 300nm of ITO as a cathode, 5nm of PEI as a hole blocking layer, 180nm of a photoactive layer (comprising PBDB-T and ITIC in a mass ratio of 1: 1), and 10nm of molybdenum oxide as an electron blocking layer, and 80nm of silver as an anode. The area of the solar cell is about 100mm2. The preparation method specifically comprises the following steps:
s1, taking glass/ITO with the thickness of 2mm as a substrate/cathode, spinning a layer of zinc acetate/ethanolamine/dimethoxy ethanol solution on the ITO, and heating at 200 ℃ for 20min to obtain a hole blocking layer with the thickness of 20 nm.
S2, PBDB-T is used as an active layer donor material, ITIC is used as an active layer acceptor material, the PBDB-T and the ITIC are dissolved in chlorobenzene solution according to the mass ratio of 1: 1 to prepare a 20mg/ml photoactive layer solution, and diiodooctane with the mass fraction of 0.5% is added as an additive. And then the prepared PBDB-T: spin-coating the ITIC chlorobenzene solution on the hole blocking layer in the step S1 at a rotation speed of 2500 rpm, and performing annealing treatment at 160 ℃ for 10min to obtain an optical active layer with the thickness of about 100 nm; in PBDB-T: scraping a round surface of the ITIC film with tweezers, wherein the area of the round surface is about 2mm2The defect of (2).
S3, coating a layer of PEI/isopropanol insulating layer solution with the mass fraction of 10% at the defect position of the optical active layer, and drying the PEI/isopropanol insulating layer solution thoroughly. A layer of molybdenum oxide 10nm thick was then deposited by vacuum thermal evaporation followed by thermal evaporation of a layer of silver 80nm thick.
Comparative example 2
Example 2 was repeated in the same procedure except that, in said step S3, molybdenum oxide and silver were directly vacuum-thermally vapor-deposited, and an insulating layer was not coated,
example 3
Example 2 was repeated with the same procedure except that in said step S3, before depositing molybdenum oxide and silver by vacuum thermal evaporation, a layer of PVA/water solution with a mass fraction of 20% (with the addition of 2% mass fraction of the surfactant PEG-TmDD) was applied at the photoactive layer defects and allowed to dry out.
Example 4
Example 2 was repeated with the same procedure, except that in said step S3, a layer of PMMA/acetone solution with a mass fraction of 15% was applied at the defect of the photoactive layer and left to dry out before the deposition of molybdenum oxide and silver by vacuum thermal evaporation.
Example 5
Example 2 was repeated with the same procedure except that in said step S3, a layer of PEO/water solution with a mass fraction of 5% (2% mass fraction of surfactant PEG-TmDD was added) was coated at the photoactive layer defects and left to dry out before the deposition of molybdenum oxide and silver by vacuum thermal evaporation.
Example 6
Example 2 was repeated with the same procedure except that in said step S3, before depositing molybdenum oxide and silver by vacuum thermal evaporation, a layer of PDMS (composition ratio of a: B10: 1) was applied at the photoactive layer defects and left to dry out.
Example 7
Example 2 was repeated in the same procedure except that in said step S3, the defect area was 1mm2. And before depositing molybdenum oxide and silver by vacuum thermal evaporation, coating a layer of PVA/water solution with the mass fraction of 20% (adding 2% of surfactant PEG-TmDD) at the defect part of the photoactive layer and allowing the PVA/water solution to dry out.
Example 8
Example 7 was repeated in the same procedure except that in said step S3, the defect area was 2mm2。
Example 9
Example 7 was repeated in the same procedure except that in said step S3, the defective area was 3mm2。
Example 10
Example 7 was repeated in the same procedure except that in said step S3, the defect area was 5mm2。
Example 11
Example 7 was repeated in the same procedure except that in said step S3, the defective area was 10mm2。
Example 12
Example 7 was repeated in the same procedure except that in said step S3, the defect area was 15mm2。
Comparative example 3
Example 2 was repeated in the same procedure except that in said step S3, the defect area was 1mm2And no insulating layer is applied.
Comparative example 4
Example 2 was repeated in the same procedure except that in said step S3, the defect area was 2mm2And no insulating layer is applied.
Comparative example 5
Example 2 was repeated in the same procedure except that in said step S3, the defect area was 3mm2And no insulating layer is applied.
Comparative example 6
Example 2 was repeated in the same procedure except that in said step S3, the defect area was 5mm2And no insulating layer is applied.
Comparative example 7
Example 2 was repeated in the same procedure except that in said step S3, the defect area was 10mm2And no insulating layer is applied.
Comparative example 8
Example 2 was repeated in the same procedure except that in said step S3, the defect area was 15mm2And no insulating layer is applied.
Analysis of Experimental results
The light intensity is 100mW/cm2FIG. 2 is a graph showing a current-voltage curve measured under AM 1.5 white light irradiation, and the solar cell prepared in comparative example 1 has an open-circuit voltage of 0.08V and a short-circuit current of 8.5mA/cm2Fill factor 0.24, efficiency 0.17%, while the open circuit voltage of 0.80V and short circuit current of 9.8mA/cm for the solar cell prepared in example 12Fill factor 0.53, efficiency 4.2%. PEI is a material commonly used for a hole blocking layer of an organic solar cell, and can only be made very thin (5-10 nm) due to insulation. However, as the insulating layer, a thick insulating layer (100nm or more) is coated on the defect by increasing the solution concentration (100 times) by utilizing the insulating property, so as to avoid short circuit caused by direct contact between the bottom electrode and the top electrode through the defect on the photoactive layer. From the comparison results, the unrepaired device (comparative example 1) has obvious short circuit, and the voltage and the fill factor are both extremely low. The photovoltaic parameters of the repaired device (example 1) were relatively normal. (area considerations are taken into account here because the device active area is 1 square centimeter, relatively large, and performance is compromised for devices of several square millimetersLost) of the twenty devices prepared by repeating this example through the brush repair method, the efficiency of the devices exceeding 4.0% reached 19, and the yield was 95%.
The light intensity is 100mW/cm2FIG. 3 shows the current-voltage curve measured under AM 1.5 white light irradiation, the open-circuit voltage of the cell prepared in comparative example 2 was 0.1V, and the short-circuit current was 11.2mA/cm2Fill factor 0.24, efficiency 0.27%, while the open circuit voltage of 0.62V and short circuit current of 13.4mA/cm for example 22Fill factor 0.42, efficiency 3.5%. In comparative example 2, similar to comparative example 1, the interface layer, the photoactive layer, the electrode, and the like are made of different materials, but the deterioration of the device performance is essentially caused by short circuit due to defects. Example 2 here employs the same strategy as example 1: defects were repaired by applying high concentrations of PEI solution, but the 3.5% efficiency did not match the PBDB-T: normal level of the ITIC material system (laboratory efficiency of the system can reach about 9% generally). This is due to the fact that ITIC acts as a non-fullerene acceptor with backbone-end donor-acceptor units in the molecule, i.e. charge transfer, and PEI acts as an electron donor (macroscopically understood as PH being basic) and reacts with the ITIC end groups, causing internal failure to transport charge, resulting in ITIC poisoning. Therefore, PEI, which is originally an insulating layer material suitable for a fullerene system receptor (such as ICBA, PCBM and the like), is not suitable for an ITIC system receptor, and in the experimental process, it can be observed that if a device is placed for a long time, the color of an optical activity layer around an insulating layer is gradually changed from dark blue to light yellow, which shows that PEI not only reacts with the optical activity layer covered by the PEI, but also diffuses and influences the whole battery. Therefore, the battery of example 2, although avoiding the short-circuit phenomenon, did not achieve the desired efficiency. PEI is not suitable as a material for repairing the insulating layer of this material system (PBDB-T: ITIC). However, of the twenty devices prepared by repeating this example by the brush repair method, 20 devices with an efficiency of more than 3.3% were obtained with a yield of 100%.
Also at a light intensity of 100mW/cm2Current measurements were made on examples 3, 4, 5, 6 under AM 1.5 white light illuminationThe voltage curves are shown in fig. 4, 5, 6, 7, respectively, and are normal, illustrating four insulating layer materials for examples 3, 4, 5, 6: PVA, PMMA, PEO, PDMS can be used as the material of the insulating layer. Area considerations need to be taken into account here because the active area of the device is 1 square centimeter, relatively large, and performance is lost for a device of a few square millimeters. The yield of twenty devices prepared by repeating the brush repair method corresponding to each example was over 95%.
The light intensity is 100mW/cm2When the current-voltage curves of examples 7 to 12 were measured under AM 1.5 white light irradiation, it can be seen that for different defect areas of the photoactive layer energy, normal and non-short-circuited cell performance can be obtained by repairing the insulating layer PVA at the defect with the brush, but only as the defect area increases, the short-circuit current density of the cell decreases slightly, resulting in the efficiency of the cell decreasing from 7.16% to 6.01%. This is because defects at the photoactive layer no longer output current under illumination due to the overlying insulating layer. In both laboratory and industrial applications, the defect rate of 15% (i.e. 15mm defects in 1cm device active area) is a hypothetical value in most cases, and generally does not reach such an exaggerated rate (considering process maturity and yield cost), but even under such severe conditions, the device after repairing the defects can still maintain more than eighty percent of the efficiency (accounting for lost area) of the intact device, and thus the repairing effect of the method is very effective and reliable.
In contrast, the intensity of light was 100mW/cm2When the current-voltage curve is measured for comparative example 3-comparative example 8 under the AM 1.5 white light irradiation condition, along with the increase of the defect area of the optical active layer, the isolation of the insulating layer does not exist at the defect position, the short circuit phenomenon of the device is serious, and the efficiency is reduced from 7.16% when no defect exists to 15mm when the defect area is 15mm20.15% of (1).
In summary, it can be seen from the analysis of the above examples that the use of the brush as a tool to repair the defects of the organic solar cell is convenient and effective, and the cost threshold is reduced compared to the professional expensive coating and printing equipment itself. In the current organic solar cell preparation process, the attention to defects of the energy thin film of the photoactive layer is less, and people are aware that the defects have great influence on the cell performance and reduce the production yield, but the attention is not paid to the defects. Particularly in the production of large-area batteries, one thin film defect may result in a battery performance degradation of several square meters. It is common practice to screen out these defective cells, which is wasteful, and the use of brushes as a tool to repair the defects of organic solar cells is a simple and effective solution to this problem. The brush, as an eastern-derived coating and painting tool, has its unique and valuable features compared to most western-derived printing technologies, and is worthy of further development in the future.
Example 13
A preparation method of a high-yield organic solar cell comprises the following steps:
(1) preparing a bottom electrode on a substrate, and preparing a light active layer on the bottom electrode; the thickness of the substrate is 100 μm, and the substrate is stainless steel.
(2) Dipping the insulating layer solution by using a brush, coating the insulating layer solution on the surface of the defect of the optical active layer, and drying to obtain an insulating layer; the thickness of the photoactive layer was 50 nm. The thickness of the insulating layer is 100nm, the solute of the insulating layer solution is polyetherimide, and the solvent of the insulating layer solution is water. The brush is animal hair with the diameter of 80 mu m, and the length of the brush is 5 mm. The density of the bristles on the brush is 2000 bristles/cm2The number of bristles of the brush is 500. The coating speed was 1mm/s, and the pressure applied during coating was 10 pa.
(3) And preparing a top electrode on the insulating layer and the photoactive layer to obtain the organic solar cell. The bottom electrode and the top electrode are made of ITO, and the thickness of the bottom electrode and the thickness of the top electrode are 50 nm.
Example 14
A preparation method of a high-yield organic solar cell comprises the following steps:
(1) preparing a bottom electrode on a substrate, and preparing a light active layer on the bottom electrode; the thickness of the substrate is 1mm, and the substrate is polymethyl methacrylate.
(2) Dipping the insulating layer solution by using a brush, coating the insulating layer solution on the surface of the defect of the optical active layer, and drying to obtain an insulating layer; the thickness of the photoactive layer was 500 nm. The thickness of the insulating layer is 100 mu m, the solute of the insulating layer solution is polyethoxy ethylene imine, and the solvent of the insulating layer solution is isopropanol. The brush is made of plant fibers with the diameter of 200 mu m, and the length of the brush is 8 cm. The density of the bristles on the brush is 10000 bristles/cm2The number of bristles of the brush was 500000. The coating speed was 20mm/s, and the pressure applied at the time of coating was 10000 pa.
(3) And preparing a top electrode on the insulating layer and the photoactive layer to obtain the organic solar cell. The bottom electrode and the top electrode are silver nanowires, and the thickness of the bottom electrode and the top electrode is 1000 nm.
Example 15
A preparation method of a high-yield organic solar cell comprises the following steps:
(1) preparing a bottom electrode on a substrate, and preparing a light active layer on the bottom electrode; the thickness of the substrate was 500 μm, and the substrate was polyethylene naphthalate.
(2) Dipping the insulating layer solution by using a brush, coating the insulating layer solution on the surface of the defect of the optical active layer, and drying to obtain an insulating layer; the thickness of the photoactive layer was 250 nm. The thickness of the insulating layer is 50 microns, the solute of the insulating layer solution is 9, 9-dioctyl fluorene-9, 9-bifluorene, and the solvent of the insulating layer solution is methoxy ethanol. The brush is a synthetic fiber with a diameter of 100 μm, and the length of the brush is 1 cm. The density of the bristles on the brush is 5000 bristles/cm2The number of the brush hairs of the brush is 10000. The coating speed was 200mm/s and the pressure applied during coating was 100 pa.
(3) And preparing a top electrode on the insulating layer and the photoactive layer to obtain the organic solar cell. The bottom electrode and the top electrode are carbon nanotubes, and the thickness of the bottom electrode and the top electrode is 500 nm.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (9)

1. A preparation method of a high-yield organic solar cell is characterized by comprising the following steps:
(1) preparing a bottom electrode on a substrate, and preparing a light active layer on the bottom electrode;
(2) dipping the insulating layer solution by using a brush, coating the insulating layer solution on the surface of the defect of the optical active layer, and drying to obtain an insulating layer;
(3) preparing a top electrode on the insulating layer and the optical activity layer to obtain the organic solar cell, wherein the insulating layer is insulated, so that the short circuit at the defect part of the optical activity layer is avoided, and the organic solar cell has high yield;
the solute of the insulating layer solution is polyetherimide, polyethenoxy ethylene imine, 9-dioctyl fluorene-9, 9-bis (N, N-dimethyl amine propyl) fluorene, polyvinyl alcohol, polyethylene oxide, polydimethylsiloxane or polymethyl methacrylate, and the solvent of the insulating layer solution is water, methanol, ethanol, isopropanol or methoxy ethanol;
the thickness of the insulating layer is 100 nm-100 mu m, and if the thickness of the insulating layer does not meet the preset requirement, the thickness of the insulating layer is increased by brushing for many times;
the brush with different thicknesses is adopted, the thickness of the pen brush can be controlled by controlling the contact area of the brush with the coating medium with different forces, and the brush is suitable for being patterned into a film to repair the defect.
2. The method according to claim 1, wherein the substrate has a thickness of 100 μm to 1mm, and is one or more of glass, stainless steel, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, and polyimide.
3. The method according to claim 1, wherein the bottom electrode and the top electrode are one or more of ITO, PEDOT PSS, silver nanowires, carbon nanotubes, gold, copper, aluminum, nickel, calcium, and chromium, and the thickness of the bottom electrode and the top electrode is 50nm to 1000 nm.
4. The method of claim 1, wherein the thickness of the photoactive layer is 50nm to 500 nm.
5. The method according to claim 1, wherein the brush is made of animal hair, plant fiber or synthetic fiber with a diameter of 80-200 μm, and the length of the brush is 5-8 cm.
6. The method according to claim 1, wherein the density of the bristles on the brush is 2000/cm210000 roots/cm2The number of the brush hairs of the brush is 500-500000.
7. The method according to claim 1, wherein the coating speed is 1mm/s to 200mm/s, and the pressure applied during coating is 10Pa to 10000 Pa.
8. A high-yield organic solar cell is prepared by the preparation method of the high-yield organic solar cell according to any one of claims 1 to 7, the organic solar cell comprises a substrate, a bottom electrode, a photoactive layer, an insulating layer on the surface of a defect of the photoactive layer and a top electrode, and when the bottom electrode is an anode, the top electrode is a cathode; when the bottom electrode is a cathode, the top electrode is an anode; an electron blocking layer is arranged between the anode and the photoactive layer, and a hole blocking layer is arranged between the photoactive layer and the cathode.
9. The high-yield organic solar cell according to claim 8, wherein the substrate has a thickness of 100 μm to 1mm, and is one or more of glass, stainless steel, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, and polyimide; the bottom electrode and the top electrode are made of one or more of ITO (indium tin oxide), PEDOT (PEDOT-lithium niobate), PSS (silver nanowire), carbon nanotube, gold, copper, aluminum, nickel, calcium and chromium, and the thickness of the bottom electrode and the top electrode is 50 nm-1000 nm; the thickness of the photoactive layer is 50 nm-500 nm, the thickness of the insulating layer is 100 nm-100 mu m, the solute of the insulating layer solution is polyetherimide, polyethoxyethyleneimine, 9-dioctylfluorene-9, 9-bifluorene, polyvinyl alcohol, polyethylene oxide, polydimethylsiloxane or polymethyl methacrylate, the solvent of the insulating layer solution is water, methanol, ethanol, isopropanol or methoxyethanol, the thickness of the hole blocking layer is 1 nm-50 nm, and the thickness of the electron blocking layer is 5 nm-30 nm.
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