CN114824102A - Method for preparing high-performance perovskite film by regulating and controlling microstructure of lead iodide layer and application of method - Google Patents
Method for preparing high-performance perovskite film by regulating and controlling microstructure of lead iodide layer and application of method Download PDFInfo
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 35
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- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 22
- 150000001412 amines Chemical class 0.000 claims description 19
- 239000010408 film Substances 0.000 claims description 17
- 239000012046 mixed solvent Substances 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000005525 hole transport Effects 0.000 claims description 8
- 230000031700 light absorption Effects 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 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 5
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003184 C60 fullerene group Chemical group 0.000 claims description 2
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims description 2
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 239000000654 additive Substances 0.000 abstract description 3
- 239000002090 nanochannel Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000007039 two-step reaction Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
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- 239000000243 solution Substances 0.000 description 26
- 238000000576 coating method Methods 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PVNJLUVGTFULAE-UHFFFAOYSA-N [NH4+].[Cl-].[K] Chemical compound [NH4+].[Cl-].[K] PVNJLUVGTFULAE-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000010345 tape casting Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 238000000861 blow drying Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 description 1
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- -1 ammonium salt ions Chemical class 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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Abstract
The invention discloses a method for preparing a high-performance perovskite thin film by regulating and controlling the microscopic morphology of a lead iodide layer, which is mainly characterized in that a composite solvent containing a THTO additive is introduced in the preparation step of the lead iodide layer of a two-step method, so that the morphological structure of the obtained lead iodide thin film is effectively improved, the lead iodide layer with a nano channel perpendicular to the direction of the thin film and rich pores is formed, the subsequent two-step reaction is facilitated, a high-quality perovskite layer is generated, and the photoelectric conversion efficiency of the obtained perovskite solar cell is effectively improved; the related preparation method is simple, convenient to operate, low in energy consumption and suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a method for preparing a high-performance perovskite thin film by regulating and controlling the micro morphology of a lead iodide layer and application of the high-performance perovskite thin film.
Background
Solar energy is clean energy with huge storage capacity, and the reasonable utilization of solar energy is beneficial to solving the problem of global energy shortage. Solar cells are devices that directly convert sunlight into electrical energy using photoelectric and photochemical effects, and have a wide range of applications, and therefore have attracted attention in recent years. The solar cell research developed to date mainly includes crystalline silicon solar cells, gallium arsenide, cadmium telluride, copper indium gallium selenide and other thin-film solar cells, and at present, dye-sensitized and perovskite solar cells and the like. Will be dedicated to the process of making high performance devices at low cost and to practical production.
The perovskite solar cell is a new star among a plurality of solar cells, and the photoelectric conversion efficiency of the perovskite solar cell is 25.7% after the perovskite solar cell is developed and certified for decades. From the view of the preparation process, the solution method is the most extensive way for preparing the light absorption layer, and accords with the expectation of preparing high-performance devices at low cost. However, current high performance devices are realized based on lab-scale spin-coating and anti-solvent assisted methods, which are not compatible with industrial-scale large area production. In the process of preparing a large-area film by the spin-coating method, the performance is greatly lost. Therefore, the realization of large-area preparation of the perovskite light absorption layer becomes a premise of commercializing perovskite.
The two-step method is a perovskite thin film large-area preparation method which is easy to realize at present, and comprises the following main steps: firstly, depositing an inorganic lead iodide layer, and then coating a layer of organic ammonium salt on the lead iodide film to form a mutual reaction diffusion process, thereby forming the perovskite film. However, it is found that the degree of reaction progress often affects the film quality, and if lead iodide remains too much, the performance of the device is reduced.
Disclosure of Invention
The invention mainly aims to provide a method for preparing a high-performance perovskite thin film by improving the appearance of lead iodide aiming at the problems of incomplete reaction and the like in the conventional two-step method for preparing a perovskite solar cell.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing a high-performance perovskite thin film by regulating and controlling the microscopic morphology of a lead iodide layer adopts a two-step preparation process, wherein in the first step of preparation of the lead iodide thin film, a DMF/THTO mixed solvent is adopted to dissolve lead iodide.
In the above scheme, the specific preparation method comprises the following steps:
1) uniformly dissolving lead iodide powder in a DMF/THTO mixed solvent to obtain a lead iodide solution; dissolving organic amine in an organic solvent to obtain an organic amine solution;
2) depositing a lead iodide solution on the surface of a substrate, performing auxiliary treatment by blowing, and heating and drying to obtain a lead iodide film;
3) depositing organic amine solution on the lead iodide thin film obtained in the step 2) under the heating condition (30-150 ℃, preferably 50-75 ℃) to obtain a black perovskite thin film, and then annealing to obtain the high-performance perovskite thin film.
In the scheme, the volume ratio of DMF to THTO in the DMF/THTO mixed solvent is 9.5 (0.3-0.9); when the THTO content is further increased, the continuity between the obtained lead iodide grains is not ensured, and meanwhile, more THTO can be remained in the subsequent perovskite thin film, so that the use performance of the obtained device is influenced.
In the scheme, the dosage ratio of the lead iodide powder to the DMF/THTO mixed solvent is 1g:1.4-10 mL.
Preferably, the dosage ratio of the lead iodide powder to the DMF/THTO mixed solvent is 1g:1.4-2.2 mL.
In the scheme, the organic amine can be one or more of formamidine iodide, ammonium potassium chloride, methyl ammonium iodide and the like.
Preferably, the organic amine is two or more of formamidine iodide, ammonium potassium chloride, methyl ammonium iodide, and the like.
Further, in the organic amine, the mass ratio of formamidine iodide to potassium ammonium chloride is 0.1-10: 1.
Preferably, the mass ratio of the formamidine iodide to the ammonium potassium chloride is 3.7-4.6: 1.
Further, a cesium salt may be further introduced into the organic amine solution.
In the scheme, the organic solvent in the step 1) is an alcohol solvent, and specifically, alcohols such as isopropanol and n-butanol can be selected.
In the scheme, the concentration of the organic amine solution is 0.01-9.99 mol/L.
Preferably, the concentration of the organic amine solution is 0.45-0.66 mol/L.
In the scheme, the lead iodide solution is deposited on the surface of the substrate by adopting a coating means in the step 2); including but not limited to spin coating, knife coating, spray coating, slot coating, or the like.
In the scheme, the volume ratio of the lead iodide solution to the organic amine solution is 1 (1.0-5.0).
Preferably, the volume ratio of the lead iodide solution to the organic amine solution is 1 (1.2-1.8).
In the scheme, the coating speed in the step 2) is 1-20 mm/s; preferably 1-5 mm/s.
In the above scheme, the blade coating process parameters include: the blade coating height is 0.01-1mm, preferably 0.2-0.5 mm; the surface of the film is purged with nitrogen or dry air (pressure about 0.3 MPa).
In the scheme, the heating and drying temperature in the step 2) is 40-150 ℃, and the time is 0-30 min.
Preferably, the heating and drying temperature in the step 2) is 50-70 ℃ and the time is 30-120 s.
In the scheme, an organic amine solution is arranged on the surface of the substrate by adopting a coating means in the step 3); including but not limited to spin coating, knife coating, spray coating, slot coating, or the like.
In the scheme, the coating speed in the step 3) is 1-20 mm/s; preferably 8-10 mm/s.
In the scheme, the annealing treatment temperature in the step 3) is 70-150 ℃, and the time is 0-60 min.
Preferably, the annealing treatment temperature in the step 3) is 130-150 ℃, and the time is 13-20 min.
The preparation method of the high-performance perovskite thin film is applied to the preparation of the high-efficiency perovskite solar cell and comprises the following steps:
1) etching the transparent conductive substrate and cleaning for later use;
2) depositing an electron transport layer or a hole transport layer on the cleaned transparent conductive substrate;
3) preparing a high-performance perovskite film as a perovskite light absorption layer (prepared by a two-step method);
4) depositing a hole transport layer or an electron transport layer on the surface of the perovskite light absorption layer;
5) and evaporating the metal electrode.
In the above scheme, the transparent conductive substrate can be FTO, ITO, or the like.
In the above scheme, the electron transport layer may be made of tin dioxide, titanium dioxide, zinc oxide, PCBM, C60, etc.; the hole transport layer can be made of Spiro-OMeTAD, PTAA, P3HT, nickel oxide, etc.
In the above scheme, the metal electrode may be gold or silver.
In the above embodiment, the two-step process for preparing the light absorbing layer includes, but is not limited to: spin coating, blade coating, spray coating, slit coating or any combination of processes and the like
In the above scheme, the perovskite solar cell structure includes but is not limited to: contains n-i-p formal and p-i-n trans structure.
The principle of the invention is as follows:
in the two-step preparation process of the organic-inorganic hybrid perovskite, firstly, a DMF/THTO mixed solvent is adopted to dissolve lead iodide powder, the microscopic morphology of a deposited lead iodide layer is effectively controlled, the drying temperature of a film is promoted to be reduced, and the formation of a nano-channel and a rich pore structure which are vertical to the direction of the film is promoted in the film forming process of the lead iodide, so that a wider reaction area is provided for subsequent organic ammonium salt ions, the complete reaction is promoted, and the film forming quality of the perovskite is effectively improved.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention firstly proposes that the DMF/THTO mixed solvent is adopted to dissolve lead iodide, and the shape structure of the obtained lead iodide film is improved by optimizing the deposition condition, thereby being beneficial to the subsequent two-step reaction (organic amine diffusion reaction) and generating a high-quality perovskite layer; the problems that the reaction cannot be completed in the traditional two-step preparation process and the like are effectively solved;
2) the preparation method provided by the invention is simple, convenient to operate and low in energy consumption, and the adopted two-step method is also an important preparation process for realizing the large-area high-quality perovskite thin film and is suitable for popularization and application.
Drawings
FIG. 1 is a schematic representation of the principle of the two-step blade process for introducing different additives (example 1 and comparative example 1).
FIG. 2 is an SEM photograph of a lead iodide thin film obtained in step 2) of example 1;
FIG. 3a is a graph of the photoelectric conversion efficiency of the perovskite solar cell obtained in comparative example 1, and FIG. 3b is a graph of the photoelectric conversion efficiency of the perovskite solar cell obtained in example 1;
FIG. 4 is an SEM photograph of the lead iodide thin film obtained in step 2) of comparative example 1.
Detailed Description
In order to better understand the present invention, the following embodiments are further illustrated, but the present invention is not limited to the following embodiments.
Example 1
A preparation method of a perovskite solar cell adopts a DMF/THTO mixed solvent in the process of dissolving lead iodide powder, the schematic diagram of the principle is shown in figure 1, and the specific steps are as follows:
1) preparation of transparent conductive substrate: etching FTO conductive glass with the thickness of 10cm multiplied by 2.2mm by using a femtosecond or nanosecond laser, wherein the laser power is 20W, the etching depth is about 670nm, then sequentially ultrasonically cleaning the etched glass in a cleaning solution (a detergent solution), pure water and ethanol for 20min respectively, and drying the glass for later use by using an air gun;
2)SnO 2 deposition of the electron transport layer: 5g of urea, 5mL of concentrated hydrochloric acid (37.5 wt%), 100. mu.L of thioglycolic acid and 1.096g of SnCl 2 ·2H 2 Adding O into 400mL of deionized water (ice water) in sequence, uniformly dispersing and placing in a refrigerator for later use; 20mL of the obtained SnCl was taken 2 Diluting the solution by 6 times and pouring the diluted solution into a glass vessel; then the cleaned conductive substrate is immersed into the obtained SnCl after being treated by UV for 15min 2 In the diluent, the glassware is placed in an oven at 90 ℃ for 2.5h for chemical bath deposition; after the reaction is finishedWashing with pure water, sequentially performing ultrasonic treatment in pure water and isopropanol for 3min, blow-drying with nitrogen, and annealing at 180 deg.C for 1h to obtain compact and uniform SnO on the surface of the conductive substrate 2 An electron transport layer;
3) preparation of perovskite light absorption layer (method for preparing high-performance perovskite thin film by regulating and controlling microstructure of lead iodide layer):
preparing a lead iodide precursor solution: weighing 600mg of lead iodide powder, dissolving in 1mL of DMF/THTO (tetramethylene sulfoxide) mixed solvent (volume ratio is 9.5:0.5), and then placing in an oscillator for full dissolution for later use;
preparing an organic ammonium salt solution: dissolving 60mg FAI and 15mg MACl in 1mL IPA (isopropanol), and placing in a shaker to dissolve thoroughly for use;
coating a lead iodide film by blade coating: the deposit obtained in the step 2) is provided with SnO 2 Cutting a substrate of the electronic layer into 5cm multiplied by 5cm, placing the substrate on a coating table, adjusting the height between a blade coating tool bit and the substrate to be about 0.48mm, taking 60 mu L of prepared lead iodide precursor solution, placing the prepared lead iodide precursor solution on the tool bit, just forming a concave liquid surface between the prepared lead iodide precursor solution and the substrate, adjusting the coating speed to be 4mm/s, taking out the glass substrate after blade coating is finished, using an air gun to assist in blow-drying, and placing the glass substrate on a 70 ℃ hot table for drying for 1min to form a yellow lead iodide film;
knife coating of organic ammonium salts: placing the obtained glass substrate with the lead iodide thin film on a 50 ℃ substrate, adjusting the height between a knife head and a substrate to be coated to be about 0.56mm, taking 80 mu L of prepared organic ammonium salt solution to be placed between the knife head and the substrate, coating at the speed of 8mm/s, obtaining a black perovskite thin film after knife coating, and then placing the black perovskite thin film on a heating table for annealing treatment at 150 ℃ for 15min to obtain a perovskite light absorption layer;
4) preparation of a Spiro-OMeTAD hole transport layer: dissolving 91.4mg of Spiro-OMeTAD powder in 1mL of chlorobenzene, adding 35.65 muL of tert-butyl pyridine, 21 muL of Li-TFSI/acetonitrile solution with the concentration of 520mg/mL and 15 muL of FK 209/acetonitrile solution with the concentration of 300mg/mL, mixing, and placing in an oscillator to shake uniformly; dripping a proper amount of the obtained Spiro-OMeTAD solution on the surface of the annealed and cooled perovskite film, and spin-coating at the rotating speed of 4000rpm for 20s to finish the preparation of the hole transport layer;
5) evaporation of metal electrode: putting the product obtained in the step 4) into an evaporation instrument, and carrying out high vacuum (2.5 multiplied by 10) -4 Pa) withAnd evaporating a gold electrode with the thickness of 80nm at a stable rate to obtain the perovskite solar cell.
Scanning electron microscope analysis is performed on the lead iodide thin film (cross section) obtained in the step 3) of the embodiment, and the result is shown in fig. 2, so that a nano channel perpendicular to the thin film direction can be formed in the obtained lead iodide thin film, and meanwhile, rich pore channel structures can be formed.
The perovskite solar cell obtained in the embodiment is subjected to a photoelectric conversion efficiency test, and the area of a mask plate is tested to be 0.16cm under standard sunlight of a sunlight simulator 2 The scanning speed is 10mV/s, and the I-V result passing the positive and negative scanning test is as follows: the reverse scan power conversion efficiency of the device prepared by using THTO as an additive can reach 22.21% (see figure 3 b).
Comparative example 1
A method for preparing a conventional perovskite solar cell (see principle figure 1), which is substantially the same as that of comparative example 1, except that conventional DMSO is used to replace THTO described in example 1 during the process of dissolving lead iodide powder, and the steps for preparing a lead iodide precursor solution are specifically as follows: 600mg of lead iodide powder was weighed, dissolved in 1mL of a DMF/DMSO mixed solvent (volume ratio: 9.5:0.5), and then placed in a shaker to be sufficiently dissolved for use.
Scanning electron microscope analysis is carried out on the lead iodide thin film (section) obtained in the step 3) of the comparative example, and the result is shown in figure 4, so that the formed lead iodide crystal grains are fine and densely stacked (only containing a small amount of cavities), and are integrally arranged along the direction parallel to the thin film, which is not beneficial to the subsequent organic ammonium salt permeation reaction.
The perovskite solar cell obtained by the comparative example is subjected to a photoelectric conversion efficiency test, and the area of a mask plate is tested to be 0.16cm under standard sunlight by using a solar simulator 2 The scanning speed is 10mV/s, and the I-V result passing the positive and negative scanning test is as follows: device reverse scanning prepared by taking DMSO (dimethyl sulfoxide) as additiveThe power conversion efficiency was 20.03% (see figure 3a for results).
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A method for preparing a high-performance perovskite thin film by regulating and controlling the microscopic morphology of a lead iodide layer adopts a two-step preparation process, and is characterized in that a DMF/THTO mixed solvent is adopted to dissolve lead iodide in the first step of preparation of the lead iodide thin film.
2. The method according to claim 1, wherein the specific preparation method comprises the following steps:
1) uniformly dissolving lead iodide powder in a DMF/THTO mixed solvent to obtain a lead iodide solution; dissolving organic amine in an organic solvent to obtain an organic amine solution;
2) depositing a lead iodide solution on the surface of a substrate, drying by blowing, and then heating and drying to obtain a lead iodide film;
3) depositing organic amine solution on the lead iodide thin film obtained in the step 2) under the heating condition to obtain a black perovskite thin film, and then carrying out annealing treatment to obtain the high-performance perovskite thin film.
3. The method according to claim 1 or 2, wherein the volume ratio of DMF to THTO in the DMF/THTO mixed solvent is 9.5 (0.3-0.9).
4. The method according to claim 2, wherein the ratio of the amount of the lead iodide powder to the DMF/THTO mixed solvent is 1g:1.4-10 mL; the volume ratio of the lead iodide solution to the organic amine solution is 1 (1.0-5.0).
5. The method of claim 2, wherein the organic amine is selected from one or more of formamidine iodide, methyl ammonium chloride, and methyl ammonium iodide; the organic solvent is an alcohol solvent.
6. The method according to claim 2, wherein the concentration of the organic amine solution is 0.01-1 mol/L.
7. The method according to claim 2, wherein the heating and drying temperature of step 2) is 40-150 ℃ and the time is 0-30 min.
8. The method as claimed in claim 2, wherein the annealing temperature in step 3) is 100-150 ℃ and the time is 0-30 min.
9. A method for preparing a high-efficiency perovskite solar cell by using the high-performance perovskite thin film as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps:
1) etching the transparent conductive substrate and cleaning for later use;
2) depositing an electron transport layer or a hole transport layer on the cleaned transparent conductive substrate;
3) preparing a high-performance perovskite thin film to obtain a perovskite light absorption layer;
4) depositing a hole transport layer or an electron transport layer on the surface of the perovskite light absorption layer;
5) and evaporating the metal electrode.
10. The method of claim 9, wherein the electron transport layer includes, but is not limited to, tin dioxide, titanium dioxide, zinc oxide, PCBM, or C60; hole transport layers include, but are not limited to, Spiro-OMeTAD, PTAA, P3HT, or nickel oxide.
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