CN117460376A - SnO prepared by blade coating process 2 Electron transport layer, preparation method and application - Google Patents
SnO prepared by blade coating process 2 Electron transport layer, preparation method and application Download PDFInfo
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- CN117460376A CN117460376A CN202311528236.8A CN202311528236A CN117460376A CN 117460376 A CN117460376 A CN 117460376A CN 202311528236 A CN202311528236 A CN 202311528236A CN 117460376 A CN117460376 A CN 117460376A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000000576 coating method Methods 0.000 title claims description 29
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 56
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 22
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000661 sodium alginate Substances 0.000 claims abstract description 8
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 8
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 8
- 239000000648 calcium alginate Substances 0.000 claims abstract description 5
- 235000010410 calcium alginate Nutrition 0.000 claims abstract description 5
- 229960002681 calcium alginate Drugs 0.000 claims abstract description 5
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims abstract description 5
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 4
- 239000000783 alginic acid Substances 0.000 claims abstract description 4
- 229960001126 alginic acid Drugs 0.000 claims abstract description 4
- 229920000615 alginic acid Polymers 0.000 claims abstract description 4
- 150000004781 alginic acids Chemical class 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 230000001360 synchronised effect Effects 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 40
- 239000010408 film Substances 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 18
- 239000010409 thin film Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- -1 rare earth ions Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/84—Layers having high charge carrier mobility
- H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
-
- 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
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention belongs to the technical field of photoelectric devices, and provides SnO prepared by a knife coating process 2 An electron transport layer, a preparation method and application. Specifically, modified SnO is prepared by adding alginic acid, sodium alginate and/or calcium alginate 2 Precursor solution is prepared on a substrate by adopting a knife coating process, and is annealed to obtain uniform and compact SnO 2 An electron transport layer; snO prepared by the method 2 The perovskite battery prepared based on the electron transport layer has excellent photoelectric property and current density of 22.12mA·cm ‑2 The method comprises the steps of carrying out a first treatment on the surface of the The filling factor reaches 81%, and the photoelectric conversion efficiency reaches 20.06%.
Description
Technical Field
The invention belongs to the technical field of photoelectric devices, and relates to SnO prepared by a knife coating process 2 An electron transport layer, a preparation method and application.
Background
Perovskite photovoltaic cell device structures are typically conductive substrates/electron transport layers/perovskite layers/hole transport layers/contact electrodes, and therefore optimizing the materials of each layer and interface contact is a necessary task to further improve cell performance. In perovskite solar cells, the electron transport layer material plays a role in transporting electrons and preventing hole transport, and is a key factor affecting the performance of the cell. The most currently used electron transport layer material is TiO 2 However, the catalyst still has higher ultraviolet catalytic activity, and can lead to perovskite decomposition under ultraviolet irradiation for a long time; and high-temperature calcination at about 500 ℃ is often required, the process is complex, the energy consumption is high, and the commercial application is not facilitated.
SnO 2 The unique advantages of low temperature preparation, high light transmittance, high electron transport capability and the like have been highly emphasized by the research community, and have been widely studied in recent years to replace the traditional TiO 2 An electron transport layer.
Chinese patent application CN104505409A discloses a SnO 2 Perovskite photovoltaic cell with porous structure and preparation method thereof, wherein electron transport layer of perovskite photovoltaic cell is SnO covered on transparent conductive substrate 2 Dense layer and cover SnO 2 SnO on dense film 2 Porous layers of such low temperature-prepared porous structure SnO 2 Perovskite porous photovoltaic cells achieved high photoelectric conversion efficiency of 12.58% and due to SnO 2 Compared with ZnO, the material is more acid and alkali resistant, has higher stability and is more than TiO 2 The ultraviolet attenuation is reduced, the stability of the device is improved, in addition, the method adopts spin coating preparation, the preparation process is simple, and the cost is lower.
Chinese patent application CN104157788A discloses a preparation method based on SnO 2 Perovskite thin film photovoltaic cell and preparation method thereof, and SnO prepared at low temperature is adopted 2 As an electron transport layer to replace the traditional TiO which needs high temperature sintering 2 An electron transport layer made of SnCl 2 ·2H 2 The O ethanol solution is uniformly spin-coated on a conductive substrate by a spin coater, and SnO is obtained by annealing 2 An electron transport layer, based on SnO 2 Perovskite solar cells with thin films as electron transport layers achieved very high photoelectric conversion efficiencies (14.6%).
Chinese patent application CN112652721a discloses a method for preparing a multifunctional thin film of solar cell, which comprises uniformly dispersing rare earth ions in a tin-containing or titanium-containing dense layer solution, forming a film on a conductive substrate material by knife coating, spin coating or spray coating, and sintering at high temperature to obtain a multifunctional thin film of rare earth ion doped tin dioxide or titanium dioxide; the film has the function of a barrier layer, and can effectively reduce the back transmission of photo-generated electrons, thereby improving the photoelectric performance of the solar cell. Although the method can adopt a knife coating method to carry out SnO 2 Film preparation, but also requires a high temperature calcination process at 500 ℃, which is not beneficial to commercial production.
SnO currently used in perovskite 2 The preparation method of the electron transport layer mainly comprises a spin coating method, a sol-gel method, a chemical deposition method and the like, and the preparation processes usually need to be treated by high-temperature calcination, are still widely suitable for laboratory preparation, and lack of preparation processes suitable for commercialization; in addition, although SnO 2 The film has excellent photoelectric property, but improper preparation process can cause obvious defect of the prepared electron transport layer film to become a carrier recombination center and SnO 2 The interface energy level matching with the perovskite thin film is not optimal, thereby causing degradation of the performance of the battery device.
Disclosure of Invention
To solve the SnO in the prior art 2 The preparation process of the electron transport layer is complex, is not suitable for industrial production, and exists in SnO 2 The invention provides SnO prepared by a knife coating process, which is used for solving the problems of low photoelectric conversion efficiency and the like of a perovskite battery prepared by an electron transport layer 2 The electron transport layer, the preparation method and the application thereof have simple method and greatly improve the preparation of SnO 2 Photoelectric conversion efficiency of perovskite battery as electron transport layer.
The technical scheme of the invention is as follows:
SnO prepared by blade coating process 2 Electron transport layerThe method specifically comprises the following steps:
(1) Preparation of modified SnO 2 Precursor solution: snO is taken 2 Adding additives, stirring and aging to obtain the gel water solution;
(2) Modified SnO by blade coating process 2 Preparing precursor solution on a substrate, and annealing to obtain SnO 2 An electron transport layer.
Further, the SnO 2 The concentration of the aqueous gelling solution is 1-7wt%; preferably 3wt%; is made of SnO with a concentration of 15wt% 2 Is diluted with aqueous gel solution.
Further, the additive is added in SnO 2 The concentration of the aqueous gelling solution is 1-10mg/mL.
Still further, the additive is at least one of alginic acid, sodium alginate and calcium alginate.
Due to SnO 2 The gelation aqueous solution has the problems of difficult film formation and the like, and the SnO is prepared by modifying the gelation aqueous solution by adopting the additive 2 The precursor solution can form uniform and compact SnO 2 A film.
Further, the doctor blade is adopted to carry out doctor blade coating under the assistance of inert atmosphere or dry air.
Still further, the humidity of the dry air is less than 20%.
Still further, the doctor blade speed is 10-40mm/s.
Further, the inert atmosphere is nitrogen or argon; preferably nitrogen.
Further, in the blade coating process, the inert atmosphere or dry air purge direction is perpendicular to the substrate, synchronous with the direction of blade movement, or opposite to the direction of blade movement.
Preferably, in the blade coating process, the inert atmosphere or dry air purge direction is synchronous with or opposite to the direction of blade movement.
Further, when the nitrogen atmosphere or dry air purge direction is synchronized with or opposite to the doctor blade, the air flow direction is at an angle of 10-60 ° to the substrate.
Preferably, in the blade coating process, the inert atmosphere or dry air purge direction is synchronized with the direction of blade movement, and the air flow direction is at an angle of 30 ° to the substrate.
The SnO prepared by the method can effectively control the thickness of the film and ensure the uniformity of the film by controlling the inert atmosphere blowing angle, the doctor-blading speed and other technological parameters in the doctor-blading film making process 2 The electron transport layer has the same thickness as a film prepared by spin coating, deposition, evaporation and other processes, and has simpler operation and higher efficiency.
Further, in the step (1), the stirring temperature is room temperature, and the stirring time is 1-3 days.
Further, in the step (1), the aging temperature is 2-5 ℃ and the aging time is 1-2 days.
Further, in the step (2), the annealing temperature is 150-180 ℃ and the annealing time is 30-60min.
The invention also provides the SnO prepared by the method 2 An electron transport layer.
The invention also provides the SnO 2 The electron transport layer is applied to perovskite solar devices.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adds modifying substances such as alginic acid, sodium alginate and/or calcium alginate to SnO 2 The modification of the gel aqueous solution solves the problem that the traditional method of scratch coating can not be used for preparing thinner SnO 2 Problems with thin films; and by controlling SnO 2 The concentration of the gelled aqueous solution and the dosage of the additive can obtain compact SnO 2 A film; with the SnO 2 The photoelectric performance of the perovskite solar cell prepared by taking the film as an electron transport layer is obviously improved; the modifier is environment-friendly, pollution-free and high in economical efficiency;
(2) The SnO prepared by spin coating, deposition and evaporation processes in the prior art is replaced by a doctor blade method 2 The film is simple in mode, the film thickness is controllable, and the distance between the scraper and the film can be adjusted;
(3) The blade coating process is improved, and in particular, the process parameters such as the ambient atmosphere, the airflow direction, the blade coating speed and the like are optimized; the photoelectric performance of the device is further improved;
(4) The preparation process has low annealing temperature, is easy to implement, and is beneficial to industrial production.
Drawings
FIG. 1 shows SnO prepared in example 1 2 Appearance of the film;
FIG. 2 is SnO prepared in example 2 2 Appearance of the film;
FIG. 3 shows SnO prepared in example 2 2 Thin film SEM morphology;
FIG. 4 is a cross-sectional morphology of SnO2 prepared in example 2;
FIG. 5 shows SnO prepared in example 3 2 Appearance of the film;
FIG. 6 shows SnO prepared in example 4 2 Appearance of the film;
FIG. 7 shows SnO prepared in comparative example 4 2 Thin film SEM morphology;
FIG. 8 shows SnO prepared in comparative example 1 2 Appearance of the film;
fig. 9 is a normal uncoated ITO glass appearance.
Detailed Description
Preferred embodiments of the present invention will be specifically described below with reference to specific embodiments, but it should be understood that reasonable variations, modifications and combinations of these embodiments can be made by those skilled in the art without departing from the scope of the present invention as defined in the appended claims, thereby obtaining new embodiments, and these new embodiments obtained by variations, modifications and combinations are also included in the scope of protection of the present invention.
SnO 2 The aqueous gel was purchased from zheng alpha chemical company, product number: A282105.
example 1
1. SnO (SnO) 2 Preparation of electron transport layer
(1) Preparing modified SnO 2 Precursor solution:
firstly, preparing SnO with the concentration of 3wt% 2 Gel water solution, weighing 3mg sodium alginate and dissolving in 2mL of SnO 2 In the gel water solution (namely, the concentration of the additive is 1.5 mg/mL), stirring for 2 days at room temperature, and aging for 1 day at 4 ℃ for later use;
(2) Blade coating SnO 2 Electron transport layer:
fixing the cleaned ITO glass substrate (5.0 cm multiplied by 5.0 cm) on a blade coating table through an adhesive tape, and blowing nitrogen before blade coating; the distance between the doctor blade and the substrate (160 μm) and the nitrogen pressure (0.20 kPa) were adjusted, respectively; snO extraction using a pipette 2 The precursor solution is arranged at the front end of the ITO glass substrate, and the scraper is perpendicular to the glass substrate at the speed of 20mm/s, so that sodium alginate-SnO can be obtained 2 Uniformly coating the precursor solution on a glass substrate;
(3) Annealing:
will be coated with SnO 2 Transferring the glass substrate of the precursor solution to a heating table for annealing at 160 ℃ for 20min to obtain uniform and compact SnO 2 An electron transport layer; the SnO 2 The electron transport layer has an appearance surface under visible light as shown in fig. 1.
2. Preparation of perovskite thin film and device:
(1) A perovskite solution (weighing 461.0mg of PbI) was prepared at a concentration of 1.0mol/mL 2 146.8mg of PbBr 2 192.6mg of formamidine hydroiodidate FAI and 59.7mg of CsI were dissolved in 1mL of DMF/DMSO at a volume ratio of 4: 1) Heating and stirring for 1h at 140 ℃;
(2) Spinning 40 μl of perovskite solution on the SnO 2 Forming a corresponding perovskite absorption layer film on the electron transmission layer by using a toluene antisolvent process;
(3) After the film was cooled, 20. Mu.L of a Spiro-OMeTAD chlorobenzene solution (180 mg/mL chlorobenzene solution) was spin-coated;
(4) Vapor deposition silver electrode (thickness 80 nm);
(5) Assembled into a corresponding perovskite solar cell.
Example 2
1. SnO (SnO) 2 Preparation of electron transport layer
(1) Preparing modified SnO 2 Precursor solution:
SnO was first formulated at a concentration of 3wt.% 2 Gel water solution, weighing 3mg sodium alginate and dissolving in 2mL of SnO 2 In the gel water solution (namely, the concentration of the additive is 1.5 mg/mL), stirring for 2 days at room temperature, and aging for 1 day at 4 ℃; standby;
(2) Blade coating SnO 2 Electron transport layer:
fixing the cleaned ITO glass substrate (5.0 cm multiplied by 5.0 cm) on a blade coating table through an adhesive tape, and blowing by inert gas flow before blade coating; the distance between the doctor blade and the substrate (160 μm) and the nitrogen pressure (0.20 kPa) were adjusted, respectively; snO extraction using a pipette 2 The precursor solution is arranged at the front end of the ITO glass substrate, the direction of nitrogen flow of the scraper is synchronous with the moving direction of the scraper at the speed of 20mm/s, and the angle between the air flow direction and the glass substrate is 30 DEG, so that sodium alginate-SnO can be obtained 2 Uniformly coating the precursor solution on a glass substrate;
(3) Annealing:
will be coated with SnO 2 Transferring the glass substrate of the precursor solution to a heating table for annealing at 160 ℃ for 20min to obtain uniform and compact SnO 2 An electron transport layer; the SnO 2 The electron transport layer has an apparent surface under visible light as shown in fig. 2, a corresponding SEM image of the film surface as shown in fig. 3, and a corresponding film thickness of about 110 μm as shown in fig. 4.
2. Preparation of perovskite thin film and device: as in example 1.
Example 3
1. SnO (SnO) 2 Preparation of electron transport layer
(1) Preparing modified SnO 2 Precursor solution:
SnO was first formulated at a concentration of 3wt.% 2 Gel water solution, weighing 3mg sodium alginate and dissolving in 2mL of SnO 2 In the gel water solution (namely, the concentration of the additive is 1.5 mg/mL), stirring for 2 days at room temperature, and aging for 1 day at 4 ℃; standby;
(2) Blade coating SnO 2 Electron transport layer:
passing the cleaned ITO glass substrate (5.0 cm. Times.5.0 cm) through a glueThe belt is fixed on a blade coating table, and is purged by inert gas flow before blade coating; the distance between the doctor blade and the substrate (180 μm) and the nitrogen pressure (0.20 kPa) were adjusted, respectively; snO extraction using a pipette 2 The precursor solution is arranged at the front end of the ITO glass substrate, the direction of nitrogen flow of the scraper is opposite to the moving direction of the scraper at the speed of 20mm/s, and the angle between the air flow direction and the glass substrate is 30 DEG, so that sodium alginate-SnO can be obtained 2 Uniformly coating the precursor solution on a glass substrate;
(3) Annealing:
will be coated with SnO 2 Transferring the glass substrate of the precursor solution to a heating table for annealing at 150 ℃ for 20min to obtain uniform and compact SnO 2 An electron transport layer; the SnO 2 The electron transport layer has an appearance surface under visible light as shown in fig. 5.
2. Preparation of perovskite thin film and device: as in example 1.
Example 4
1. SnO (SnO) 2 Preparation of electron transport layer
(1) Preparing modified SnO 2 Precursor solution:
firstly, preparing SnO with the concentration of 3wt% 2 Gel aqueous solution, 3mg of calcium alginate was weighed and dissolved in 2mL of the SnO 2 In the gel water solution (namely, the concentration of the additive is 1.5 mg/mL), stirring for 2 days at room temperature, and aging for 1 day at 4 ℃; standby;
(2) Blade coating SnO 2 Electron transport layer:
fixing the cleaned ITO glass substrate (5.0 cm multiplied by 5.0 cm) on a blade coating table through an adhesive tape, and blowing by inert gas flow before blade coating; the distance between the doctor blade and the substrate (160 μm) and the nitrogen pressure (0.20 kPa) were adjusted, respectively; snO extraction using a pipette 2 The precursor solution is arranged at the front end of the ITO glass substrate, the direction of nitrogen flow of the scraper is the same as the moving direction of the scraper at the speed of 20mm/s, and the angle between the air flow direction and the glass substrate is 30 DEG, so that calcium alginate-SnO can be obtained 2 Uniformly coating the precursor solution on a glass substrate;
(3) Annealing:
will be coated with SnO 2 Transfer of the glass substrate of the precursor solution to the applicatorAnnealing for 20min at 180 ℃ on a hot table to obtain uniform and compact SnO 2 An electron transport layer; the SnO 2 The apparent surface of the electron transport layer under visible light is shown in fig. 6, and the corresponding SEM image is shown in fig. 7.
2. Preparation of perovskite thin film and device: as in example 1.
Comparative example 1
1. SnO (SnO) 2 And (3) preparing an electron transport layer: compared with example 1, only no nitrogen gas flow was used for assistance; the SnO 2 The electron transport layer has an appearance surface under visible light as shown in fig. 8.
2. Preparation of perovskite thin film and device: as in example 1.
Fig. 9 is the appearance of a normal uncoated ITO glass (for comparison).
Comparative example 2
1. SnO (SnO) 2 And (3) preparing an electron transport layer: compared with example 1, snO 2 Sodium alginate is not added into the gel water solution.
2. Preparation of perovskite thin film and device: as in example 1.
Test case
At 100 mW.cm by a solar simulator -2 The perovskite solar cells prepared in the above examples and comparative examples were tested for their photoelectric properties under irradiation of standard light; the effective area of the battery is 0.04cm 2 The results are shown in Table 1;
table 1 photovoltaic properties of perovskite solar cells
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. SnO prepared by blade coating process 2 A method of forming an electron transport layer comprising the steps of:
(1) Preparation of modified SnO 2 Precursor solution: snO is taken 2 Adding additives, stirring and aging to obtain the gel water solution;
(2) Modified SnO by blade coating process 2 Preparing precursor solution on a substrate, and annealing to obtain SnO 2 An electron transport layer.
2. The method according to claim 1, wherein the SnO 2 The concentration of the aqueous gelling solution is 1-7wt%.
3. The method of claim 1, wherein the additive is at least one of alginic acid, sodium alginate, and calcium alginate; the additive is SnO 2 The concentration of the aqueous gelling solution is 1-10mg/mL.
4. The method according to claim 1, wherein the doctor blade process is performed with the aid of an inert atmosphere or dry air using a doctor blade.
5. The method of claim 4, wherein the inert atmosphere is nitrogen or argon; the humidity of the dry air is less than 20%; the direction of the purge of the inert atmosphere or dry air is perpendicular to the substrate, synchronous with the direction of movement of the doctor blade or opposite to the direction of movement of the doctor blade and at an angle of 10-60 ° to the glass substrate.
6. The method of claim 4, wherein the inert atmosphere or dry air purge direction is synchronized with the direction of blade movement and is at an angle of 30 ° to the glass substrate during the blade coating process.
7. The method of claim 4, wherein the doctor blade process has a doctor blade speed of 10-40mm/s.
8. The method of claim 1, wherein in step (1), the stirring temperature is room temperature for 1 to 3 days; the aging temperature is 2-5 ℃ and the time is 1-2 days; in the step (2), the annealing temperature is 150-180 ℃; the annealing time is 20-60min.
9. SnO produced by the process according to any one of claims 1 to 8 2 An electron transport layer.
10. SnO according to claim 9 2 The electron transport layer is applied to perovskite solar devices.
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