CN116744704A - Perovskite solar cell based on passivating agent and preparation method thereof - Google Patents
Perovskite solar cell based on passivating agent and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 73
- 238000002161 passivation Methods 0.000 claims abstract description 53
- 239000005416 organic matter Substances 0.000 claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 43
- 239000000758 substrate Substances 0.000 claims description 40
- 230000005525 hole transport Effects 0.000 claims description 37
- 239000011248 coating agent Substances 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 32
- IQJSZNXSTUXHMV-UHFFFAOYSA-N 4-phenyl-3h-dithiole Chemical compound C1SSC=C1C1=CC=CC=C1 IQJSZNXSTUXHMV-UHFFFAOYSA-N 0.000 claims description 24
- 230000031700 light absorption Effects 0.000 claims description 24
- 238000000137 annealing Methods 0.000 claims description 23
- 238000004528 spin coating Methods 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- CWTBRJLMUOHWQG-UHFFFAOYSA-N 3-phenyl-3h-dithiole Chemical compound C1=CSSC1C1=CC=CC=C1 CWTBRJLMUOHWQG-UHFFFAOYSA-N 0.000 claims description 10
- KPVQGIJRXCXXQK-UHFFFAOYSA-N C1[S+](C2=CC=CC=C2)SC=C1 Chemical compound C1[S+](C2=CC=CC=C2)SC=C1 KPVQGIJRXCXXQK-UHFFFAOYSA-N 0.000 claims description 9
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229910002367 SrTiO Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000007547 defect Effects 0.000 abstract description 10
- 230000005540 biological transmission Effects 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000005684 electric field Effects 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 2
- 238000001727 in vivo Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 41
- 239000011259 mixed solution Substances 0.000 description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- 239000010409 thin film Substances 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000012296 anti-solvent Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229960003424 phenylacetic acid Drugs 0.000 description 2
- 239000003279 phenylacetic acid Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- NRPFNQUDKRYCNX-UHFFFAOYSA-N 4-methoxyphenylacetic acid Chemical compound COC1=CC=C(CC(O)=O)C=C1 NRPFNQUDKRYCNX-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing 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
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
-
- 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
- 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
- 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)
- Photovoltaic Devices (AREA)
Abstract
The invention belongs to the field of perovskite solar cell preparation, and particularly relates to a perovskite solar cell based on a passivating agent and a preparation method thereof. The passivating agent-based perovskite solar cell includes a passivation layer; the passivating agent in the passivation layer comprises an organic matter; the functional groups of the organic matter at least comprise phenyl and mercapto. The passivation layer of the perovskite solar cell can passivate defects on the perovskite surface and at the grain boundary, so that the charge transmission performance is effectively improved; the perovskite can be isolated from contact with water vapor and oxygen, degradation of the perovskite is inhibited, stability of the device is improved, and photoelectric conversion efficiency of the solar cell is improved. The organic matter at least comprising phenyl and sulfhydryl is used as a passivating agent, so that the defect density of the perovskite film or in vivo can be effectively reduced, non-radiative recombination induced by the defect is inhibited, the energy loss is reduced, the built-in electric field of the perovskite film is enhanced, and the separation of photo-generated carriers is accelerated.
Description
Technical Field
The invention belongs to the field of perovskite solar cell preparation, and particularly relates to a perovskite solar cell based on a passivating agent and a preparation method thereof.
Background
Organic-inorganic lead halide perovskite solar cells have been one of the most active research directions in the photovoltaic field in the last decade, with a rapid increase in Photoelectric Conversion Efficiency (PCE) from the initial 3.8% to 25.8%. The advent of perovskite solar cells has created many possibilities for future applications. While perovskite solar cells hold promise for the next generation of photovoltaic devices, they still suffer from poor operational stability and degradation under ambient conditions, as well as potential negative environmental impact of toxic lead components. Scientists around the world have made tremendous efforts to solve these problems. Surface passivation of perovskite is considered to be the most effective method to suppress non-radiative recombination losses while increasing photovoltage.
The passivating agents commonly used in the prior art comprise organic molecules such as anisole, phenylacetic acid and the like, all the passivating agents contain Lewis base molecules of oxygen donors, and the passivating agents have good passivation effect, but the passivated perovskite film still has energy level defects, the crystallization activation energy is higher, the charge still has larger energy loss in the transmission process, and the photoelectric conversion efficiency of the solar cell still needs to be further improved.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is that the prior art has defects on the surface and the grain boundary of the perovskite material by using the passivating agent, the efficiency is required to be further improved, and the like, so that the perovskite solar cell based on the passivating agent and the preparation method thereof are provided.
For this purpose, the invention provides the following technical scheme.
The invention provides a perovskite solar cell based on a passivating agent, which comprises a passivation layer; the passivating agent in the passivating layer comprises an organic matter;
the functional groups of the organic matter at least comprise phenyl and mercapto.
The organic matter is at least one of 1, 4-phenyl dithiol, 1, 2-phenyl dithiol, 1, 3-phenyl dithiol and thiophenol.
The perovskite solar cell further comprises an electron transport layer; and/or a perovskite light absorbing layer; and/or, a hole transport layer; and/or a metal electrode.
The electron transport layer is an inorganic electron transport material or an organic electron transport material; preferably, the electron transport layer is SnO 2 、TiO 2 、ZnO、BaNO 3 、SrTiO 3 Or C 60 ；
Preferably, the perovskite light absorbing layer is a lead-based perovskite light absorbing layer; more preferably, the perovskite light absorbing layer is (FAPbI 3 ) 0.93 (MAPbBr 3 ) 0.05 (CsPbI 3 ) 0.02 ；
Preferably, the hole transport layer is a thin layer of Spiro-ome tad;
preferably, the thickness of the metal electrode is 65-75nm.
In addition, the invention also provides a preparation method of the perovskite solar cell, which is characterized by comprising the following steps:
and coating a passivating agent solution on the perovskite light absorption layer, and performing first annealing to obtain the passivation layer.
Further, the content of the passivating agent in each 1ml of the passivating agent solution is 0.1-10mg;
preferably, every 1cm 2 The volume of passivating agent solution applied to the substrate is 11-18 μl.
The temperature of the first annealing is 70-120 ℃ and the time is 10-15min.
The preparation method further comprises the steps of coating perovskite precursor solution and then carrying out second annealing to obtain a perovskite light absorption layer;
preferably, the coating is performed using spin coating;
preferably, the coating is carried out at 800-1000rpm for 10-12s and 4500-5000rpm for 25-30s.
Preferably, the temperature of the second annealing is 100-150 ℃ and the time is 10-40min;
preferably, every 1cm 2 The volume of the perovskite precursor solution coated on the substrate is 11-14 mu L;
preferably, the concentration of the perovskite precursor solution is 1.4-1.8mol/L.
Further, coating an electron transport layer precursor solution and then carrying out third annealing to obtain an electron transport layer;
preferably, the temperature of the third annealing is 100-150 ℃ and the time is 20-60min;
preferably, the electron transport layer precursor solution is applied using a two-step process;
preferably, the coating is performed using spin coating;
preferably, in the first coating step, the concentration of the electron transport layer precursor solution is 2-3mg/mL;
in the second coating step, the concentration of the precursor solution of the electron transport layer is 4-6mg/mL;
preferably, the two-step coating is carried out at a speed of 4000 to 5000rpm;
preferably, in performing the two-step coating, the coating amount per step is: every 1cm 2 The volume of the electron transport layer precursor solution coated on the substrate was 19.0-28.0 μl.
Further, coating a hole transport layer precursor solution to obtain a hole transport layer;
preferably, the hole transport layer precursor solution comprises Spiro-ome tad;
preferably, every 1cm 2 The volume of the hole transport layer precursor solution coated on the substrate is 6.0-14 mu L;
preferably, the concentration of the Spiro-OMeTAD in the hole transport layer precursor solution is 73.0mg/mL-90mg/mL.
The technical scheme of the invention has the following advantages:
1. the perovskite solar cell based on the passivating agent comprises a passivation layer; the passivating agent in the passivation layer comprises an organic matter; the functional groups of the organic matter at least comprise phenyl and mercapto. The passivation layer of the perovskite solar cell can passivate defects on the perovskite surface and at the grain boundary, so that the charge transmission performance is effectively improved; the perovskite can be isolated from contact with water vapor and oxygen, degradation of the perovskite is inhibited, stability of the device is improved, and photoelectric conversion efficiency of the solar cell is improved. The organic matter at least comprising phenyl and sulfhydryl is used as a passivating agent, so that the defect density of the perovskite film or in vivo can be effectively reduced, non-radiative recombination induced by the defect is inhibited, the energy loss is reduced, the built-in electric field of the perovskite film is enhanced, and the separation of photo-generated carriers is accelerated; meanwhile, deep energy level defects can be greatly reduced after passivation, so that crystallization activation energy is greatly reduced, the size of polycrystalline grains is improved, crystallization time is shortened, a more compact and uniform perovskite layer and a smoother perovskite layer are obtained, a hole transport layer can be more uniformly covered on a perovskite light absorption layer, charge transmission and extraction are facilitated, energy loss of charges in the transmission process is reduced, the fluorescence intensity of a passivated perovskite film is obviously improved, and photoelectric conversion efficiency and stability are also obviously improved.
2. According to the perovskite solar cell based on the passivating agent, the passivating agent such as 1, 4-phenyl dithiol, 1, 3-phenyl dithiol and 1, 2-phenyl dithiol can passivate the surface or the inside of the perovskite film, interface non-radiative recombination loss can be greatly reduced after the passivating agent is introduced, defect density on the surface or the inside of the perovskite film is reduced, ion migration and performance degradation of interfaces of a light absorption layer and a hole transmission layer are inhibited, a built-in electric field of the perovskite film is enhanced, and carrier transmission performance is improved; in addition, the passivating agent provided by the invention can also play a role in isolating water vapor and oxygen, inhibit the decomposition of perovskite, improve the photoelectric conversion efficiency and long-term stability of the device, and has a wide application prospect.
The hole transport layer, the passivation layer and the perovskite energy level in the battery are reasonably matched, and the extraction and the transmission of charges are facilitated.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a J-V plot of a perovskite solar cell of the invention for a control test, example 4, example 8, example 9;
FIG. 2 is an XRD pattern of the perovskite absorber layer of the control test and example 4 of the invention;
FIG. 3 is a schematic diagram of a thin film scanning electron microscope in a control test group according to the present invention;
FIG. 4 is a schematic view of a scanning electron microscope of the thin film after the passivation layer is formed in example 4;
FIG. 5 is a schematic view of a scanning electron microscope of the thin film after the passivation layer is formed in example 8;
fig. 6 is a schematic view of a scanning electron microscope of the thin film after the passivation layer is formed in example 9.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
In a specific embodiment, the perovskite solar cell based on the passivating agent comprises a flat hard transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a passivation layer, a hole transport layer and a metal electrode which are sequentially arranged;
wherein the passivating agent comprises an organic matter; the functional groups of the organic matter at least comprise phenyl and mercapto; preferably, the organic matter is at least one of 1, 4-phenyl dithiol, 1, 2-phenyl dithiol, 1, 3-phenyl dithiol and thiophenol.
The electron transport layer is SnO 2 、TiO 2 、ZnO、BaNO 3 、SrTiO 3 Or C 60 。
The perovskite light absorption layer is a lead-based perovskite light absorption layer; preferably, the perovskite light absorbing layer is (FAPbI 3 ) 0.93 (MAPbBr 3 ) 0.05 (CsPbI 3 ) 0.02 。
The hole transport layer is a thin layer of Spiro-OMeTAD.
The preparation method of the perovskite solar cell based on the passivating agent comprises the following steps:
cleaning the conductive substrate;
preparing an electron transport layer by adopting a two-step method, firstly coating a low-concentration electron transport layer precursor solution on a conductive substrate, starting a spin coater, dripping a high-concentration electron transport layer precursor solution in the spin coating process, stopping rotating, annealing on a heating table at 100-150 ℃ for 20-60min, and cooling to obtain the electron transport layer; at each coating time, every 1cm 2 The volume of the electron transport layer precursor solution coated on the substrate is 19-28 muThe rotating speed of the spin coater is 4000-5000rpm. Wherein the concentration of the low-concentration electron transport layer precursor solution is 2-3mg/mL, and the concentration of the high-concentration electron transport layer precursor solution is 4-6mg/mL.
Coating perovskite precursor solution on an electron transport layer by adopting a two-step method, firstly coating for 10-12s at a rotating speed of 800-1000rpm, then coating for 25-30s at a rotating speed of 4500-5000rpm, dripping antisolvent for 15-20s before the coating of the two-step method is finished, annealing for 10-40min at 100-150 ℃, and cooling to obtain a perovskite light absorption layer; wherein the concentration of the perovskite precursor solution is 1.4-1.8mol/L, per 1cm 2 The volume of the perovskite precursor solution coated on the substrate is 11-14 mu L, and the solvent in the perovskite precursor solution can comprise various solvents, such as dimethylformamide DMF, dimethyl sulfoxide DMSO and the like, and further, the solvent is DMF with the volume ratio of 4:1: DMSO; every 1cm 2 The volume of the anti-solvent applied to the substrate is 16. Mu.L to 27.5. Mu.L, and the anti-solvent may be, but is not limited to, ethyl acetate.
Starting a spin coater, setting the rotating speed to be 3000rpm-5000rpm, setting the time to be 30s, coating a passivating agent solution on the perovskite light absorbing layer 20-24s before spin coating is finished, and annealing for 10-15min at 70-120 ℃ to obtain the passivating layer, wherein the passivating agent content in each 1ml of the passivating agent solution is 0.1-10mg. The solvent in the passivating agent solution may be, but is not limited to, isopropyl alcohol; every 1cm 2 The volume of passivating agent solution applied to the substrate is 11-18 μl.
Coating a hole transport layer precursor solution on the passivation layer to obtain a hole transport layer; wherein, every 1cm 2 The volume of the hole transport layer precursor solution coated on the substrate is 6.0-14 mu L; the concentration of the Spiro-OMeTAD in the hole transport layer precursor solution is 73.5mg/mL-90mg/mL; the hole transport layer precursor solution comprises Spiro-OMeTAD, tributyl phosphate, lithium bistrifluoromethylsulfonylimide, FK 209Co (III) TFSI salt and the like; the rotation speed of the hole transport layer solution is 2000-4000rpm.
Evaporating metal to obtain an electrode layer.
Example 1
The embodiment provides a perovskite solar cell based on a passivating agent, which comprises a flat hard transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a passivation layer, a hole transport layer and a metal electrode which are sequentially arranged; the passivating agent in the passivation layer comprises 1, 4-phenyl dithiol, and the hard transparent conductive substrate is ITO.
The preparation method of the perovskite solar cell based on the passivating agent comprises the following steps:
preparing a conductive substrate: cutting the flat hard transparent conductive substrate into 2.5X2.5 cm pieces 2 And (3) cleaning the substrate with clear water, deionized water and ethanol respectively, drying the substrate with dry air, and cleaning the surface with UVO for 30min to obtain the ITO transparent conductive substrate.
Preparing SnO of 2.5mg/mL and 5mg/mL respectively 2 Stirring the aqueous solution at room temperature to obtain SnO with two different concentrations 2 An aqueous solution. 120 mu L of low-concentration SnO is firstly added 2 The aqueous solution is dripped in the center of the conductive substrate, a spin coater is started, spin coating is carried out at 4500rpm and timing is carried out, and 120 mu L of high-concentration SnO is dripped 20-25s before the spin coating is finished 2 And (3) continuously spin-coating the aqueous solution for 50s, and annealing at 120 ℃ for 30min after the spin-coating is finished to obtain the electron transport layer.
Preparing perovskite precursor solution, and weighing PbI 2 ：735.756mg、FAI：255.8mg、MABr：8.95mg、PbBr 2 :29.36mg, csI:8.31mg, MACl:27mg dissolved in DMF: DMSO = 4:1 in an organic solvent to prepare 1.6mol/L (FAPbI 3 ) 0.93 (MAPbBr 3 ) 0.05 (CsPbI 3 ) 0.02 Stirring for 2 hours at room temperature to obtain perovskite precursor solution. And (3) dripping 80 mu L of perovskite precursor solution on the electron transmission layer, spin-coating for 10s at a rotating speed of 1000rpm, spin-coating for 30s at a rotating speed of 4500rpm, dripping 120 mu L of anti-solvent ethyl acetate at 18s before spin-coating, and annealing at 150 ℃ for 10min after spin-coating to obtain the perovskite light absorption layer.
1, 4-phenyl dithiol is taken and dissolved in isopropanol, and stirred for 2 hours at room temperature to be uniformly mixed and transparent, so as to obtain a mixed solution of 2 mg/mL; and (3) taking 85 mu L of the mixed solution, dripping the mixed solution on the perovskite light absorption layer, spin-coating at 5000rpm for 20s, and annealing at 70 ℃ for 5min to obtain the passivation layer.
The Spiro-OMeTAD is used as a hole transport layer, and a hole transport layer precursor solution is prepared before use, and the specific preparation method comprises the following steps: 73.5mg of Spiro-OMeTAD, 29. Mu.L of tributyl phosphate, 17. Mu.L of lithium bistrifluoromethylsulfonylimide (Li-TFSI) and 8. Mu.L of FK 209Co (III) TFSI salt were taken and dissolved in 1mL of chlorobenzene solvent in N 2 Stirring for 2 hours in the environment to obtain a hole transport layer precursor solution; and cooling to room temperature, taking 60 mu LSpiro-OMeTAD solution drops, spin-coating on the passivation layer, wherein the spin-coating speed is 3500rpm, the time is 25s, and obtaining the hole transport layer after spin-coating is finished.
Vacuum coater was used at 1X 10 -5 Evaporating 80nm gold under Pa to obtain perovskite solar cell.
Example 2
The embodiment provides a perovskite solar cell based on a passivating agent, which comprises a flat hard transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a passivation layer, a hole transport layer and a metal electrode which are sequentially arranged; the passivating agent in the passivation layer comprises 1, 4-phenyl dithiol, and the hard transparent conductive substrate is ITO.
The above-mentioned method for preparing perovskite solar cell based on passivating agent is different from example 1 in that the annealing temperature of this example is 100 ℃ when preparing the passivation layer, otherwise the same as example 1.
Example 3
The embodiment provides a perovskite solar cell based on a passivating agent, which comprises a flat hard transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a passivation layer, a hole transport layer and a metal electrode which are sequentially arranged; the passivating agent in the passivation layer comprises 1, 4-phenyl dithiol, and the hard transparent conductive substrate is ITO.
The above-mentioned method for preparing perovskite solar cell based on passivating agent is different from example 1 in that the annealing temperature of this example is 120 deg.c when preparing the passivation layer, otherwise the same as example 1.
Example 4
The embodiment provides a perovskite solar cell based on a passivating agent, which comprises a flat hard transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a passivation layer, a hole transport layer and a metal electrode which are sequentially arranged; the passivating agent in the passivation layer comprises 1, 4-phenyl dithiol, and the hard transparent conductive substrate is ITO.
The above-described method for producing a perovskite solar cell based on a passivating agent differs from example 1 in that: when the passivation layer is prepared, 1, 4-phenyl dithiol is taken and dissolved in isopropanol, and stirred for 2 hours at room temperature to be uniformly mixed and transparent, so as to obtain a mixed solution of 4 mg/mL; taking 85 mu L of the mixed solution, dripping the mixed solution on the perovskite light absorption layer, spin-coating the mixed solution at 5000rpm for 22s, and annealing the mixed solution at 100 ℃ for 5min to obtain a passivation layer; otherwise, the same as in example 1 was conducted.
Example 5
The embodiment provides a perovskite solar cell based on a passivating agent, which comprises a flat hard transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a passivation layer, a hole transport layer and a metal electrode which are sequentially arranged; the passivating agent in the passivation layer comprises 1, 4-phenyl dithiol, and the hard transparent conductive substrate is ITO.
The above-described method for producing a perovskite solar cell based on a passivating agent differs from example 1 in that: when the passivation layer is prepared, 1, 4-phenyl dithiol is taken and dissolved in isopropanol, and stirred for 2 hours at room temperature to be uniformly mixed and transparent, so as to obtain a mixed solution of 6mg/mL; taking 85 mu L of the mixed solution, dripping the mixed solution on the perovskite light absorption layer, spin-coating the mixed solution at 5000rpm for 24s, and annealing the mixed solution at 100 ℃ for 5min to obtain a passivation layer; otherwise, the same as in example 1 was conducted.
Example 6
The embodiment provides a perovskite solar cell based on a passivating agent, which comprises a flat hard transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a passivation layer, a hole transport layer and a metal electrode which are sequentially arranged; the passivating agent in the passivation layer comprises 1, 4-phenyl dithiol, and the hard transparent conductive substrate is ITO.
The above-described method for producing a perovskite solar cell based on a passivating agent differs from example 1 in that: when the passivation layer is prepared, 1, 4-phenyl dithiol is taken and dissolved in isopropanol, and stirred for 2 hours at room temperature to be uniformly mixed and transparent, so as to obtain 8mg/mL mixed solution; taking 85 mu L of the mixed solution, dripping the mixed solution on the perovskite light absorption layer, spin-coating the mixed solution at 5000rpm for 24s, and annealing the mixed solution at 100 ℃ for 5min to obtain a passivation layer; otherwise, the same as in example 1 was conducted.
Example 7
The embodiment provides a perovskite solar cell based on a passivating agent, which comprises a flat hard transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a passivation layer, a hole transport layer and a metal electrode which are sequentially arranged; the passivating agent in the passivation layer comprises 1, 4-phenyl dithiol, and the hard transparent conductive substrate is ITO.
The above-described method for producing a perovskite solar cell based on a passivating agent differs from example 1 in that: when the passivation layer is prepared, 1, 4-phenyl dithiol is taken and dissolved in isopropanol, and stirred for 2 hours at room temperature to be uniformly mixed and transparent, so as to obtain a mixed solution of 10 mg/mL; taking 85 mu L of the mixed solution, dripping the mixed solution on the perovskite light absorption layer, spin-coating the mixed solution at 5000rpm for 24s, and annealing the mixed solution at 100 ℃ for 5min to obtain a passivation layer; otherwise, the same as in example 1 was conducted.
Example 8
The embodiment provides a perovskite solar cell based on a passivating agent, which comprises a flat hard transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a passivation layer, a hole transport layer and a metal electrode which are sequentially arranged; the passivating agent in the passivation layer comprises 1, 3-phenyl dithiol, and the hard transparent conductive substrate is ITO.
The preparation method of the perovskite solar cell based on the passivating agent is the same as that of the example 4.
Example 9
The embodiment provides a perovskite solar cell based on a passivating agent, which comprises a flat hard transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a passivation layer, a hole transport layer and a metal electrode which are sequentially arranged; the passivating agent in the passivation layer comprises 1, 2-phenyl dithiol, and the hard transparent conductive substrate is ITO.
The preparation method of the perovskite solar cell based on the passivating agent is the same as that of the example 4.
Comparative example 1
This comparative example provides a perovskite solar cell differing from example 4 in that phenylacetic acid was used in place of 1, 4-phenyl dithiol and the perovskite solar cell was prepared in the same manner as in example 4.
Comparative example 2
This comparative example provides a perovskite solar cell differing from example 4 in that p-methoxyphenylacetic acid was used instead of 1, 4-phenyl dithiol, and the perovskite solar cell was prepared in the same manner as in example 4.
Test examples
The test example provides performance tests of perovskite solar cells of examples and comparative examples, with perovskite thin films without passivating agent added as a control test, which is in contrast to example 4, and specifically:
FIG. 1 is a J-V plot of a perovskite solar cell under standard test conditions (AM 1.5, 1000W/m 2 The battery electrode was subjected to J-V test at 25 ℃. The results are shown in Table 1.
TABLE 1 Performance test results
Wherein, the perovskite solar cell without the passivating agent is 24.80mA/cm 2 The short-circuit current density of 1.124V, the open voltage of 75.5 percent of filling factor, and finally reach 2104% efficiency. Perovskite solar cell with 1, 2-phenyl dithiol (example 9) as passivating agent obtained 24.71mA/cm 2 The open voltage of 1.119V, a fill factor of 76.6%, and finally an efficiency of 21.27% is achieved. Perovskite solar cell with 1, 3-phenyl dithiol (example 8) as passivating agent obtained 25.15mA/cm 2 The short circuit current density of 1.128V, the open voltage of 78.8% fill factor, and finally 22.36% efficiency. Perovskite solar cell with 1, 4-phenyl dithiol (example 4) as passivating agent obtained 25.02mA/cm 2 The open voltage of 1.157V, a fill factor of 80.2%, and finally an efficiency of 23.14% is achieved.
FIG. 2 is an XRD pattern of the perovskite light absorbing layer in the control test group and example 4, specifically, the XRD pattern of the perovskite light absorbing layer was tested before the application of the passivating agent precursor solution, then the 1, 4-phenyl dithiol was spin-coated on the perovskite light absorbing layer, annealed at 100℃for 5min, cooled to room temperature, and then the XRD pattern of the perovskite light absorbing layer was tested again, and it can be seen from the figure that there was a distinct crystallization peak, the peak intensity of perovskite pamo was enhanced after passivation, indicating the enhancement of the crystallinity of the perovskite film after the addition of the passivating agent.
FIG. 3 is a schematic diagram of a thin film scanning electron microscope in a control test group; FIG. 4 is a schematic view of a scanning electron microscope of the thin film after the passivation layer is formed in example 4; FIG. 5 is a schematic view of a scanning electron microscope of the thin film after the passivation layer is formed in example 8; fig. 6 is a schematic view of a scanning electron microscope of the thin film after the passivation layer is formed in example 9. As can be seen from fig. 4-6, after the passivating agent is added, the holes of the film are few, the grains are densely distributed, and the overall quality is better.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A passivating agent-based perovskite solar cell comprising a passivation layer; the passivating agent in the passivating layer comprises an organic matter;
the functional groups of the organic matter at least comprise phenyl and mercapto.
2. The perovskite solar cell of claim 1, wherein the organic matter is at least one of 1, 4-phenyl dithiol, 1, 2-phenyl dithiol, 1, 3-phenyl dithiol, and thiophenol.
3. The perovskite solar cell of claim 1 or 2, further comprising an electron transport layer; and/or a perovskite light absorbing layer; and/or, a hole transport layer; and/or a metal electrode.
4. A perovskite solar cell according to claim 3, wherein the electron transport layer is an inorganic electron transport material and/or an organic electron transport material;
preferably, the electron transport layer is SnO 2 、TiO 2 、ZnO、BaNO 3 、SrTiO 3 And C 60 At least one of (a) and (b);
preferably, the perovskite light absorbing layer is a lead-based perovskite light absorbing layer;
preferably, the perovskite light absorbing layer is (FAPbI 3 ) 0.93 (MAPbBr 3 ) 0.05 (CsPbI 3 ) 0.02 ；
Preferably, the hole transport layer is a thin layer of Spiro-ome tad;
preferably, the thickness of the metal electrode is 65-75nm.
5. A method of manufacturing a perovskite solar cell as claimed in any one of claims 1 to 4, comprising the steps of:
and coating a passivating agent solution on the perovskite light absorption layer, and performing first annealing to obtain the passivation layer.
6. The method of claim 5, wherein the passivating agent is present in an amount of 0.1-10mg per 1ml of said passivating agent solution;
preferably, every 1cm 2 The volume of passivating agent solution applied to the substrate is 11-18 μl.
7. The method according to claim 5 or 6, wherein the first annealing is performed at a temperature of 70-120 ℃ for a time of 10-15min.
8. The method of any one of claims 5 to 7, further comprising coating the perovskite precursor solution and then performing a second anneal to obtain the perovskite light absorbing layer;
preferably, the coating is performed using spin coating;
preferably, during coating, the coating is carried out at a speed of 800-1000rpm for 10-12s and then at a speed of 4500-5000rpm for 25-30s;
preferably, the temperature of the second annealing is 100-150 ℃ and the time is 10-40min;
preferably, every 1cm 2 The volume of the perovskite precursor solution coated on the substrate is 11-14 mu L;
preferably, the concentration of the perovskite precursor solution is 1.4-1.8mol/L.
9. The method according to any one of claims 5 to 8, wherein the electron transport layer is obtained by applying an electron transport layer precursor solution and then performing a third annealing;
preferably, the temperature of the third annealing is 100-150 ℃ and the time is 20-60min;
preferably, the electron transport layer precursor solution is applied using a two-step process;
preferably, the coating is performed using spin coating;
preferably, in the first coating step, the concentration of the electron transport layer precursor solution is 2-3mg/mL;
in the second coating step, the concentration of the precursor solution of the electron transport layer is 4-6mg/mL;
preferably, the two-step coating is carried out at a speed of 4000 to 5000rpm;
preferably, in performing the two-step coating, the coating amount per step is: every 1cm 2 The volume of the electron transport layer precursor solution coated on the substrate was 19.0-28.0 μl.
10. The method according to any one of claims 5 to 9, wherein a hole transport layer is obtained by coating a hole transport layer precursor solution;
preferably, the hole transport layer precursor solution comprises Spiro-ome tad;
preferably, every 1cm 2 The volume of the hole transport layer precursor solution coated on the substrate is 6.0-14 mu L;
preferably, the concentration of the Spiro-OMeTAD in the hole transport layer precursor solution is 73.0mg/mL-90mg/mL.
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