CN115835744A - Perovskite thin film, preparation method thereof and perovskite photoelectric device - Google Patents
Perovskite thin film, preparation method thereof and perovskite photoelectric device Download PDFInfo
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Abstract
The invention discloses a perovskite thin film, a preparation method thereof and a perovskite photoelectric device. The preparation method comprises the following steps: providing a precursor solution, wherein the precursor solution contains a perovskite precursor and a selected solvent, the selected solvent comprises any one or the combination of two or more of gamma-butyrolactone, delta-valerolactone, gamma-valerolactone, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide, preparing a film precursor by using the precursor solution through a solution method, and carrying out post-treatment on the film precursor to form the perovskite film. The preparation method provided by the invention effectively avoids the harm of a large amount of toxic solvents to the health of people and the ecological environment, is more suitable for the industrialized green production of the perovskite solar cell under large-area preparation, and the prepared metal halide perovskite thin film has higher crystal quality, full phase transformation, high phase purity, better fluorescence property of the perovskite thin film, and more excellent photovoltaic performance and stability.
Description
Technical Field
The invention relates to the technical field of perovskite photoelectric devices, in particular to a perovskite thin film, a preparation method thereof and a perovskite photoelectric device.
Background
In recent years, photovoltaic solar cells have been developed unprecedentedly, the energy conversion efficiency of non-light-condensing monocrystalline silicon solar cells reaches 26.1%, the efficiency of polycrystalline silicon cells reaches 23.3%, and the efficiency of commercialized crystalline silicon cells also breaks through 23%.
The search for different photovoltaic materials has never been stopped, and since 2009 metal halide perovskite solar cells were first reported, new semiconductor materials, such as metal halide perovskites, have attracted great attention in the scientific research community and the industrial community. The novel perovskite material has the advantages of adjustable band gap, high defect tolerance, long carrier diffusion length and mobility, strong light absorption, solution method-based processability and the like, so that the metal halide perovskite and semiconductor devices such as photovoltaics, photoelectricity and the like based on the perovskite are deeply and widely researched. However, the combination of high performance devices with high efficiency, stability and low cost has been a great challenge in the process of commercializing metal halide perovskite semiconductor devices.
Although the maximum efficiency of the current small-area laboratory-grade perovskite solar cell reaches 25.7%, the green preparation problem of the perovskite solar cell is still one of important problems to be solved in the field.
The existing solution method for preparing perovskite solar cells, especially for preparing perovskite light absorption layers therein, still needs to use a large amount of toxic and harmful solvents, which is obviously disadvantageous for the wide application of perovskite solar cells, on one hand, the health risk of practitioners is increased, on the other hand, the environment is also polluted, and the corresponding need to invest additional treatment cost. Therefore, the realization of the high-performance metal halide perovskite solar cell device which is prepared in an efficient, stable and green manner is a practical challenge for people to explore and utilize new perovskite photovoltaic energy and is one of the ultimate goals to be achieved.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a perovskite thin film, a preparation method thereof and a perovskite photoelectric device.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
in a first aspect, the present invention provides a method for preparing a perovskite thin film, comprising:
providing a precursor solution, wherein the precursor solution contains a perovskite precursor and a selected solvent, and the selected solvent comprises any one or the combination of more than two of gamma-butyrolactone, delta-valerolactone, gamma-valerolactone, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide;
and preparing a film precursor by using the precursor solution through a solution method, and carrying out post-treatment on the film precursor to form the perovskite film.
In a second aspect, the invention also provides a perovskite thin film prepared by the preparation method.
In a third aspect, the present invention further provides a perovskite photoelectric device, which includes a hole transport layer, a photoelectric conversion layer and an electron transport layer, which are sequentially stacked; the photoelectric conversion layer includes the perovskite thin film.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that at least:
the solvent used in the preparation method provided by the invention is a specific green environment-friendly solvent with extremely low toxicity, is safe to human bodies, and avoids the problems that solvents used in the preparation of perovskite films by the traditional solution method, such as N, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and the like, have obvious or even higher toxicity and easily cause health hazards to practitioners, so that the preparation process of the metal halide perovskite film is more green and environment-friendly, is safer and more friendly to practitioners, effectively avoids the harm of a large amount of toxic solvents to the health and ecological environment of the personnel, and is more suitable for the industrialized green production of perovskite solar cells under large-area preparation.
The metal halide perovskite thin film prepared by the preparation method provided by the invention has the advantages of higher crystal quality, sufficient phase transformation, high phase purity, better fluorescence performance and more excellent photovoltaic performance.
The above description is only an overview of the technical solutions of the present invention, and in order to enable those skilled in the art to more clearly understand the technical means of the present invention and to implement the technical means according to the content of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1a is a schematic structural diagram of a perovskite solar cell provided in an exemplary embodiment of the present invention;
FIG. 1b is a schematic diagram of a perovskite solar cell provided in accordance with another exemplary embodiment of the present invention;
FIG. 2 is a graph showing the comparison of fluorescence intensity of a perovskite thin film provided in an exemplary embodiment of the present invention with that of a perovskite thin film of the prior art;
fig. 3 is a comparative test chart of power conversion efficiency of a perovskite solar cell provided by an exemplary embodiment of the present invention and a perovskite solar cell in the prior art.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention has made extensive research and practice to propose the technical solution of the present invention. The invention aims to provide a method for preparing a metal halide perovskite thin film by a solution method based on a green solvent, and also aims to provide a perovskite solar cell based on a green solvent and a preparation method thereof. The perovskite solar cell prepared from the green solvent by a solution method has the advantages that the fluorescence performance and the photovoltaic performance are remarkably improved, and more importantly, the selected solvent has the requirements of environmental protection, extremely low toxicity and safety to human bodies.
The technical solution, its implementation and principles, etc. will be further explained as follows. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein and, therefore, the scope of the present invention is not limited by the specific embodiments disclosed below.
Referring to fig. 1a, fig. 1b and fig. 2 to fig. 3, a method for preparing a perovskite thin film according to an embodiment of the present invention includes the following steps:
providing a precursor solution, wherein the precursor solution contains a perovskite precursor and a selected solvent, and the selected solvent comprises any one or a combination of more than two of gamma-butyrolactone, delta-valerolactone, gamma-valerolactone, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide.
And preparing a thin film precursor by a solution method by using the precursor solution, and performing post-treatment on the thin film precursor to form the perovskite thin film.
In the technical scheme, the specific green solvent is adopted, the performance of the perovskite thin film can be improved on the premise of ensuring green and low toxicity in the preparation process, and the obtained technical effect is double, rather than only replacing the adopted solvent with an environment-friendly solvent. The choice of environmentally friendly solvents is very large, but not all environmentally friendly solvents can achieve the enhancement of the perovskite thin film performance, or at least the performance of the film layer should not be significantly reduced compared to the traditional non-environmentally friendly solvents, such as DMF and the like.
The invention provides a preparation method adopting the specific solvent only in long-term practice, thereby realizing double effects of environmental protection and good film performance.
Although the prior art provides some technical solutions for preparing perovskite single crystal by using dimethyl sulfoxide and lactone solvents, unlike the present invention, the process of preparing single crystal does not involve volatilization of a large amount of solvent, and thus does not face the technical problems of environmental protection and toxicity of a large amount of solvent in the present invention.
As some typical application examples of the technical scheme, the invention provides a method for preparing a perovskite thin film and a perovskite solar cell by a solution method based on a green solvent, which comprises the following specific implementation steps:
a. and dissolving the perovskite precursor material by using a green solvent to prepare a perovskite precursor solution.
b. Preparation of metal halide perovskite thin film by solution method and post-treatment using perovskite precursor solution of green solvent
c. The perovskite thin film prepared by using the green solvent is used as a light absorption layer, and the perovskite solar cell is prepared.
The green solvent is selected in the technical scheme provided by the invention, and the proper solvent combination is preferably selected, so that the green environmental protection property of the perovskite layer preparation process is realized on the basis of ensuring that the perovskite layer has good film performance, and the solvent is not simply replaced by the solvent with the green environmental protection property.
In some embodiments, the selected solvent is a mixed solvent of two or more solvents.
In some embodiments, the selected solvent is selected from the group consisting of mixed solvents of dimethyl sulfoxide and any one or combination of two or more of gamma-butyrolactone, delta-valerolactone, gamma-valerolactone, 1,3-dimethyl-2-imidazolidinone.
The inventor of the present invention has found in long-term practice that, with the above-mentioned green solvent combination, the thin film performance of the perovskite thin film and the photoelectric conversion performance of the perovskite solar cell can also be improved, and the specific principle thereof should be: lead ions or univalent cations in the perovskite precursor, especially lead ions or univalent cations in the perovskite precursor, and dimethyl sulfoxide in the solvent combination have specific strong chemical coordination effect, but the viscosity and boiling point of dimethyl sulfoxide are high, and the lead ions or univalent cations need to be matched and combined with other specific low-viscosity and low-boiling-point lactones or imidazolones and other green solvents for use, so that finally, when a perovskite precursor solution is subjected to film forming crystallization, a high-quality perovskite thin film with a cubic phase or tetragonal phase crystal structure is more prone to be formed, and the thin film performance of the perovskite thin film and the photoelectric conversion performance of a perovskite solar cell are improved.
As some typical application examples of the above technical solutions, the green solvent is one or more solvents selected from gamma (γ) -butyrolactone (GBL), delta (δ) -valerolactone (DVL), gamma (γ) -valerolactone (GVL) 1,3-dimethyl-2-imidazolidinone (DMI), and dimethyl sulfoxide (DMSO), and the selected solvent is characterized by being green, environmentally friendly, extremely low toxic, safer for human body, and environmentally friendly.
In some embodiments, the volume fraction of dimethyl sulfoxide in the mixed solvent is 10% to 70%.
In some embodiments, the molar concentration of the perovskite precursor in the precursor solution is from 0.5 to 2.0mol/L.
In some embodiments, the thickness of the perovskite thin film is 10 to 2000nm, preferably 100 to 1000nm.
In some embodiments, the perovskite thin film is made of a material satisfying ABX 3 An ionic crystal of the structure or satisfy A' m A n-1 B n X 3n+1 The structural ionic crystal, m =1 or 2,n is an integer of 1 or more.
Wherein A is a monovalent organic or inorganic cation, B is a divalent metal cation, X is a monovalent anion, and A' is a monovalent or divalent long-chain organic cation.
In some embodiments, a comprises any one or a combination of two or more of methylammonium ions, formamidine ions, cesium ions, rubidium ions; wherein, methyl ammonium ion (MA) + ) Formamidine (FA) + ) And the like, an amine ion containing an aliphatic or aromatic alkyl group, an alkali metal ion such as cesium or rubidium, or a mixture containing the foregoing ions.
In some embodiments, B comprises leadIon (Pb 2) + ) Tin ion (Sn) 2+ ) Germanium ion (Ge) 2+ ) Copper ion (Cu) 2 + ) Any one or a combination of two or more of the divalent metal cations.
In some embodiments, iodide (I-), bromide (Br) - ) Chloride ion (Cl) - ) Plasma halide ions, or thiocyanate ions (SCN) - ) And the like, or a combination of two or more thereof.
In some embodiments, a' is a monovalent or divalent cation, including butylammonium ion (BA) + ) Phenethylammonium ion (PEA) + ) Ammonium Valerate (AVA) + ) Ethylenediamine ion (EDA) 2+ ) Propane diammonium ion (PDA) 2+ ) Ding Eran ion (BDA) 2+ ) Any one or a combination of two or more of them.
As some typical application examples of the above technical solution, the material of the perovskite thin film may be selected from any one or a combination of two or more of the following material formulas:
(MA) x (FA) 1-x Pb(I y Br 1-y ) 3 wherein x is more than 0, y is less than 1, (MA) x Cs 1-x Pb(I y Br 1-y ) 3 Wherein 0 < x, y < 1, (FA) xCs 1-x Pb(I y Br 1-y ) 3 Where 0 < x, y < 1, cs z (FA)x(MA) y Pb(I n Br 1-n ) 3 Wherein 0 < x, y, z, n < 1, and x + y + z =1, (BA) 2 (MA) n-1 Pb n I 3n+1 Wherein n is more than or equal to 1, (PEA) 2 (MA) n-1 Pb n I 3n+1 Wherein n is more than or equal to 1, (AVA) 2 (MA) n-1 Pb n I 3n+1 Wherein n is not less than 1, (EDA) (MA) n-1 Pb n I 3n+1 Wherein n is more than or equal to 1, (PDA) (MA) n-1 Pb n I 3n+1 Wherein n is more than or equal to 1; wherein MA is methyl ammonium ion, FA is formamidine cation, cs is cesium ion, pb is divalent lead ion, sn is divalent tin ion, BA is butyl ammonium ion, PEA is phenethyl ammonium ion, AVA is pentanoyl ammonium ion, EDA is ethyl diammonium ionAnd PDA is propyl diammonium ion. For the above preferred perovskite material formulation, the green solvent combination is preferably dimethyl sulfoxide (DMSO) or gamma (γ) -butyrolactone (GBL), or delta (δ) -valerolactone (DVL), or gamma (γ) -valerolactone (GVL), in a mixture ratio of 10% to 70% by volume of dimethyl sulfoxide.
In some embodiments, the solution method may include any one or a combination of two or more of a spin coating method, a blade coating method, a slit extrusion coating method, a spray coating method, a screen printing method, and an inkjet printing method.
In some embodiments, the post-treatment may include any one or a combination of two or more of anti-solvent extraction treatment, air blow solvent treatment, vacuum desolvation treatment, and heat annealing treatment.
In some embodiments, the anti-solvent that may be employed in the anti-solvent extraction treatment includes any one or a combination of two or more of ethyl acetate, methyl acetate, propyl acetate, anisole, and phenetole.
It should be noted that the above specific methods for forming the perovskite thin film are all common methods known in the art, and the specific conditions, parameters and other implementation details can be determined by those skilled in the art with reference to the existing technical solutions.
According to another aspect of the embodiment of the present invention, there is provided a perovskite thin film prepared by the preparation method provided in any one of the above embodiments.
The embodiment of the invention also provides a perovskite photoelectric device, which comprises a hole transport layer, a photoelectric conversion layer and an electron transport layer which are sequentially stacked; the photoelectric conversion layer includes the perovskite thin film provided in the above embodiment.
In some embodiments, the perovskite optoelectronic device is a perovskite solar cell and the photoelectric conversion layer is a light absorbing layer.
In some embodiments, the perovskite solar cell includes a transparent conductive electrode substrate, an electron transport layer, a photoelectric conversion layer, a hole transport layer, and a top electrode, which are sequentially stacked.
Or, the perovskite solar cell comprises a transparent conductive electrode substrate, a hole transport layer, a photoelectric conversion layer, an electron transport layer and a top electrode which are sequentially stacked.
Specifically, the perovskite solar cell device provided by the embodiment of the invention comprises an upright device structure and an inverted device structure, wherein the upright device structure sequentially comprises a transparent conductive electrode substrate, an electron transport layer, a perovskite thin film light absorption layer, a hole transport layer (containing a hole type interface modification layer possibly included) and a top electrode; the inverted device structure sequentially comprises a transparent conductive electrode substrate, a hole transport layer, a perovskite thin film light absorption layer, an electron transport layer (containing an electron type interface modification layer possibly included) and a top electrode. The structural schematic diagram of the perovskite solar cell is shown in the attached figures 1a and 1 b.
The perovskite thin film light absorption layer is prepared by the preparation method of the green solvent solution provided by the embodiment of the invention. In the perovskite solar cell, the perovskite thin film light absorption layer is prepared from the metal halide perovskite material.
Further, the transparent conductive electrode may include at least one of Indium Tin Oxide (ITO), fluorine-doped tin oxide (FTO), silver nanowire or copper nanowire, for example.
The substrate comprises at least one of a rigid glass substrate and a flexible transparent polymer material substrate.
The electron transport layer may include titanium oxide, tin oxide, zinc oxide, fullerene C60, fullerene derivatives (6,6) -phenyl-C61-methyl butyrate (PCBM), (6,6) -phenyl-C71-methyl butyrate (PC 71 BM), N' -methylenebisacrylamide-fullerene C60 (Bis-C60), [1,2:2,3';56,60: 2', 3' ] [5,6] fullerene-C60-IH (ICBA), 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi) and the like, or a combination of two or more thereof.
The electron transport layer also comprises an electron type interface modification layer which can be used in combination with the electron transport layer, such as 2,9-dimethyl-4,7-diphenyl-1, 10-phenanthroline (BCP), ethoxylated Polyethyleneimine (PEIE), tin oxide and the like.
The hole transport layer comprises nickel oxide, lithium manganese doped nickel oxide, molybdenum oxide, tungsten oxide, cuprous thiocyanate (CuSCN), cuprous iodide (CuI) and cuprous oxide (Cu) 2 O), reduced graphene oxide (rGO), 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino]-9,9' -spirobifluorene (Spiro-OMeTAD), poly [ bis (4-phenyl) (2,4,6-trimethylphenyl) amine](PTAA), PTB7, 3-hexyl-substituted polythiophene (P3 HT), poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS), poly (9-vinylcarbazole) (PVK), 1,2,4,5-tetrakis (trifluoromethyl) benzene (TFB), poly [ bis (4-phenyl) (4-butylphenyl) amine](ploy-TPD), and organic hole transport materials based on phosphoric acid and carbazole groups (e.g., nPACz, me-nPACz, meO-nPACz, ph-nPACz, where n =2, 4, etc.), and the like.
The hole transport layer may also include a hole-type interface modification layer, such as molybdenum oxide, tungsten oxide, tantalum-doped tungsten oxide, etc., which may be used in combination therewith.
The top electrode comprises at least one of gold, silver, copper, aluminum, indium Tin Oxide (ITO), indium tungsten oxide (IWO), fluorine-doped tin oxide (FTO) and carbon electrode.
Further, the thickness of the electron transport layer and the hole transport layer is preferably 1 to 500 nm, and more preferably 10 to 100 nm.
Further, the thickness of the top electrode is preferably 50 to 5000 nm, and more preferably 80 to 200nm.
Of course, the key point of the technical solution provided by the present invention lies in the preparation process of the perovskite thin film as the light absorbing layer (or called photoelectric conversion layer), which is green, low-toxicity and environment-friendly, and the thin film performance of the obtained perovskite thin film and the photoelectric performance of the perovskite solar cell are both excellent, while the material selection of the remaining layers can realize the functions of the corresponding layers, and is not limited to the various selection ranges of the specific examples disclosed above.
The method for manufacturing the perovskite device may include, for example, the following steps for manufacturing an upright perovskite solar cell:
s1, preparing an electron transmission layer on the transparent conductive electrode substrate.
And S2, preparing a perovskite thin film light absorption layer on the electron transmission layer.
And S3, preparing a hole transport layer or a hole transport layer and a hole type interface modification layer on the perovskite thin film light absorption layer.
And S4, preparing a top electrode on the hole transport layer to obtain the perovskite solar cell.
Alternatively, for the preparation of the inverted perovskite solar cell device, for example, the following steps may be included:
s1, preparing a hole transport layer on the transparent conductive electrode substrate.
And S2, preparing a perovskite thin film light absorption layer on the hole transport layer.
And S3, preparing an electron transmission layer or an electron transmission layer and an electron type interface modification layer on the perovskite thin film light absorption layer.
And S4, preparing a top electrode on the electron transmission layer to obtain the perovskite solar cell.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention. Further, since the thickness of each film is not absolutely uniform, the thickness of each film in the following examples is a statistical value.
Example 1
The present example is exemplified by a preparation method and specific steps of a laboratory-scale typical positive perovskite solar cell device (the structure of which is shown in fig. 1 a), and the specific process is as follows:
a) Preparing a perovskite precursor solution: selecting mixed ionic perovskite FA 0.90 MA 0.05 Cs 0.05 Pb(I 0.9 Br 0.1 ) 3 The precursor components of the compound are formamidine iodide (FAI) and lead iodide (PbI) 2 ) Methyl ammonium bromide (MABr), lead bromide (PbBr) 2 ) The weight ratio of the substances is prepared according to the stoichiometric ratio, and lead iodide (PbI) with the molar ratio of 4 percent is additionally added 2 ) And 20% methylammonium chloride (MAC 1). The solvent is a mixed solvent with the volume ratio of dimethyl sulfoxide (DMSO) to delta (delta) -valerolactone (DVL) being 1: 1, the mass concentration of the perovskite precursor solution (calculated by lead element) is 1.3 mol/L, and the perovskite precursor solution is weighed, stirred, dissolved and filtered for standby.
b) Cleaning and pretreating a substrate: and sequentially and ultrasonically cleaning the FTO/glass substrate by adopting surfactant/water, deionized water and isopropanol for about 20 minutes, and then drying by using a drying oven or drying by using nitrogen for later use. The cleaned FTO/glass substrate is subjected to a uv-ozone or oxygen plasma pretreatment for about 10 minutes.
c) Preparation of an electron transport layer: taking a proper amount of titanium oxide precursor solution prepared from titanium tetraisopropoxide and isopropanol, spin-coating the titanium oxide precursor solution on an FTO glass substrate, transferring the FTO glass substrate to an atmosphere laboratory environment with lower humidity, and annealing the FTO glass substrate on a hot bench at 450 ℃ for about 30 minutes to finish the TiO electron transport layer with the thickness of about 20-30 nanometers x And (4) preparing.
d) Preparing a perovskite light absorption layer: in a glove box, taking a proper amount of perovskite precursor solution prepared by the green solvent in the step a) and coating the perovskite precursor solution on TiO in a rotating way x And (3) treating the rotating film by using an anti-solvent 10-15 seconds before the spin coating is finished on the substrate, and finally, annealing the spin-coated substrate on a 110 ℃ hot table for about 15 minutes to finish the preparation of the perovskite film light absorption layer with the thickness of 550-750 nanometers.
e) Preparation of hole transport layer: doping hole transport materials Spiro-MeOTAD, lithium Salt (Li-TFSI), cobalt Salt (FK 209 Co (II I) TFSI Salt) and 4-tert-butylpyridine (tBP) according to the mass concentration of 1: 0.5: 0.03: 2, and then spin-coating a proper amount of prepared solution on the perovskite film to finish the preparation of the hole transport layer Spiro-MeOTAD with the thickness of 50-80 nanometers. The devices prepared by spin coating above were then transferred to an electron oven for about 12 hours of oxidation treatment.
f) Vapor deposition of a metal electrode: and finally transferring the oxidized device to a glove box vacuum evaporation coating instrument system, and evaporating 7-10 nanometer molybdenum trioxide and 100 nanometer metal silver to finish the preparation of the whole green solvent-based perovskite solar cell device.
g) And (3) testing the performance of the device: the current-voltage test of the device was performed under a standard simulated solar illumination.
As shown in fig. 3, compared with the photovoltaic efficiency of the perovskite solar cell with the positive structure prepared from the conventional solvent DMF to DMSO (the volume ratio is 9: 1) and the green solvent provided in this example, it can be seen that the perovskite solar cell prepared from the green solvent has higher photoelectric conversion efficiency.
Example 2
This example illustrates a preparation method and specific steps of a typical laboratory-scale inverted perovskite solar cell device (the device structure of which is shown in fig. 1 b), and the specific process is as follows:
a) Preparing a perovskite precursor solution: selecting mixed ionic perovskite FA 0.90 MA 0.05 Cs 0.05 Pb(I 0.9 Br 0.1 ) 3 The precursor components of the compound are formamidine iodide (FAI) and lead iodide (PbI) 2 ) Methyl ammonium bromide (MABr), lead bromide (PbBr) 2 ) The amount ratio of the intermediate substances is prepared according to the stoichiometric ratio of the molecular formula, and 5 percent of lead iodide (PbI) is additionally added 2 ) And 10% methylammonium chloride (MACl). The solvent is a mixed solvent with the volume ratio of dimethyl sulfoxide (DMSO) to gamma (gamma) -valerolactone (GVL) of 2: 1, the mass concentration of the perovskite precursor solution (calculated by lead element) is 1.3 mol/L, and the perovskite precursor solution is weighed, stirred, dissolved and filtered for later use.
b) Cleaning and pretreating a substrate: and (3) respectively ultrasonically cleaning the FTO/glass substrate by adopting surfactant/water, deionized water and isopropanol for about 20 minutes in sequence, and then drying by using a drying oven or drying by using nitrogen for later use. The cleaned FTO/glass substrate is subjected to a uv-ozone or oxygen plasma pretreatment for about 10 minutes.
c) Preparation of hole transport layer: taking a proper amount of nickel oxide nanocrystal solution to spin-coat on an FTO glass substrate, then transferring the FTO glass substrate to a heating table at 120 ℃ to anneal for about 15 minutes,completing a hole transport layer NiO with the thickness of 15-20 nm x And (4) preparing.
d) Preparing a perovskite light absorption layer: in a glove box, a perovskite precursor solution prepared by taking a proper amount of green solvent is coated on NiO in a rotating way x And (3) carrying out anti-solvent treatment on the rotating film by adopting chlorobenzene 10-15 seconds before the spin coating is finished on the substrate, and finally, annealing the spin-coated substrate on a 110 ℃ hot table for about 15 minutes to finish the preparation of the perovskite film light absorption layer with the thickness of 450-650 nanometers.
e) Preparation of an electron transport layer: coating an organic electron transport material PCBM solution on the perovskite thin film in a spinning mode, and then placing the perovskite thin film on a heating table at 110 ℃ for annealing for about 10 minutes; spin coating BCP solution, annealing at 110 deg.C for 10 min to obtain 20-30 nm thick electron transport layer.
f) Evaporation of metal electrode: and finally transferring the device to a glove box vacuum evaporation coating instrument system, evaporating 100 nanometer metal silver, and finally completing the preparation of the whole perovskite solar cell device based on the green solvent.
g) And (3) testing of the device: the current-voltage test of the device was performed under a standard simulated solar illumination. The perovskite solar cell device prepared in this example was found to have the same photovoltaic efficiency as example 1 over conventional solvents.
As shown in fig. 2, comparing DMF based conventional solvents: the steady-state fluorescence spectrum of the perovskite thin film with the same device structure of NMP (the volume ratio is 9:1) and a green solvent shows that the perovskite thin film prepared by the green solvent provided by the embodiment has higher fluorescence intensity and shows lower non-radiative recombination, and the preparation of a high-performance photovoltaic or photoelectric device is beneficial.
Example 3
This example illustrates a preparation method and specific steps of a typical laboratory-scale inverted perovskite solar cell device (the device structure of which is shown in fig. 1 b), and the specific process is as follows:
a) Preparing a perovskite precursor solution: selecting mixed ionic perovskite FA 0.90 MA 0.02 Cs 0.03 Pb(I 0.97 Br 0.03 ) 3 The precursor components of the compound are formamidine iodide (FAI) and lead iodide (PbI) 2 ) The quantity ratio of the substances among the methylammonium bromide (MABr) and the lead bromide (PbBr 2) is prepared according to the stoichiometric ratio, and 2 percent of lead iodide (PbI) is additionally added 2 ) And 30% methylammonium chloride (MACl). The solvent is a mixed solvent with the volume ratio of dimethyl sulfoxide (DMSO) to 1,3-dimethyl-2-imidazolidinone (DMI) being 1: 3, the mass concentration of the perovskite precursor solution (calculated by lead element) is 1.3 mol/L, and the perovskite precursor solution is weighed, stirred, dissolved and filtered for standby.
b) Cleaning and pretreating a substrate: and (3) respectively ultrasonically cleaning the FTO/glass substrate by using liquid detergent/water, deionized water and isopropanol for about 20 minutes in sequence, and then drying by using a drying oven or drying by using nitrogen for later use. The cleaned FTO/glass substrate is subjected to a uv-ozone or oxygen plasma pretreatment for about 10 minutes.
c) Preparation of hole transport layer: taking a proper amount of nickel oxide nanocrystal solution to spin-coat on an FTO glass substrate, then transferring the FTO glass substrate to a heating table at 120 ℃ for annealing for about 15 minutes to finish a hole transport layer NiO with the thickness of 15-20 nanometers x And (4) preparing.
d) Preparing a perovskite light absorption layer: in a glove box, a proper amount of green solvent is taken to prepare perovskite precursor solution, and the perovskite precursor solution is coated on NiO in a rotating way x And (3) carrying out anti-solvent treatment on the rotating film by adopting chlorobenzene 10-15 seconds before the spin coating is finished on the substrate, and finally, annealing the spin-coated substrate on a heating table at 110 ℃ for about 15 minutes to finish the preparation of the perovskite film light absorption layer with the thickness of 450-650 nanometers.
e) Preparation of an electron transport layer: coating an organic electron transport material PCBM solution on the perovskite thin film in a spinning mode, and then placing the perovskite thin film on a heating table at 110 ℃ for annealing for about 10 minutes; spin coating BCP solution, annealing at 110 deg.C for 10 min to obtain 20-30 nm thick electron transport layer.
f) Evaporation of metal electrode: and finally transferring the device to a glove box vacuum evaporation coating instrument system, evaporating 100 nanometer metal silver, and finally completing the preparation of the whole perovskite solar cell device based on the green solvent.
g) And (3) testing of the device: the current-voltage test of the device was performed under a standard simulated solar illumination. The perovskite solar cell device prepared in this example was found to have the same photovoltaic efficiency as example 1 over conventional solvents.
Example 4
This example illustrates the fabrication of a perovskite solar cell, substantially the same as in example 1, with the main differences:
the concentration of the prepared perovskite precursor solution is 0.5mol/L, and the thickness of the formed perovskite thin film is about 200nm.
Through tests, the photovoltaic efficiency of the perovskite solar cell prepared in the embodiment is similar to that of the perovskite solar cell prepared in the embodiment 1, and is still remarkably superior to that of the perovskite solar cell prepared by the traditional solvent.
Example 5
This example illustrates the fabrication of a perovskite solar cell, substantially the same as in example 1, with the main differences:
the concentration of the prepared perovskite precursor solution is 2.0mol/L, and the thickness of the formed perovskite thin film is about 1000nm.
Through tests, the photovoltaic efficiency of the perovskite solar cell prepared in the embodiment is similar to that of the perovskite solar cell prepared in the embodiment 1, and is still remarkably superior to that of the perovskite solar cell prepared by the traditional solvent.
Comparative example 1
This comparative example is substantially the same as example 1, except that:
when the perovskite precursor solution is prepared, the solvent is replaced by an alcohol green solvent such as ethanol or isopropanol or a mixed green solvent of dimethyl sulfoxide and alcohol such as ethanol or isopropanol.
Although the solution of the alcohol solvent is still a low-toxicity and environmentally-friendly solvent, the alcohol solvent shows very poor solubility to the perovskite precursor material, so that the solvent selected in the comparative example cannot obtain a perovskite solution with good solubility, and cannot prepare a good perovskite thin film. This is because the selection of the solvent does not match the dissolution and film-forming characteristics of the perovskite precursor material, and thus a normal perovskite solution cannot be obtained, and a good perovskite thin film cannot be prepared.
Comparative example 2
This comparative example is substantially the same as example 1, except that:
when the perovskite precursor solution is prepared, the solvent is replaced by an ester green solvent such as ethyl acetate or methyl acetate, or a mixed green solvent of dimethyl sulfoxide and esters such as ethyl acetate or methyl acetate.
Although the comparative example still uses a low-toxicity and environment-friendly solvent scheme, the ester solvent shows extremely poor solubility to the perovskite precursor material, so that the solvent selected in the comparative example cannot obtain a perovskite solution with good solubility even and cannot prepare a good perovskite thin film. This is because the selection of the solvent does not match the dissolution and film-forming characteristics of the perovskite precursor material, and thus a normal perovskite solution cannot be obtained, and a good perovskite thin film cannot be prepared.
Based on the above embodiments, it is clear that the solvent used in the preparation method provided by the embodiment of the present invention is a specific green and environment-friendly solvent with extremely low toxicity, which is safe to human body, and the problem that solvents used in the preparation of perovskite thin films by the conventional solution method, such as N, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), etc., have obvious or even high toxicity and easily cause health hazards to practitioners is solved, so that the preparation process of metal halide perovskite thin films is more green and environment-friendly, is safer and more friendly to practitioners, effectively avoids the hazards of a large amount of toxic solvents to ecological environment and personnel health, and is more suitable for the industrial green production of large-area perovskite solar cells.
In addition, the metal halide perovskite thin film prepared by the preparation method provided by the embodiment of the invention has the advantages of higher crystal quality, sufficient phase transformation, high phase purity, better fluorescence performance of the perovskite thin film and more excellent photovoltaic performance of the corresponding perovskite solar cell.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. 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 perovskite thin film, comprising:
providing a precursor solution, wherein the precursor solution contains a perovskite precursor and a selected solvent, and the selected solvent comprises any one or the combination of more than two of gamma-butyrolactone, delta-valerolactone, gamma-valerolactone, 1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide;
and preparing a film precursor by using the precursor solution through a solution method, and carrying out post-treatment on the film precursor to form the perovskite film.
2. The production method according to claim 1, wherein the selected solvent is a mixed solvent of two or more solvents;
preferably, the selected solvent is selected from dimethyl sulfoxide and any one or more than two of gamma-butyrolactone, delta-valerolactone, gamma-valerolactone and 1,3-dimethyl-2-imidazolidinone;
preferably, the volume fraction of the dimethyl sulfoxide in the mixed solvent is 10-70%.
3. The production method according to claim 1, wherein the molar concentration of the perovskite precursor in the precursor solution is 0.5 to 2.0mol/L;
and/or the thickness of the perovskite thin film is 10-2000nm, preferably 100-1000nm.
4. The method according to claim 1, wherein the perovskite thin film is made of a material satisfying ABX 3 An ionic crystal of the structure or satisfy A' m A n-1 B n X 3n+1 An ionic crystal of the structure m =1 or 2,n ofAn integer of not less than 1;
wherein A is a monovalent organic or inorganic cation, B is a divalent metal cation, X is a monovalent anion, and A' is a monovalent or divalent long-chain organic cation.
5. The preparation method according to claim 4, wherein A comprises any one or a combination of two or more of methylammonium ions, formamidine ions, cesium ions and rubidium ions;
and/or B comprises any one or the combination of more than two of lead ions, tin ions, germanium ions and copper ions;
and/or X comprises any one or the combination of more than two of iodide ion, bromide ion, chloride ion and thiocyanate ion;
and/or A' comprises any one or the combination of more than two of butylammonium ion, phenethylammonium ion, ammonium valerate ion, ethylenediamine ion, propylenediammonium ion and Ding Eran ion.
6. The production method according to claim 1, wherein the solution method includes any one or a combination of two or more of a spin coating method, a blade coating method, a slit extrusion coating method, a spray coating method, a screen printing method, and an inkjet printing method;
and/or the post-treatment comprises any one or the combination of more than two of anti-solvent extraction treatment, airflow drying solvent treatment, vacuum solvent removal treatment and heating annealing treatment.
7. The method according to claim 6, wherein the anti-solvent used in the anti-solvent extraction treatment comprises one or more of ethyl acetate, methyl acetate, propyl acetate, anisole, and phenetole.
8. A perovskite thin film produced by the production method as set forth in any one of claims 1 to 7.
9. A perovskite photoelectric device comprises a hole transport layer, a photoelectric conversion layer and an electron transport layer which are sequentially stacked;
characterized in that the photoelectric conversion layer comprises the perovskite thin film as defined in claim 8;
preferably, the perovskite photoelectric device is a perovskite solar cell, and the photoelectric conversion layer is a light absorption layer.
10. The perovskite optoelectronic device of claim 9, wherein the perovskite solar cell comprises a transparent conductive electrode substrate, an electron transport layer, a photoelectric conversion layer, a hole transport layer, and a top electrode, sequentially stacked;
or, the perovskite solar cell comprises a transparent conductive electrode substrate, a hole transport layer, a photoelectric conversion layer, an electron transport layer and a top electrode which are sequentially stacked.
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