CN111180588A - Thick-film organic solar cell based on continuous blade coating double-body heterojunction and preparation method thereof - Google Patents
Thick-film organic solar cell based on continuous blade coating double-body heterojunction and preparation method thereof Download PDFInfo
- Publication number
- CN111180588A CN111180588A CN201911401558.XA CN201911401558A CN111180588A CN 111180588 A CN111180588 A CN 111180588A CN 201911401558 A CN201911401558 A CN 201911401558A CN 111180588 A CN111180588 A CN 111180588A
- Authority
- CN
- China
- Prior art keywords
- active layer
- heterojunction
- solar cell
- organic solar
- blade coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- H10K30/211—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions comprising multiple junctions, e.g. double heterojunctions
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to a thick film organic solar cell based on continuous blade coating double-body heterojunction, which adopts an inversion structure, an active layer consists of a bottom heterojunction active layer and a top heterojunction active layer, and the bottom heterojunction active layer and the top heterojunction active layer form a continuous and mutually-permeable vertical gradient distribution phase. The quaternary efficient thick-film organic solar cell device is prepared, the problems of poor vertical phase separation in an optical active layer of the organic solar cell and low separation and transmission efficiency of photo-generated carriers are solved under the condition of effectively improving the optical absorption capacity of the organic solar cell device, ohmic contact with a cathode/anode buffer layer can be effectively formed by further using different system double-body heterojunction structures, and the problems of large interface contact resistance of the organic solar cell, high carrier recombination probability and finally reduced device performance are effectively solved.
Description
Technical Field
The invention relates to the technical field of organic polymer photovoltaic devices or new energy solar cells, in particular to a thick film organic solar cell based on continuous blade coating double-body heterojunction and a preparation method thereof.
Background
With the rapid development of the world economy and the gradual update of scientific technology, the demand of human beings on energy is increasing day by day, however, the two major problems of the sudden decrease of the fossil energy reserves and the environmental pollution caused by the excessive use of the traditional fossil energy also appear, so the development and utilization of novel clean energy are considered as a key project of the new century. Under the background, solar energy is a renewable green energy source, and is widely concerned by researchers due to the characteristics of inexhaustibility, wide distribution, complete greenness, no pollution and the like. Solar cells are becoming the leading-edge research field as a means for developing and utilizing solar energy that can directly convert solar energy into electrical energy. Solar cells can be simply classified into inorganic and organic semiconductor material solar cells according to the difference of the materials of the photoactive layer of the solar cell. Inorganic semiconductor material solar cells are widely researched due to early development and initiation, and have already been applied to commercial cells. However, the battery device of this type has a complex preparation process, high manufacturing cost and environmental pollution, and the like, which limits the further development of the battery device. On the contrary, the organic solar cell prepared based on the organic semiconductor material not only has the highest theoretical photoelectric conversion efficiency as the inorganic solar cell, but also has a series of advantages of simple process, wide material source, capability of being prepared based on a flexible substrate, large-area production, environmental friendliness, no pollution, light weight, low cost and the like, so that the organic solar cell becomes a hope for solving the energy crisis.
In the past 10 years, in order to solve the problems of narrow spectral absorption range and insufficient photoelectric conversion efficiency of a single-junction active layer organic solar cell device, researchers have proposed different strategies such as ternary mixing, quaternary mixing, thick film preparation and laminated device preparation, and the researches effectively improve the performance of the organic solar cell device from the initial performance of less than 2.5% to the current maximum performance of 17.3%.
However, these current improvement methods have advantages and disadvantages, such as the multi-component mixed mode can effectively broaden the spectrum absorption, but the work mechanism and efficacy explanation research of each part is insufficient when multiple materials are mixed in a single film; the preparation of thick film devices can also improve the photoproduction current, but due to the influence of the film thickness and the aggregation characteristic of organic materials, organic molecules are easy to aggregate in the active layer to form a large-scale pure phase state, thereby preventing the exciton separation of photoproduction charges in the active layer; the laminated device, as a high-performance organic solar cell preparation process which is widely paid attention by researchers at present, has high preparation cost and more complicated preparation processes, and is therefore not beneficial to the commercial production of organic solar cells. Therefore, research on how to realize the preparation of the multi-component mixed thick-film high-efficiency organic solar cell by using a simple preparation process becomes the focus of current research.
Disclosure of Invention
The invention aims to: the thick film organic solar cell and the preparation method thereof based on continuous blade coating double-body heterojunction are provided, a quaternary efficient thick film organic solar cell device is prepared, the problems of separation and low transmission efficiency of photo-generated carriers caused by poor vertical phase separation in an optical active layer of the organic solar cell are solved under the condition of effectively improving the light absorption capacity of the organic solar cell device, ohmic contact can be effectively formed between the organic solar cell device and a cathode/anode buffer layer by using different system double-body heterojunction structures, and the problems of large interface contact resistance, high carrier recombination probability and finally reduced device performance of the organic solar cell are effectively solved.
The technical scheme adopted by the invention is as follows: the thick film organic solar cell based on continuous blade coating double-body heterojunction adopts an inversion structure and comprises an active layer, wherein the active layer consists of a bottom heterojunction active layer and a top heterojunction active layer, and the bottom heterojunction active layer and the top heterojunction active layer form a continuous and mutually-permeable vertical gradient distribution phase state.
The organic solar cell adopts an inverted structure and sequentially comprises a substrate, a transparent conductive cathode ITO, a ZnO cathode buffer layer, a photoactive layer and MoO from bottom to top3An anode buffer layer, a metal anode; the continuous blade coating process comprisesFirstly, coating a bottom layer bulk heterojunction solution on a ZnO cathode buffer layer in a scraping mode to prepare a bottom layer bulk heterojunction active layer, heating and annealing properly, and then coating a top layer bulk heterojunction solution on the bottom layer bulk heterojunction active layer heated at constant temperature in a scraping mode to prepare a top layer bulk heterojunction active layer.
Furthermore, the thickness range of the active layer is 100-400 nm.
Further, the substrate heterojunction active layer is formed by an electron donor material PffBT4T-2OD (poly [ (4, 7-bis (4- (2-ethylhexyl) thiophen-2-yl) -5, 6-difluorobenzo [ C ]][1，2，5]Thiadiazole-5, 5-diyl) ([2, 2']Bithiophene-5, 5' -diyl)]) And receptor material PC71Preparing BM mixed solution; the thickness range is 120-220 nm.
Further, the top bulk heterojunction active layer is prepared from a mixed solution of a donor material PBDB-T-SF and an acceptor non-fullerene material IT-4F.
Furthermore, the inversion structure comprises a substrate, a transparent conductive cathode ITO, a cathode buffer layer, a light activity layer, an anode buffer layer and a metal anode from bottom to top in sequence.
Furthermore, the cathode buffer layer is made of ZnO, and the thickness range is 20-50 nm.
Further, the transparent conductive cathode ITO material is one or more of Ag, Al or Au, and the thickness range is 100-200 nm.
Further, the substrate material is glass or a transparent polymer, and the transparent polymer material is one or more of polyethylene, polymethyl methacrylate, polycarbonate, polyurethane, polyimide, vinyl chloride-vinyl acetate resin and polyacrylic acid.
A method for preparing a thick film organic solar cell based on continuous blade coating double-body heterojunction comprises mixing a base heterojunction active layer mixed solution PffBT4T-2OD to PC71After BM is dripped on the cathode buffer layer, a blade coating process is used for preparing a substrate heterojunction active layer, and heating treatment is carried out; then placing on a constant temperature heating table, dripping a top heterojunction active layer mixed solution PBDB-T-SF: IT-4F on the bottom heterojunction active layer, and preparing the top heterojunction active layer by using a blade coating processAnd carrying out thermal annealing.
The method effectively utilizes the characteristic that the bottom heterojunction active layer needs to be dissolved at high temperature, ensures that the top heterojunction solution can not completely dissolve the bottom heterojunction active layer under the same solvent condition, and simultaneously leads the top heterojunction solution to penetrate into the bottom heterojunction active layer due to the eutectic property of the solvent, thereby promoting the double-body heterojunction to form a vertical gradient distribution phase state with continuous mutual penetration. Based on the structure, the thick film organic solar cell can capture more incident photons to further improve the short-circuit current of the device, meanwhile, the vertical gradient distribution phase state of mutual permeation can effectively enhance the charge separation and transmission capacity in the photoactive layer, further, by selecting a proper bulk heterojunction active layer as a bottom/top bulk heterojunction active layer, the contact between the photoactive layer and a cathode/anode buffer layer can be improved, the ohmic contact is promoted to be formed, the contact resistance formed between interfaces is reduced, the charge transmission capacity between different functional layers is further improved, and finally the purpose of improving various performance parameters of the organic solar cell device is achieved.
Further, the mixed solution PffBT4T-2OD PC of the substrate heterojunction active layer71The mass percentage of BM is 1: 6-6: 1, and the concentration is 10-30 mg/ml; the mixed solution PBDB-T-SF of the top heterojunction active layer: the mass percentage of IT-4F is 1: 6-6: 1, and the concentration is 10-30 mg/ml.
Furthermore, the heating treatment and the annealing mode adopt one or more of constant temperature heating table heating, oven heating, far infrared heating and hot air heating.
Further, the heating temperature treatment range is 50-100 ℃.
A preparation method of a thick film organic solar cell based on continuous blade coating double-body heterojunction comprises the following specific steps:
(1) cleaning a base plate consisting of a substrate and a conductive cathode, and drying by using nitrogen after cleaning;
(2) rotationally coating, printing or spraying a cathode buffer layer on the surface of the transparent conductive cathode ITO, and carrying out thermal annealing;
(3) a bottom bodyMixed solution PffBT4T-2OD PC of heterojunction active layer71After BM is dripped on the cathode buffer layer, a blade coating process is used for preparing a substrate heterojunction active layer, and heating treatment is carried out;
(4) placing the substrate processed in the step (3) on a constant-temperature heating table, dripping a top heterojunction active layer solution PBDB-T-SF: IT-4F on the bottom heterojunction active layer, preparing the top heterojunction active layer by using a blade coating process, and carrying out thermal annealing;
(5) at a vacuum degree of 3 x 10-3Under the condition of Pa, MoO is evaporated on the surface of the optical active layer3Preparing an anode buffer layer;
(6) at a vacuum degree of 3 x 10-4And (6) evaporating the metal anode under the Pa condition.
Further, rotationally coating, printing or spraying a cathode buffer layer ZnO sol-gel precursor solution on the surface of the transparent conductive cathode ITO, and carrying out thermal annealing; the thermal annealing temperature range is 200-250 ℃, and the time range is 1-2 h.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) PpfBT 4T-2OD used in the present invention: PC (personal computer)71The BM substrate heterojunction active layer solution is a mixed system which has low solubility in chlorobenzene and needs high-temperature dissolution, and based on the BM substrate heterojunction active layer solution, the scraping coating of the top heterojunction active layer PBDB-T-SF is ensured: when the IT-4F chlorobenzene solution is used, the chlorobenzene solution cannot excessively damage the bottom heterojunction active layer, and the problem that the performance of the traditional laminated device is reduced by using an orthogonal solvent is avoided;
(2) by using the structure of the double-body heterojunction, 4 organic materials are combined in a single active layer, and the 4 materials are arranged in a continuous energy level manner, so that the absorption spectrum range of the unijunction organic solar cell is effectively widened, the short-circuit current density (Jsc) of the device is further improved, and the transmission efficiency of a photon-generated carrier in the active layer is guaranteed;
(3) by using two proper system body heterojunctions, the bottom/top heterojunctions can be ensured to form good ohmic contact with the cathode/anode buffer layer respectively, the transmission capability of charge carriers between interfaces is effectively improved, and further, the bottom/top heterojunctions are coated with a top heterojunction active layer PBDB-T-SF by blade coating: in the case of IT-4F chlorobenzene solution, since the same solvent was used, PBDB-T-SF: the IT-4F chlorobenzene solution can partially permeate into the active layer of the substrate heterojunction to form a phase state of mutual permeation of the double-body heterojunction, so that the separation and the transmission capability of charge carriers in the active layer are effectively improved, and the performance of the organic solar cell device is further improved.
Drawings
FIG. 1 is a schematic structural diagram of a thick film organic solar cell based on continuous scrape coating double-body heterojunction according to the invention;
FIG. 2 is a schematic diagram of the phase state of the inner part of the photoactive layer of the thick film organic solar cell with continuous blade coating double-bulk heterojunction;
the reference signs are: 1-substrate, 2-transparent conductive cathode ITO, 3-cathode buffer layer, 4-optical active layer, 5-anode buffer layer and 6-metal anode; 401-substrate heterojunction active layer PffBT4T-2OD PC71BM phase morphology, 402-top-bulk heterojunction active layer PBDB-T-SF: IT-4F phase morphology.
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 detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will be further described with reference to FIGS. 1 to2 and examples 1 to 12.
Example 1 (control group):
(1) cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive cathode ITO2, and drying by using nitrogen after cleaning;
(2) coating ZnO (5000rpm, 50s and 40nm) on the surface of the transparent conductive cathode ITO2 in a rotating manner to prepare a cathode buffer layer 33, and carrying out thermal annealing treatment (200 ℃, 2h) on the formed film;
(3) dripping PffBT4T-2OD, PC71BM, PBDB-T-SF, ITT-4F (1: 1.2: 1, 31mg/m1) solution on the cathode buffer layer 3, preparing an optical active layer 4(300nm) by adopting a blade coating process, and carrying out thermal annealing treatment (110 ℃, 10 min);
(4) an anode buffer layer 5MoO3(15nm) is evaporated on the photoactive layer 4;
(5) metal anode Ag (100nm) is evaporated on the anode buffer layer 5;
(6) under standard test conditions: AM 1.5, 100mW/cm2, and the open-circuit Voltage (VOC), short-circuit current (JSC), Fill Factor (FF), and Photoelectric Conversion Efficiency (PCE) of the device were measured to be 0.83V, 19.21mA/cm2, 0.67, and 10.68%, respectively.
Example 2:
(1) cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive cathode ITO2, and drying by using nitrogen after cleaning;
(2) coating ZnO (5000rpm, 50s and 40nm) on the surface of the transparent conductive cathode ITO2 in a rotating manner to prepare a cathode buffer layer 3, and carrying out thermal annealing treatment (200 ℃, 2h) on the formed film;
(3) dripping PffBT4T-2 OD: PC71BM (1: 1.2, 11mg/ml) solution on the cathode buffer layer 3, preparing a bottom light active layer 4(120nm) by adopting a blade coating process, and heating (50 ℃ for 10 min);
(4) placing the substrate on a constant temperature heating table at 50 ℃, dripping PBDB-T-SF: ITT-4F (1: 1, 18mg/ml) solution on the bottom heterojunction active layer, preparing a top light active layer 4(100nm) by adopting a blade coating process, and carrying out thermal annealing treatment (110 ℃, 10 min);
(5) an anode buffer layer 5MoO3(15mm) is evaporated on the photoactive layer 4;
(6) metal anode Ag (100nm) is evaporated on the anode buffer layer 5;
(7) under standard test conditions: AM 1.5, 100mW/cm2, and the open-circuit Voltage (VOC) of the device was measured to be 0.85V, the short-circuit current (JSC) was measured to be 20.34mA/cm2, the Fill Factor (FF) was measured to be 0.69, and the Photoelectric Conversion Efficiency (PCE) was measured to be 11.93%.
Example 3:
(1) cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive cathode ITO2, and drying by using nitrogen after cleaning;
(2) coating ZnO (5000rpm, 50s and 40nm) on the surface of the transparent conductive cathode ITO2 in a rotating manner to prepare a cathode buffer layer 3, and carrying out thermal annealing treatment (200 ℃, 2h) on the formed film;
(3) dripping PffBT4T-2 OD: PC71BM (1: 1.2, 13.2mg/ml) solution on the cathode buffer layer 3, preparing a bottom light active layer 4(140nm) by adopting a blade coating process, and carrying out heating treatment (50 ℃ for 10 min);
(4) placing the substrate on a constant temperature heating table at 50 ℃, dripping PBDB-T-SF: ITT-4F (1: 1, 18mg/ml) solution on the bottom heterojunction active layer, preparing a top light active layer 4(100nm) by adopting a blade coating process, and carrying out thermal annealing treatment (110 ℃, 10 min);
(5) an anode buffer layer 5MoO3(15nm) is evaporated on the photoactive layer 4;
(6) metal anode Ag (100nm) is evaporated on the anode buffer layer 5;
(7) under standard test conditions: AM 1.5, 100mW/cm2, and the open-circuit Voltage (VOC), short-circuit current (JSC), Fill Factor (FF), and Photoelectric Conversion Efficiency (PCE) of the device were measured to be 0.86V, 20.98mA/cm2, and 12.45%.
Example 4:
(1) cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive cathode ITO2, and drying by using nitrogen after cleaning;
(2) coating ZnO (5000rpm, 50s and 40nm) on the surface of the transparent conductive cathode ITO2 in a rotating manner to prepare a cathode buffer layer 3, and carrying out thermal annealing treatment (200 ℃, 2h) on the formed film;
(3) the cathode buffer layer 3 was coated with PffBT4T-2 OD: preparing a bottom light active layer 4(160nm) from a PC71BM (1: 1.2, 15.4mg/ml) solution by a blade coating process, and heating (50 ℃ for 10 min);
(4) placing the substrate on a constant temperature heating table at 50 ℃, dripping PBDB-T-SF: ITT-4F (1: 1, 18mg/ml) solution on the bottom heterojunction active layer, preparing a top light active layer 4(100nm) by adopting a blade coating process, and carrying out thermal annealing treatment (110 ℃, 10 min);
(5) an anode buffer layer 5MoO3(15nm) is evaporated on the photoactive layer 4;
(6) metal anode Ag (100nm) is evaporated on the anode buffer layer 5;
(7) under standard test conditions: AM 1.5, 100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.87V, the short-circuit current (JSC) was measured to be 21.52mA/cm2, the Fill Factor (FF) was measured to be 0.70, and the Photoelectric Conversion Efficiency (PCE) was measured to be 13.11%.
Example 5:
(1) cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive cathode ITO2, and drying by using nitrogen after cleaning;
(2) coating ZnO (5000rpm, 50s and 40nm) on the surface of the transparent conductive cathode ITO2 in a rotating manner to prepare a cathode buffer layer 3, and carrying out thermal annealing treatment (200 ℃, 2h) on the formed film;
(3) dripping PffBT4T-2 OD: PC71BM (1: 1.2, 17.6mg/ml) solution on the cathode buffer layer 3, preparing a bottom light active layer 4(180nm) by adopting a blade coating process, and performing heating treatment (50 ℃ for 10 min);
(4) placing the substrate on a constant temperature heating table at 50 ℃, dripping PBDB-T-SF: ITT-4F (1: 1, 18mg/ml) solution on the bottom heterojunction active layer, preparing a top light active layer 4(100nm) by adopting a blade coating process, and carrying out thermal annealing treatment (110 ℃, 10 min);
(5) an anode buffer layer 5MoO3(15nm) is evaporated on the photoactive layer 4;
(6) metal anode Ag (100nm) is evaporated on the anode buffer layer 5;
(7) under standard test conditions: AM 1.5, 100mW/cm2, and the open-circuit Voltage (VOC), short-circuit current (JSC), Fill Factor (FF), and Photoelectric Conversion Efficiency (PCE) of the device were measured to be 0.88V, 22.92mA/cm2, 0.71, and 13.70%, respectively.
Example 6:
(1) cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive cathode ITO2, and drying by using nitrogen after cleaning;
(2) coating ZnO (5000rpm, 50s and 40nm) on the surface of the transparent conductive cathode ITO2 in a rotating manner to prepare a cathode buffer layer 3, and carrying out thermal annealing treatment (200 ℃, 2h) on the formed film;
(3) dripping PffBT4T-2 OD: PC71BM (1: 1.2, 19.8mg/ml) solution on the cathode buffer layer 3, preparing a bottom light active layer 4(200nm) by adopting a blade coating process, and performing heating treatment (50 ℃ for 10 min);
(4) placing the substrate on a constant temperature heating table at 50 ℃, dripping PBDB-T-SF: ITT-4F (1: 1, 18mg/ml) solution on the bottom heterojunction active layer, preparing a top light active layer 4(100nm) by adopting a blade coating process, and carrying out thermal annealing treatment (110 ℃, 10 min);
(5) an anode buffer layer 5MoO3(15nm) is evaporated on the photoactive layer 4;
(6) metal anode Ag (100nm) is evaporated on the anode buffer layer 5;
(7) under standard test conditions: AM 1.5, 100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.88V, the short-circuit current (JSC) was measured to be 22.13mA/cm2, the Fill Factor (FF) was measured to be 0.69, and the Photoelectric Conversion Efficiency (PCE) was measured to be 12.83%.
Example 7:
(1) cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive cathode ITO2, and drying by using nitrogen after cleaning;
(2) coating ZnO (5000rpm, 50s and 40nm) on the surface of the transparent conductive cathode ITO2 in a rotating manner to prepare a cathode buffer layer 3, and carrying out thermal annealing treatment (200 ℃, 2h) on the formed film;
(3) dripping PffBT4T-2 OD: PC71BM (1: 1.2, 22mg/ml) solution on the cathode buffer layer 3, preparing a bottom light active layer 4(220nm) by adopting a blade coating process, and carrying out heating treatment (50 ℃ for 10 min);
(4) placing the substrate on a constant temperature heating table at 50 ℃, dripping PBDB-T-SF: ITT-4F (1: 1, 18mg/ml) solution on the bottom heterojunction active layer, preparing a top light active layer 4(100nm) by adopting a blade coating process, and carrying out thermal annealing treatment (110 ℃, 10 min);
(5) an anode buffer layer 5MoO3(15nm) is evaporated on the photoactive layer 4;
(6) metal anode Ag (100nm) is evaporated on the anode buffer layer 5;
(7) under standard test conditions: AM 1.5, 100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.86V, the short-circuit current (JSC) was measured to be 19.31mA/cm2, the Fill Factor (FF) was measured to be 0.67, and the Photoelectric Conversion Efficiency (PCE) was measured to be 11.13%.
Example 8:
(1) cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive cathode ITO2, and drying by using nitrogen after cleaning;
(2) coating ZnO (5000rpm, 50s and 40nm) on the surface of the transparent conductive cathode ITO2 in a rotating manner to prepare a cathode buffer layer 3, and carrying out thermal annealing treatment (200 ℃, 2h) on the formed film;
(3) dripping PffBT4T-2 OD: PC71BM (1: 1.2, 17.6mg/ml) solution on the cathode buffer layer 3, preparing a bottom light active layer 4(180nm) by adopting a blade coating process, and performing heating treatment (50 ℃ for 10 min);
(4) placing the substrate on a constant temperature heating table at 60 ℃, dripping PBDB-T-SF: ITT-4F (1: 1, 18mg/ml) solution on the bottom heterojunction active layer, preparing a top light active layer 4(100nm) by adopting a blade coating process, and carrying out thermal annealing treatment (110 ℃, 10 min);
(5) an anode buffer layer 5MoO3(15nm) is evaporated on the photoactive layer 4;
(6) metal anode Ag (100nm) is evaporated on the anode buffer layer 5;
(7) under standard test conditions: AM 1.5, 100mW/cm2, and the open-circuit Voltage (VOC), short-circuit current (JSC), Fill Factor (FF), and Photoelectric Conversion Efficiency (PCE) of the device were measured to be 0.88V, 23.05mA/cm2, 0.72, and 14.60%, respectively.
Example 9:
(1) cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive cathode ITO2, and drying by using nitrogen after cleaning;
(2) coating ZnO (5000rpm, 50s and 40nm) on the surface of the transparent conductive cathode ITO2 in a rotating manner to prepare a cathode buffer layer 3, and carrying out thermal annealing treatment (200 ℃, 2h) on the formed film;
(3) dripping PffBT4T-2 OD: PC71BM (1: 1.2, 17.6mg/ml) solution on the cathode buffer layer 3, preparing a bottom light active layer 4(180nm) by adopting a blade coating process, and performing heating treatment (50 ℃ for 10 min);
(4) placing the substrate on a constant temperature heating table at 70 ℃, and dripping PBDB-T-SF: preparing a top light active layer 4(100nm) from an ITT-4F (1: 1, 18mg/m1) solution by adopting a blade coating process, and carrying out thermal annealing treatment (110 ℃, 10 min);
(5) an anode buffer layer 5MoO3(15nm) is evaporated on the photoactive layer 4;
(6) metal anode Ag (100nm) is evaporated on the anode buffer layer 5;
(7) under standard test conditions: AM 1.5, 100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.88V, the short-circuit current (JSC) 23.16mA/cm2, the Fill Factor (FF) 0.73, and the Photoelectric Conversion Efficiency (PCE) 14.88%.
Example 10:
(1) cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive cathode ITO2, and drying by using nitrogen after cleaning;
(2) coating ZnO (5000rpm, 50s and 40nm) on the surface of the transparent conductive cathode ITO2 in a rotating manner to prepare a cathode buffer layer 3, and carrying out thermal annealing treatment (200 ℃, 2h) on the formed film;
(3) dripping PffBT4T-2 OD: PC71BM (1: 1.2, 17.6mg/ml) solution on the cathode buffer layer 3, preparing a bottom light active layer 4(180nm) by adopting a blade coating process, and performing heating treatment (50 ℃ for 10 min);
(4) placing the substrate on a constant temperature heating table at 80 ℃, dripping PBDB-T-SF: ITT-4F (1: 1, 18mg/m1) solution on the bottom heterojunction active layer, preparing a top light active layer 4(100nm) by adopting a blade coating process, and carrying out thermal annealing treatment (110 ℃, 10 min);
(5) an anode buffer layer 5MoO3(15nm) is evaporated on the photoactive layer 4;
(6) metal anode Ag (100nm) is evaporated on the anode buffer layer 5;
(7) under standard test conditions: AM 1.5, 100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.88V, the short-circuit current (JSC) 23.20mA/cm2, the Fill Factor (FF) 0.73, and the Photoelectric Conversion Efficiency (PCE) 13.90%.
Example 11:
(1) cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive cathode ITO2, and drying by using nitrogen after cleaning;
(2) coating ZnO (5000rpm, 50s and 40nm) on the surface of the transparent conductive cathode ITO2 in a rotating manner to prepare a cathode buffer layer 3, and carrying out thermal annealing treatment (200 ℃, 2h) on the formed film;
(3) dripping PffBT4T-2 OD: PC71BM (1: 1.2, 17.6mg/m1) solution on the cathode buffer layer 3, preparing a bottom light active layer 4(180nm) by adopting a blade coating process, and heating (50 ℃ for 10 min);
(4) placing the substrate on a constant temperature heating table at 90 ℃, dripping a PBDB-T-SF: ITT-4F (1: 1, 18mg/ml) solution on the bottom heterojunction active layer, preparing a top light active layer 4(100nm) by adopting a blade coating process, and carrying out thermal annealing treatment (110 ℃, 10 min);
(5) an anode buffer layer 5MoO3(15nm) is evaporated on the photoactive layer 4;
(6) metal anode Ag (100nm) is evaporated on the anode buffer layer 5;
(7) under standard test conditions: AM 1.5, 100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.87V, the short-circuit current (JSC) was measured to be 22.83mA/cm2, the Fill Factor (FF) was measured to be 0.69, and the Photoelectric Conversion Efficiency (PCE) was measured to be 13.70%.
Example 12:
(1) cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive cathode ITO2, and drying by using nitrogen after cleaning;
(2) coating ZnO (5000rpm, 50s and 40nm) on the surface of the transparent conductive cathode ITO2 in a rotating manner to prepare a cathode buffer layer 3, and carrying out thermal annealing treatment (200 ℃, 2h) on the formed film;
(3) dripping PffBT4T-2 OD: PC71BM (1: 1.2, 17.6mg/ml) solution on the cathode buffer layer 3, preparing a bottom light active layer 4(180nm) by adopting a blade coating process, and performing heating treatment (50 ℃ for 10 min);
(4) placing the substrate on a constant temperature heating table at 100 ℃, dripping PBDB-T-SF: ITT-4F (1: 1, 18mg/ml) solution on the bottom heterojunction active layer, preparing a top light active layer 4(100nm) by adopting a blade coating process, and carrying out thermal annealing treatment (110 ℃, 10 min);
(5) an anode buffer layer 5MoO3(15nm) is evaporated on the photoactive layer 4;
(6) metal anode Ag (100nm) is evaporated on the anode buffer layer 5;
(7) under standard test conditions: AM 1.5, 100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.86V, the short-circuit current (JSC) was measured to be 20.68mA/cm2, the Fill Factor (FF) was measured to be 0.65, and the Photoelectric Conversion Efficiency (PCE) was measured to be 11.56%.
It can be seen that: compared with an organic solar cell prepared without treatment (namely the organic solar cell prepared in the example 1), the organic solar cell with the interpenetrating double-bulk heterojunction photoactive layer 4 prepared by the continuous blade coating method (namely the organic solar cell prepared in the examples 2-12) has the advantages of large Jsc, high FF and high Voc. Compared with the examples 1 and 2 to 7, the performance of the double-body heterojunction organic solar cell prepared by a continuous blade coating mode is higher than that of a single-blade-coated single-active-layer device prepared by mixing 4 materials, namely the performance of the double-body heterojunction organic solar cell prepared by the continuous blade coating mode is much higher than that of the single-blade-coated single-active-layer device prepared by mixing 4 materials, the reason is that the donor and acceptor phases in the active layer are not uniformly distributed, the two-body heterojunction systems can be effectively distinguished by using a continuous blade coating process, and the double-body heterojunction is organically combined in the same active layer by utilizing the solubility difference, so that the separation condition of the donor and acceptor phases in the active layer is optimized, and the separation and transmission capacity of photo. Further, by using two appropriate system bulk heterojunctions, the bottom/top heterojunction can be ensured to form good ohmic contact with the cathode/anode buffer layer respectively, and the transport capability of charge carriers between interfaces is effectively improved, so that, as shown in example 5, the short-circuit current density (Jsc) is improved to 22.93mA/cm2, and the Power Conversion Efficiency (PCE) is optimized to 13.70%. In addition, in comparison between examples 5 and 8 to 12, when the substrate of the bottom heterojunction active layer is under different heating conditions, the performance of the organic solar cell prepared by coating the solution of the top heterojunction active layer by blade coating is improved again, because the higher temperature promotes more dissolution of the bottom heterojunction active layer PffBT4T-2 OD: PC71BM in the solution of the top heterojunction active layer PBDB 402-T-SF: ITT-4F chlorobenzene, promotes the formation of a more appropriate mutual osmotic phase of the double heterojunction, further promotes the separation and transmission capability of photo-generated charge carriers in the active layer, improves the photo-generated current intensity, and further improves the performance of the thick film single junction organic solar cell.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.
Claims (10)
1. The thick-film organic solar cell based on continuous blade coating double-body heterojunction adopts an inversion structure and comprises an active layer, and is characterized in that the active layer consists of a bottom heterojunction active layer and a top heterojunction active layer, and the bottom heterojunction active layer and the top heterojunction active layer form a continuous and mutually-permeable vertical gradient distribution phase state.
2. The thick film organic solar cell based on continuous doctor blade coating double-bulk heterojunction as claimed in claim 1, wherein the thickness of the bottom and top heterojunction active layers is in the range of 100-400 nm.
3. The thick film organic solar cell based on continuous doctor blade coating double-body heterojunction as claimed in claim 1 or 2, wherein the bottom heterojunction active layer is formed by an electron donor material PffBT4T-2OD and an acceptor material PC71Preparing BM mixed solution; the thickness range is 120-220 nm.
4. The thick film organic solar cell based on continuous doctor blade coating double-body heterojunction as claimed in claim 1 or 2, wherein the top-body heterojunction active layer is prepared from a mixed solution of donor material PBDB-T-SF and acceptor non-fullerene material IT-4F.
5. The thick film organic solar cell based on continuous scrape coating double-body heterojunction as claimed in claim 1, wherein the inversion structure comprises a substrate, a transparent conductive cathode, a cathode buffer layer, a photoactive layer, an anode buffer layer and a metal anode from bottom to top.
6. A preparation method of a thick film organic solar cell based on continuous blade coating double-body heterojunction is characterized by comprising the following steps of mixing a base heterojunction active layer mixed solution PffBT4T-2 OD: PC (personal computer)71After BM is dripped on the cathode buffer layer, a blade coating process is used for preparing a substrate heterojunction active layer, and heating treatment is carried out; then placing the substrate on a constant temperature hot table, and dripping a top heterojunction active layer mixed solution PBDB-T-SF: preparing a top heterojunction active layer by using a blade coating process after IT-4F, and carrying out thermal annealing.
7. The continuous doctor blade coating double-bulk heterojunction based thick-film organic solar cell of claim 6, wherein the bulk heterojunction active layer mixed solution PffBT4T-2 OD: PC (personal computer)71The mass percentage of BM is 1: 6-6: 1, and the concentration is 10-30 mg/ml; the mixed solution PBDB-T-SF of the top heterojunction active layer: the mass percentage of IT-4F is 1: 6-6: 1, and the concentration is 10-30 mg/ml.
8. The method for preparing the thick-film organic solar cell based on the continuous doctor blade coating double-body heterojunction as claimed in claim 6, wherein the heating treatment and the thermal annealing mode adopt any one or more of constant-temperature heating table heating, oven heating, far infrared heating and hot air heating.
9. The method for preparing the thick-film organic solar cell based on the continuous doctor-blade coating double-bulk heterojunction as claimed in claim 7, wherein the heating temperature treatment range is 50-100 ℃.
10. The method for preparing the thick film organic solar cell based on the continuous doctor blade coating double-body heterojunction as claimed in any one of claims 6 to 9, wherein the specific preparation method comprises the following steps:
(1) cleaning a base plate consisting of a substrate and a conductive cathode, and drying by using nitrogen after cleaning;
(2) rotationally coating, printing or spraying a cathode buffer layer on the surface of the transparent conductive cathode ITO, and carrying out thermal annealing;
(3) mixing a substrate heterojunction active layer mixed solution PffBT4T-2 OD: PC (personal computer)71After BM is dripped on the cathode buffer layer, a blade coating process is used for preparing a substrate heterojunction active layer, and heating treatment is carried out;
(4) placing the substrate processed in the step (3) on a constant-temperature hot table, and dripping a top heterojunction active layer solution PBDB-T-SF: preparing a top heterojunction active layer by using a blade coating process after IT-4F, and carrying out thermal annealing;
(5) at a vacuum degree of 3 x 10-3Under the condition of Pa, MoO is evaporated on the surface of the optical active layer3Preparing an anode buffer layer;
(6) at a vacuum degree of 3 x 10-4And (6) evaporating the metal anode under the Pa condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911401558.XA CN111180588B (en) | 2019-12-30 | 2019-12-30 | Thick-film organic solar cell based on continuous blade coating double-body heterojunction and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911401558.XA CN111180588B (en) | 2019-12-30 | 2019-12-30 | Thick-film organic solar cell based on continuous blade coating double-body heterojunction and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111180588A true CN111180588A (en) | 2020-05-19 |
| CN111180588B CN111180588B (en) | 2023-03-24 |
Family
ID=70654217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911401558.XA Active CN111180588B (en) | 2019-12-30 | 2019-12-30 | Thick-film organic solar cell based on continuous blade coating double-body heterojunction and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111180588B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111883661A (en) * | 2020-08-28 | 2020-11-03 | 电子科技大学 | Thick-film large-area organic photovoltaic device and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102456837A (en) * | 2010-10-22 | 2012-05-16 | 施乐公司 | Photovoltaic device |
| CN103022358A (en) * | 2012-12-26 | 2013-04-03 | 东南大学 | Double-active-layer polymer solar cell and manufacturing method thereof |
| CN104733614A (en) * | 2015-04-10 | 2015-06-24 | 电子科技大学 | Organic thin-film solar cell based on dual mixed active layers and preparation method thereof |
| CN104795500A (en) * | 2015-04-10 | 2015-07-22 | 电子科技大学 | Organic thin-film solar cell using bulk heterojunctions as linking layers and production method of solar cell |
| CN109378385A (en) * | 2018-10-08 | 2019-02-22 | 电子科技大学 | A kind of organic perovskite combination solar battery based on full spectral absorption |
-
2019
- 2019-12-30 CN CN201911401558.XA patent/CN111180588B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102456837A (en) * | 2010-10-22 | 2012-05-16 | 施乐公司 | Photovoltaic device |
| CN103022358A (en) * | 2012-12-26 | 2013-04-03 | 东南大学 | Double-active-layer polymer solar cell and manufacturing method thereof |
| CN104733614A (en) * | 2015-04-10 | 2015-06-24 | 电子科技大学 | Organic thin-film solar cell based on dual mixed active layers and preparation method thereof |
| CN104795500A (en) * | 2015-04-10 | 2015-07-22 | 电子科技大学 | Organic thin-film solar cell using bulk heterojunctions as linking layers and production method of solar cell |
| CN109378385A (en) * | 2018-10-08 | 2019-02-22 | 电子科技大学 | A kind of organic perovskite combination solar battery based on full spectral absorption |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111883661A (en) * | 2020-08-28 | 2020-11-03 | 电子科技大学 | Thick-film large-area organic photovoltaic device and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111180588B (en) | 2023-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zou et al. | Fiber-shaped flexible solar cells | |
| CN104134711B (en) | A kind of preparation method of perovskite solar cell | |
| CN111180587B (en) | Special doped perovskite solar cell and preparation method thereof | |
| CN110459680A (en) | A kind of perovskite solar battery and preparation method thereof | |
| CN111430544B (en) | Perovskite solar cell based on organic material mixed doping and preparation method thereof | |
| CN103594627A (en) | Inversed organic thin-film solar cell and manufacturing method of inversed organic thin-film solar cell | |
| CN105244441A (en) | Tetraphenyl ethylene polymer hole transport layer-based perovskite solar cell | |
| CN108598269B (en) | Thick-film organic solar cell based on non-fullerene receptor and preparation method | |
| CN107369764A (en) | A kind of perovskite solar cell and preparation method for adulterating lead acetate trihydrate | |
| CN107946466B (en) | Perovskite type solar cell and modification method of PEDOT (polymer doped tin oxide) PSS (patterned sapphire substrate) layer thereof | |
| CN103296211B (en) | Heterojunction solar battery device of organic-two dimensional crystal-inorganic hybridization and preparation method thereof | |
| CN106025084A (en) | Organic solar cell based on ZnO nano particle cathode buffer layer and preparation method thereof | |
| CN108987583A (en) | The perovskite solar battery that defect is passivated | |
| CN110854273A (en) | Organic bulk heterojunction-doped perovskite solar cell and preparation method thereof | |
| CN110429179A (en) | A kind of AZO/ titanium dioxide/stannic oxide-graphene oxide film and utilize its perovskite solar battery obtained | |
| CN109216554B (en) | Perovskite solar cell with P3 HT/graphene as hole transport layer and preparation method thereof | |
| CN110676385A (en) | Carbon-based perovskite solar cell based on multifunctional interface modification layer | |
| CN107180914B (en) | A kind of preparation method of perovskite thin film battery | |
| CN111180588B (en) | Thick-film organic solar cell based on continuous blade coating double-body heterojunction and preparation method thereof | |
| CN111162176B (en) | Preparation method for preparing organic solar cell with vertical phase gradient distribution photoactive layer by oscillation-assisted spin coating process | |
| CN111063806B (en) | Perovskite solar cell and preparation method thereof | |
| CN111223989B (en) | Amphoteric molecule modified perovskite photovoltaic device and preparation method and application thereof | |
| CN115768222A (en) | Perovskite solar cell and rapid preparation method thereof | |
| CN114335348B (en) | PN heterojunction antimony selenide/perovskite solar cell and preparation method thereof | |
| CN103400941A (en) | Organic solar cell based on heteropoly acid anode modifying layer and preparation method of organic solar cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |