CN113937245B - Efficient white light organic-inorganic hybrid zinc-based two-dimensional perovskite material and preparation method thereof - Google Patents
Efficient white light organic-inorganic hybrid zinc-based two-dimensional perovskite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-efficiency white light organic-inorganic hybrid zinc-based two-dimensional perovskite material and a preparation method thereof, and belongs to the technical field of photoelectric materials. The preparation method comprises the following steps: respectively dissolving zinc halide and organic amine in the same volatile polar solvent to obtain a premix X and a premix Y; after mixing, dropwise adding halogen acid to enable organic amine to be protonated to form organic amine ions, and reacting with zinc ions and halogen ions to obtain premix Z; after the solvent is volatilized, organic-inorganic hybrid zinc-based two-dimensional perovskite crystals are separated out, and the general formula A 2 ZnX 4 Wherein A is aromatic amine cation, X is one or more of halogen elements F, cl and Br. The organic-inorganic hybrid zinc-based two-dimensional perovskite material provided by the invention has high purity, nontoxic zinc metal ions are used for replacing heavy metal lead ions, the emission spectrum of the organic-inorganic hybrid zinc-based two-dimensional perovskite material covers the whole visible light range (400-750 nm), the photoluminescence quantum yield is high, and the stability is good.
Description
Technical Field
The invention belongs to the technical field of photoelectric materials, and particularly relates to a high-efficiency white organic-inorganic hybrid zinc-based two-dimensional perovskite material and preparation thereof.
Background
White Light Emitting Diodes (WLEDs) are used as a new generation of lighting products, and replace fluorescent lamps to enter thousands of households due to the advantages of energy conservation, environmental protection, high efficiency, stability, durability and the like. Conventional artificial white light is generally obtained by incandescent lamps, fluorescent lights, etc., however, light Emitting Diodes (LEDs) gradually come into the field of view of people due to higher electroluminescent efficiency, which is important for achieving the sustainability of energy sources. However, a broad-spectrum white light emitting LED is generally obtained by coating a yellow fluorescent powder on a blue LED chip or coating a plurality of fluorescent powders with different colors on an ultraviolet LED chip, and the WLED obtained by the conventional method has a loss of efficiency due to a self-absorption effect caused by overlapping spectra of the plurality of fluorescent powders. Moreover, due to the different aging rates of different fluorescent powders, the light-emitting spectrum of the WLED can be gradually shifted in the use process, so that the WLED is limited to be widely used. Thus, finding a single phosphor that emits highly efficient and stable intrinsic white light is a major goal of solid state lighting technology.
In recent years, organic-inorganic hybrid perovskite materials have been rapidly developed in the emerging photoelectric fields of solar cells, nonlinear optics, lasers, light-emitting diodes and the like due to the advantages of excellent photoelectric properties, simple and convenient experimental methods, low manufacturing cost and the like. Organic-inorganic halide perovskites can be classified as 3D, 2D, 1D, and even 0D perovskites according to structural classification, depending on how the metal halide octahedra are interconnected. The two-dimensional hybridized perovskite greatly increases the diversity of the perovskite, namely, long-chain organic cations are used for replacing A sites, the dimension of the electronic structure of the material can be reduced from three dimensions to two dimensions, and the selectable range of the long-chain organic cations is very wide. Due to quantum confinement effects, two-dimensional perovskite has a large exciton binding energy, so the number of excitons dominates over free charge even at lower excitation densities. The special excitonic properties of two-dimensional perovskite make their photophysical characteristics very different from those of 3D perovskite, and two-dimensional perovskite exhibits extremely broad spectrum and large stokes shift in photoluminescence spectrum. The two-dimensional perovskite has the characteristics of solution processing, molecular scale self-assembly, excellent film forming property and the like of the two-dimensional material, and also has the advantages of excellent light emitting characteristic, higher quantum yield, higher color purity and the like of the perovskite, so that the perovskite becomes a new generation candidate material of electronic and photoelectric integrated devices such as light emitting diodes, field effect transistors, lasers and the like.
However, the photoluminescence quantum yield of the current organic-inorganic hybrid two-dimensional perovskite materials with white luminescence is very low, such as (N-MEDA) PbBr 4 The quantum yield was only 0.5% (C) 4 H 9 NH 3 ) 2 PbCl 4 Exhibiting a quantum yield of 1%. Since the broad-spectrum white luminescence mainly originates from self-trapping exciton recombination luminescence caused by strong phonon-electron coupling in the low-dimensional perovskite, an effective method for improving the luminous efficiency of the two-dimensional hybrid perovskite material is to increase the twistability of the crystal structure of the material by a halogen mixing method. And, lead is a major component of perovskite, which is greatly toxicThe application of the lead-free alloy in the photoelectric field is restricted, and therefore, the lead needs to be replaced by non-toxic or less toxic elements. There have been many reports that it has been demonstrated that toxic Pb elements can be effectively replaced with nontoxic metal elements such as Sn, ge, sb, and Bi, to obtain a green lead-free perovskite material. However, the resulting lead-free perovskite after substitution of these elements typically significantly reduces its photoluminescence quantum yield, well below that of lead-based perovskite materials, and even makes its stability significantly compromised.
Disclosure of Invention
The invention solves the technical problem that the photoluminescence quantum yield of the white-light-emitting organic-inorganic hybrid two-dimensional perovskite material is very low in the prior art, and provides the high-efficiency white-light organic-inorganic hybrid zinc-based two-dimensional perovskite material and the preparation method.
According to a first aspect of the present invention, there is provided a method for preparing an organic-inorganic hybrid zinc-based two-dimensional perovskite material, comprising the steps of:
(1) Respectively dissolving zinc halide and organic amine in a volatile polar solvent to obtain a premix X and a premix Y;
(2) Mixing the premix liquid X and the premix liquid Y obtained in the step (1), then dropwise adding halogen acid to enable organic amine to be protonated to form organic amine ions, and reacting with zinc ions and halogen ions to obtain premix liquid Z;
(3) And (3) volatilizing the solvent in the premix Z obtained in the step (2), and separating out the organic-inorganic hybrid zinc-based two-dimensional perovskite crystal.
Preferably, the zinc halide is at least one of zinc fluoride, zinc chloride and zinc bromide; the hydrohalic acid is at least one of hydrofluoric acid, hydrochloric acid and hydrobromic acid.
Preferably, the organic amine is an aromatic amine.
Preferably, the aromatic amine is benzyl amine, phenethyl amine, phenylpropyl amine, p-methyl phenethyl amine, o-fluorobenzene methyl amine, m-fluorobenzene methyl amine, o-fluorobenzene ethyl amine, m-fluorobenzene ethyl amine or p-fluorobenzene ethyl amine.
Preferably, the volatile polar solvent is at least one of methanol, absolute ethanol, isopropanol and acetone.
Preferably, the ratio of the concentration of the organic amine ion to the concentration of the zinc ion in the premix Z is (0.1-10): 1.
Preferably, the concentration of the organic amine ions in the premix Z is 0.05mol/L-10mol/L, and the concentration of the zinc ions is 0.05mol/L-10mol/L.
According to another aspect of the invention, there is provided an organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by any one of the methods.
Preferably, the organic-inorganic hybrid zinc-based two-dimensional perovskite material has a general formula of A 2 ZnX 4 Wherein A is aromatic amine cation, X is at least one of halogen element F, cl and Br;
preferably, the aromatic amine cation is a benzylamine ion, a phenethylamine ion, an amphetamine ion, a p-methylphenylethylamine ion, an o-fluorophenylmethylamine ion, a m-fluorophenylmethylamine ion, an o-fluorophenylethylamine ion, a m-fluorophenylethylamine ion, or a p-fluorophenylethylamine ion.
According to another aspect of the invention, a white light LED device is provided, comprising the organic-inorganic hybrid zinc-based two-dimensional perovskite material.
In general, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) The organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by the method has high purity, the emission spectrum covers the whole visible light range (400-750 nm), the photoluminescence quantum yield is high and can reach more than 20%, the quantum yield is far higher than that of the existing white light two-dimensional hybrid lead halide perovskite, and the stability of the material is good.
(2) The luminescent property of the organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by the preparation method can be regulated and controlled by halogen doping, and the radiation recombination probability of the zinc-based two-dimensional perovskite is improved, so that the luminescent property of the zinc-based two-dimensional perovskite material is improved.
(3) Compared with the organic-inorganic hybrid zinc-based two-dimensional perovskite material obtained by a hydrothermal method, the organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by the method is prepared by adopting an evaporation crystallization method to crystallize, and the system belongs to an anhydrous system, so that fluorescence quenching caused by the generation of non-fluorescent perovskite complex can be avoided.
(4) The organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by the invention has the luminescence center wavelength of 502-521nm, the half-peak width of 115-175nm and the photoluminescence quantum yield of 3-21%. White light is derived from self-trapping exciton recombination luminescence caused by strong phonon-electron coupling in low-dimensional perovskite.
(5) The organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by the preparation method disclosed by the invention has excellent thermal stability; the specific expression is that the photoluminescent intensity of the material still maintains 70-98% of the original intensity after continuously heating for 1000 hours at 80 ℃.
(6) The organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by the preparation method disclosed by the invention has excellent light stability; the method is characterized in that the photoluminescence intensity of the LED with the rated power of 6W and the wavelength of 365nm is continuously irradiated for 240 minutes, and the photoluminescence intensity still keeps 50-75% of the original intensity.
(7) The organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by the method has excellent storage stability; the specific expression is that the photoluminescent intensity is almost unchanged when the product is stored for 4 months under the environmental conditions that the temperature is 20-25 ℃ and the humidity is 50-70%.
(8) The invention utilizes the principle of an evaporation crystallization method, uses volatile polar liquid as a solvent, slowly evaporates a solution containing a solute with stoichiometric ratio, and prepares the high-efficiency white light organic-inorganic hybrid zinc-based two-dimensional perovskite material through the steps of filtering, washing, vacuum drying and the like. In the whole preparation process of the organic-inorganic hybrid zinc-based two-dimensional perovskite material, no toxic raw materials or reagents are used, and the preparation method is environment-friendly and environment-friendly.
(9) The organic-inorganic hybrid zinc-based two-dimensional perovskite material provided by the invention has high purity, uses nontoxic zinc metal ions to replace heavy metal lead ions, has high photoluminescence quantum yield and good stability, is simple in preparation process, mild in production condition, low in cost, high in repeatability, short in preparation period and environment-friendly, can be effectively applied to the field of solid-state illumination, and is hopeful to design a high-efficiency single-component white light emitting diode.
Drawings
FIG. 1 is an XRD pattern of the organic-inorganic hybrid zinc-based two-dimensional perovskite materials of examples 1-7.
FIG. 2 is an ultraviolet visible absorption spectrum of the organic-inorganic hybrid zinc-based two-dimensional perovskite materials of examples 1-7.
FIG. 3 is a fluorescence spectrum of an organic-inorganic hybrid zinc-based two-dimensional perovskite material of examples 1-7.
FIG. 4 is a fluorescence lifetime spectrum of organic-inorganic hybrid zinc-based two-dimensional perovskite materials of examples 1-7.
FIG. 5 is a microscopic pattern of the organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 5.
FIG. 6 is an EDS spectrum of an organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 5.
FIG. 7 is a CIE chromaticity diagram corresponding to the fluorescence spectrum of the organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 5.
Fig. 8 is an excitation spectrum of the organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 5 at different emission wavelengths.
FIG. 9 is a two-dimensional profile of fluorescence at different excitation wavelengths for the organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 5.
FIG. 10 is a fluorescence spectrum at different temperatures of the organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 5.
FIG. 11 is a graph of the photostability of the organic-inorganic hybrid zinc-based two-dimensional perovskite materials of examples 1 and 5 heated continuously at 80℃for 1000 hours.
FIG. 12 is a graph of the photostability of the organic-inorganic hybrid zinc-based two-dimensional perovskite materials of examples 1 and 5 upon continuous illumination for 240 minutes under a 365nm violet lamp having a power of 6W.
FIG. 13 is a graph showing the comparison of fluorescence spectra of organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 5 stored for 4 months under ambient conditions of temperature 20-25deg.C and humidity 50-70%.
Fig. 14 is a schematic diagram describing the white light principle of an organic-inorganic hybrid zinc-based two-dimensional perovskite material.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention relates to a preparation method of a high-efficiency white light organic-inorganic hybrid zinc-based two-dimensional perovskite material, which mainly comprises the following steps:
(1) Weighing zinc halide with certain mass under inert atmosphere, dissolving the zinc halide in a volatile polar solvent, and stirring until the solution is clear to obtain a premix X;
(2) Dissolving organic amine containing A in stoichiometric ratio in the same volatile polar solvent, and stirring until the solution is clear to obtain premix Y;
(3) Mixing the premix X with the premix Y, then dropwise adding halogen acid with corresponding molar volume, and stirring until the solution is clear to obtain premix Z;
(4) Sealing the premix Z obtained in the step (3) by using a sealing film, stamping a plurality of small holes to control the solvent volatilization rate, slowly evaporating the premix Z for a plurality of days at room temperature, and separating out colorless non-lead organic-inorganic hybrid zinc-based two-dimensional perovskite material crystals at the bottom of a container;
(5) And (3) washing the crystal obtained in the step (4) with a detergent for three times, and then drying the crystal in a vacuum drying oven at 60 ℃.
Preferably, in step (1), the volatile solvent is methanol or absolute ethanol.
Preferably, in the step (3), the halogen acid is one or a mixture of hydrofluoric acid HF, hydrochloric acid HCl and hydrobromic acid HBr.
Preferably, in the step (5), the detergent is one or a mixture of more than one of isopropanol, acetone, diethyl ether and ethyl acetate.
Preferably, the concentration ratio of A to zinc ions in the premix Z is (0.1-10): 1.
Preferably, the concentration of A in the premix Z is 0.05-10mol/L, and the concentration of B ions is 0.05-10mol/L.
The general formula of the high-efficiency white light organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by the preparation method meets A 2 ZnX 4 Wherein A is a long chain aromatic amine cation including a benzylamine ion (C 6 H 5 CH 2 NH 3 + ，BA + ) Phenethylamine ion (C) 6 H 5 C 2 H 4 NH 3 + ，PEA + ) Amphetamine ion (C) 6 H 5 C 3 H 6 NH 3 + ，PPA + ) P-methylphenylamine ion (CH) 3 C 6 H 5 C 2 H 4 NH 3 + ，4-MPEA + ) O-fluorobenzylamine ion (FC) 6 H 4 CH 2 NH 3 + ，2-FBA + ) M-fluorobenzylamine ion (FC) 6 H 4 CH 2 NH 3 + ，3-FBA + ) O-fluorophenylethylamine ion (FC) 6 H 4 C 2 H 4 NH 3 + ，2-FPEA + ) M-fluorophenylethylamine ion (FC) 6 H 4 C 2 H 4 NH 3 + ，3-FPEA + ) Para-fluorophenylethylamine ion (FC) 6 H 4 C 2 H 4 NH 3 + ，4-FPEA + ) One or more of halogen elements F, cl and Br.
Example 1
1mmol of zinc chloride (ZnCl) 2 ) And 2mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 2ml of methanol, uniformly mixing the two premix solutions, adding 160 μl of hydrochloric acid, and vigorously stirring at room temperature for 4h at 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol for three times, and drying in a vacuum drying oven at 60 ℃ for one day to obtain the organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA 2 ZnCl 4 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 2.9%, the fluorescence lifetime is 3.19ns, the luminescence center is located at 521nm, and the half-peak width is 175nm.
Example 2
1mmol of zinc chloride (ZnCl) 2 ) And 2mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 2ml of methanol, uniformly mixing the two premix solutions, then adding a mixed acid solution containing 150 mu l of hydrochloric acid and 5 mu l of hydrofluoric acid, and vigorously stirring for 4 hours at room temperature at a rotating speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol for three times, and drying in a vacuum drying oven at 60 ℃ for one day to obtain the organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA 2 Zn(F x Cl 1-x ) 4 (x=1/16). The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 7.5%, the fluorescence lifetime is 3.78ns, the luminescence center is located at 517nm, and the half-peak width is 122nm.
Example 3
1mmol of zinc chloride (ZnCl) 2 ) And 2mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 2ml methanol, mixing the two pre-mixed solutions, adding mixed acid solution containing 142 μl hydrochloric acid and 10 μl hydrofluoric acid, and stirring vigorously at room temperature for 4 hr at 800-1000rpm/min to obtain clear transparent solutionAnd (3) liquid. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol for three times, and drying in a vacuum drying oven at 60 ℃ for one day to obtain the organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA 2 Zn(F x Cl 1-x ) 4 (x=1/9). The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 11.2%, the fluorescence lifetime is 5.38ns, the luminescence center is located at 516nm, and the half-peak width is 116nm.
Example 4
1mmol of zinc chloride (ZnCl) 2 ) And 2mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 2ml of methanol, uniformly mixing the two premix solutions, then adding mixed acid solution containing 133 mu l of hydrochloric acid and 15 mu l of hydrofluoric acid, and vigorously stirring for 4 hours at room temperature at a rotating speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol for three times, and drying in a vacuum drying oven at 60 ℃ for one day to obtain the organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA 2 Zn(F x Cl 1-x ) 4 (x=1/6). The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 14.3%, the fluorescence lifetime is 5.46ns, the luminescence center is located at 510nm, and the half-peak width is 119nm.
Example 5
1mmol of zinc chloride (ZnCl) 2 ) And 2mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 2ml of methanol, uniformly mixing the two premix solutions, then adding mixed acid solution containing 120 mu l of hydrochloric acid and 23 mu l of hydrofluoric acid, and vigorously stirring for 4 hours at room temperature at a rotating speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in vacuum oven at 60deg.C for one dayObtaining the organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA 2 Zn(F x Cl 1-x ) 4 (x=1/4). The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 21.0%, the fluorescence lifetime is 6.07ns, the luminescence center is located at 509nm, and the half-peak width is 115nm.
Example 6
1mmol of zinc chloride (ZnCl) 2 ) And 2mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 2ml of methanol, uniformly mixing the two premix solutions, then adding mixed acid solution containing 80 mu l of hydrochloric acid and 46 mu l of hydrofluoric acid, and vigorously stirring for 4 hours at room temperature at a rotating speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol for three times, and drying in a vacuum drying oven at 60 ℃ for one day to obtain the organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA 2 Zn(F x Cl 1-x ) 4 (x=1/2). The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 7.0%, the fluorescence lifetime is 5.53ns, the luminescence center is located at 509nm, and the half-peak width is 126nm.
Example 7
1mmol of zinc chloride (ZnCl) 2 ) And 2mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 2ml of methanol, uniformly mixing the two premix solutions, then adding mixed acid solution containing 40 mu l of hydrochloric acid and 69 mu l of hydrofluoric acid, and vigorously stirring for 4 hours at room temperature at a rotating speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol for three times, and drying in a vacuum drying oven at 60 ℃ for one day to obtain the organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA 2 Zn(F x Cl 1-x ) 4 (x=3/4). The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 6.2 percent, the fluorescence lifetime is 5.18ns,the luminescence center is located at 502nm, and the half-peak width is 146nm.
Example 8
1mmol of zinc chloride (ZnCl) 2 ) And 2mmol of benzylamine (C) 6 H 5 CH 2 NH 2 ) Dissolving in 2ml of methanol, uniformly mixing the two premix solutions, adding 170. Mu.l of hydrochloric acid, and vigorously stirring at room temperature for 4 hours at 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol for three times, and drying in a vacuum drying oven at 60 ℃ for one day to obtain the organic-inorganic hybrid zinc-based two-dimensional perovskite material BA 2 ZnCl 4 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 5.2%, the fluorescence lifetime is 3.82ns, the luminescence center is 446nm, and the half-peak width is 157nm.
Example 9
1mmol of zinc bromide (ZnBr) 2 ) And 2mmol of benzylamine (C) 6 H 5 CH 2 NH 2 ) Dissolving in 2ml of absolute ethanol, uniformly mixing the two premix solutions, then adding 235 mu l of hydrobromic acid, and vigorously stirring for 4 hours at room temperature at a rotating speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol for three times, and drying in a vacuum drying oven at 60 ℃ for one day to obtain the organic-inorganic hybrid zinc-based two-dimensional perovskite material BA 2 ZnBr 4 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 3.4%, the fluorescence lifetime is 2.72ns, the luminescence center is positioned at 459nm, and the half-peak width is 162nm.
Example 10
1mmol of zinc chloride (ZnCl) 2 ) And 2mmol amphetamine (C) 6 H 5 C 3 H 6 NH 2 ) Dissolving in 2ml isopropanol, mixing the two pre-mixed solutions, adding 170 μl hydrochloric acid, and stirring vigorously at room temperature for 4 hr at 800-1000rpm/min, a clear transparent solution was obtained. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol for three times, and drying in a vacuum drying oven at 60 ℃ for one day to obtain the organic-inorganic hybrid zinc-based two-dimensional perovskite material PPA 2 ZnCl 4 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 1.3%, the fluorescence lifetime is 3.47ns, the luminescence center is located at 441nm, and the half-peak width is 124nm.
Example 11
1mmol of zinc bromide (ZnBr) 2 ) And 2mmol amphetamine (C) 6 H 5 C 3 H 6 NH 2 ) Dissolving in 2ml of acetone, uniformly mixing the two premix solutions, adding 235 mu l hydrobromic acid, and vigorously stirring at room temperature for 4 hours at 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol for three times, and drying in a vacuum drying oven at 60 ℃ for one day to obtain the organic-inorganic hybrid zinc-based two-dimensional perovskite material PPA 2 ZnBr 4 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 10.6%, the fluorescence lifetime is 2.87ns, the luminescence center is positioned at 465nm, and the half-peak width is 130nm.
Example 12
1mmol of zinc chloride (ZnCl) 2 ) And 2mmol of p-methylphenylethylamine (CH) 3 C 6 H 5 C 2 H 4 NH 2 ) Dissolving in 2ml of mixed solution of methanol and absolute ethanol, uniformly mixing the two premix solutions, then adding 170 μl of hydrochloric acid, and vigorously stirring at room temperature for 4h at 800-1000rpm/min to obtain clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol for three times, and drying in a vacuum drying oven at 60deg.C for one day to obtain organic-inorganic hybrid zinc-based two-dimensional perovskite material (4-MPEA) 2 ZnCl 4 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 8.94%, the fluorescence lifetime is 4.49ns, the luminescence center is located at 506nm, and the half-peak width is 137nm.
Example 13
1mmol of zinc bromide (ZnBr) 2 ) And 2mmol of p-methylphenylethylamine (CH) 3 C 6 H 5 C 2 H 4 NH 2 ) Dissolving in 2ml of mixed solution of methanol and isopropanol, uniformly mixing the two premix solutions, adding 235 mu l hydrobromic acid, and vigorously stirring at room temperature for 4 hours at a speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol for three times, and drying in a vacuum drying oven at 60deg.C for one day to obtain organic-inorganic hybrid zinc-based two-dimensional perovskite material (4-MPEA) 2 ZnBr 4 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 3.63%, the fluorescence lifetime is 3.68ns, the luminescence center is located at 490nm, and the half-peak width is 176nm.
Example 14
1mmol of zinc chloride (ZnCl) 2 ) And 2mmol of o-fluoro-substituted benzylamine (FC) 6 H 4 CH 2 NH 2 ) Dissolving in 2ml of mixed solution of methanol and acetone, uniformly mixing the two premix solutions, then adding mixed acid solution containing 120 mu l of hydrochloric acid and 23 mu l of hydrofluoric acid, and vigorously stirring for 4 hours at room temperature at a rotating speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60deg.C for one day to obtain organic-inorganic hybrid zinc-based two-dimensional perovskite material (2-FBA) 2 ZnFCl 3 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 10.60%, the luminescence center is located at 590nm, and the half-peak width is 130nm.
Example 15
Will respectively0.2mmol zinc bromide (ZnBr) 2 ) And 2mmol of o-fluoro-substituted benzylamine (FC) 6 H 4 CH 2 NH 2 ) Dissolving in 2ml of methanol, uniformly mixing the two premix solutions, then adding mixed acid solution containing 180 mu l hydrobromic acid and 23 mu l hydrofluoric acid, and vigorously stirring for 4 hours at room temperature at a speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60deg.C for one day to obtain organic-inorganic hybrid zinc-based two-dimensional perovskite material (2-FBA) 2 ZnFBr 3 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 15.58%, the luminescence center is at 575nm, and the half-peak width is 107nm.
Example 16
10mmol of zinc chloride (ZnCl) 2 ) And 2mmol of m-fluoro-substituted benzylamine (FC) 6 H 4 CH 2 NH 2 ) Dissolving in 2ml of methanol, uniformly mixing the two premix solutions, then adding mixed acid solution containing 120 mu l of hydrochloric acid and 23 mu l of hydrofluoric acid, and vigorously stirring for 4 hours at room temperature at a rotating speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60deg.C for one day to obtain organic-inorganic hybrid zinc-based two-dimensional perovskite material (3-FBA) 2 ZnFCl 3 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 7.97%, the luminescence center is located at 505nm, and the half-peak width is 206nm.
Example 17
1mmol of zinc bromide (ZnBr) 2 ) And 2mmol of m-fluoro-substituted benzylamine (FC) 6 H 4 CH 2 NH 2 ) Dissolving in 2ml methanol, mixing the two pre-mixed solutions, adding mixed acid solution containing 180 μl hydrobromic acid and 23 μl hydrofluoric acid, and stirring vigorously at room temperature for 4 hr at 800-1000rpm/min to obtain clear transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60deg.C for one day to obtain organic-inorganic hybrid zinc-based two-dimensional perovskite material (3-FBA) 2 ZnFBr 3 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 2.60%, the luminescence center is 492nm, and the half-peak width is 114nm.
Example 18
1mmol of zinc chloride (ZnCl) 2 ) And 2mmol of o-fluoro-substituted phenethylamine (FC) 6 H 4 C 2 H 4 NH 2 ) Dissolving in 2ml of methanol, uniformly mixing the two premix solutions, then adding mixed acid solution containing 120 mu l of hydrochloric acid and 23 mu l of hydrofluoric acid, and vigorously stirring for 4 hours at room temperature at a rotating speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60deg.C for one day to obtain organic-inorganic hybrid zinc-based two-dimensional perovskite material (2-FPEA) 2 ZnFCl 3 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 4.46%, the luminescence center is located at 512nm, and the half-peak width is 138nm.
Example 19
1mmol of zinc bromide (ZnBr) 2 ) And 2mmol of o-fluoro-substituted phenethylamine (FC) 6 H 4 C 2 H 4 NH 2 ) Dissolving in 2ml of methanol, uniformly mixing the two premix solutions, then adding mixed acid solution containing 180 mu l hydrobromic acid and 23 mu l hydrofluoric acid, and vigorously stirring for 4 hours at room temperature at a speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60deg.C for one day to obtain organic-inorganic hybrid zinc-based two-dimensional perovskite material (2-FPEA) 2 ZnFBr 3 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 8.85%, the luminescence center is located at 500nm, and the half-peak width is 133nm.
Example 20
1mmol of zinc chloride (ZnCl) 2 ) And 2mmol of m-fluoro-substituted phenethylamine (FC) 6 H 4 C 2 H 4 NH 2 ) Dissolving in 2ml of methanol, uniformly mixing the two premix solutions, then adding mixed acid solution containing 120 mu l of hydrochloric acid and 23 mu l of hydrofluoric acid, and vigorously stirring for 4 hours at room temperature at a rotating speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60deg.C for one day to obtain organic-inorganic hybrid zinc-based two-dimensional perovskite material (3-FPEA) 2 ZnFCl 3 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 10.42%, the luminescence center is located at 508nm, and the half-peak width is 127nm.
Example 21
1mmol of zinc bromide (ZnBr) 2 ) And 2mmol of m-fluoro-substituted phenethylamine (FC) 6 H 4 C 2 H 4 NH 2 ) Dissolving in 2ml of methanol, uniformly mixing the two premix solutions, then adding mixed acid solution containing 180 mu l hydrobromic acid and 23 mu l hydrofluoric acid, and vigorously stirring for 4 hours at room temperature at a speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60deg.C for one day to obtain organic-inorganic hybrid zinc-based two-dimensional perovskite material (3-FPEA) 2 ZnFBr 3 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 24.17%, the luminescence center is 492nm, and the half-peak width is 119nm.
Example 22
1mmol of zinc chloride (ZnCl) 2 ) And 2mmol of p-fluoro-substituted phenethylamine (FC) 6 H 4 C 2 H 4 NH 2 ) Dissolving in 2ml of methanol, uniformly mixing the two premix solutions, then adding mixed acid solution containing 120 mu l of hydrochloric acid and 23 mu l of hydrofluoric acid, and vigorously stirring for 4 hours at room temperature at a rotating speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60deg.C for one day to obtain organic-inorganic hybrid zinc-based two-dimensional perovskite material (4-FPEA) 2 ZnFCl 3 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 16.38%, the luminescence center is located at 517nm, and the half-peak width is 129nm.
Example 23
1mmol of zinc bromide (ZnBr) 2 ) And 2mmol of p-fluoro-substituted phenethylamine (FC) 6 H 4 C 2 H 4 NH 2 ) Dissolving in 2ml of methanol, uniformly mixing the two premix solutions, then adding mixed acid solution containing 180 mu l hydrobromic acid and 23 mu l hydrofluoric acid, and vigorously stirring for 4 hours at room temperature at a speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution by using a sealing film with a plurality of small holes, slowly evaporating for a plurality of days at room temperature, and separating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60deg.C for one day to obtain organic-inorganic hybrid zinc-based two-dimensional perovskite material (4-FPEA) 2 ZnFBr 3 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 26.68%, the luminescence center is located at 516nm, and the half-peak width is 112nm.
FIG. 1 is an XRD pattern of the organic-inorganic hybrid zinc-based two-dimensional perovskite materials of examples 1-7. From the graph, it can be seen that as the doping amount of fluorine increases, the XRD diffraction characteristic peak is unchanged and the diffraction peak of the low angle region gradually shifts to a low angle, which indicates that fluorine enters the zinc-based perovskite lattice, and doping of fluorine causes the perovskite lattice constant to become large, since the radius of fluorine ions is smaller than that of chlorine ions, which indicates that fluorine enters the zinc-based perovskite lattice in a gap doping form.
FIG. 2 is an ultraviolet visible absorption spectrum of the organic-inorganic hybrid zinc-based two-dimensional perovskite materials of examples 1-7. From the figure, it is known that after doping fluorine, i.e. examples 2-7, there is a shoulder at 400nm, indicating that fluorine doping causes an enhancement of exciton absorption, thus forming stable excitons, which is beneficial to improving the photoluminescence quantum efficiency.
FIG. 3 is a fluorescence spectrum of an organic-inorganic hybrid zinc-based two-dimensional perovskite material of examples 1-7. From the graph, it is known that the highest fluorescence intensity of example 5 under the same excitation condition, and the fluorescence intensity increases and decreases with increasing fluorine doping concentration, indicates that there is an optimum doping concentration for fluorine ion doping.
FIG. 4 is a fluorescence lifetime spectrum of organic-inorganic hybrid zinc-based two-dimensional perovskite materials of examples 1-7. From the graph, it is known that the fluorescence lifetime curve of the zinc-based perovskite satisfies the double exponential decay formula, and the fluorescence lifetime increases and decreases with increasing fluorine doping concentration, wherein the fluorescence lifetime of example 5 is longest, indicating that it has a higher probability of radiative recombination and more self-trapped exciton states, thereby explaining the phenomenon that the fluorescence intensity of example 5 is highest.
FIG. 5 is a microscopic pattern of the organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 5.
FIG. 6 is an EDS spectrum of an organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 5. From the figure, characteristic peaks of C, N, zn, cl and F elements can be observed, and it is further confirmed that fluorine ions successfully enter the zinc-based perovskite lattice, and the actual doping concentration is 9%.
FIG. 7 is a CIE chromaticity diagram corresponding to the fluorescence spectrum of the organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 5. From the figure, the CIE chromaticity coordinate of example 5 was found to be (0.29,0.40), and the correlated color temperature was found to be 7173K.
Fig. 8 is an excitation spectrum of the organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 5 at different emission wavelengths. From the figure, it is clear that the excitation spectrum of example 5 maintains the same pattern at different emission wavelengths from 495 nm to 600 nm, indicating that the fluorescence emissions are all from the same excited state.
FIG. 9 is a two-dimensional profile of fluorescence at different excitation wavelengths for the organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 5. From the graph, it is known that the photoluminescence peak position and half-width of example 5 remain substantially unchanged at different excitation wavelengths of 300 nm to 410 nm, indicating that only one emission center exists.
FIG. 10 is a fluorescence spectrum at different temperatures of the organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 5. From the graph, it is known that the integrated fluorescence intensity of example 5 is continuously increased with the decrease of the half-peak width, and by fitting the dependence relationship between the integrated fluorescence intensity and the half-peak width with the temperature, it is known that there is strong phonon-electron coupling action in the zinc-based perovskite, and there is strong exciton localization action, confirming the existence of self-trapped excitons, thereby realizing the emission of broad-spectrum white light.
FIG. 11 is a graph of the photostability of the organic-inorganic hybrid zinc-based two-dimensional perovskite materials of examples 1 and 5 heated continuously at 80℃for 1000 hours. From the graph, it is known that the fluorescence intensity of example 5 is hardly attenuated under the heating condition of 1000 hours, whereas the intensity of example 1 is attenuated by 27.5%, which indicates that the fluorine doping can improve the thermal stability of the zinc-based perovskite.
FIG. 12 is a graph of the photostability of the organic-inorganic hybrid zinc-based two-dimensional perovskite materials of examples 1 and 5 upon continuous illumination for 240 minutes under a 365nm violet lamp having a power of 6W. From the graph, it is known that the fluorescence intensity of example 5 is attenuated to 72% of the original fluorescence intensity under the condition of 240 minutes of light excitation, while the fluorescence intensity of example 1 is attenuated by 55%, which indicates that fluorine doping can improve the light stability of zinc-based perovskite.
FIG. 13 is a graph showing the comparison of fluorescence spectra of organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 5 stored for 4 months under ambient conditions of temperature 20-25deg.C and humidity 50-70%. From the figure, it can be seen that the fluorescence intensity of example 5 is substantially unchanged from that just synthesized even when stored for 4 months under ambient conditions, indicating that zinc-based perovskite has superior environmental storage.
Fig. 14 is a schematic diagram describing the white light principle of an organic-inorganic hybrid zinc-based two-dimensional perovskite material. As can be seen from the figure, under photoexcitation conditions, electrons transition from the ground state to the excited state to form free excitons, which can transfer from the free exciton state to the self-trapped exciton state due to strong lattice coupling, and potential energy recombines during self-trapping to cause the self-trapped state to form a distribution of energy relative to the ground state, resulting in broad-spectrum photoluminescence with large stokes shift. When fluorine ions are doped, photon energy is more efficiently utilized due to exciton absorption, potential barriers of an self-trapping process are greatly reduced, and the fluorine ions can be used as lattice defects to help exciton localization, so that the excitons can directly reach a self-trapping state without overcoming the potential barriers in the self-trapping process, more self-trapping states are caused, a radiation recombination process is enhanced, and the luminous quantum efficiency of the zinc-based perovskite is improved.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (11)
1. The preparation method of the organic-inorganic hybrid zinc-based two-dimensional perovskite material is characterized by comprising the following steps of:
(1) Respectively dissolving zinc halide and organic amine in a volatile polar solvent to obtain a premix X and a premix Y;
(2) Mixing the premix liquid X and the premix liquid Y obtained in the step (1), then dropwise adding halogen acid to enable organic amine to be protonated to form organic amine ions, and reacting with zinc ions and halogen ions to obtain premix liquid Z; the halogen acid is two halogen acids with different halogens, wherein one of the two halogen acids is hydrofluoric acid;
(3) And (3) volatilizing the solvent in the premix Z obtained in the step (2), and separating out the organic-inorganic hybrid zinc-based two-dimensional perovskite crystal.
2. The method for preparing an organic-inorganic hybrid zinc-based two-dimensional perovskite material according to claim 1, wherein the zinc halide is at least one of zinc fluoride, zinc chloride and zinc bromide.
3. The method for preparing an organic-inorganic hybrid zinc-based two-dimensional perovskite material according to claim 1 or 2, wherein the organic amine is aromatic amine.
4. The method for preparing an organic-inorganic hybrid zinc-based two-dimensional perovskite material according to claim 3, wherein the aromatic amine is benzylamine, phenethylamine, amphetamine, p-methylphenylethylamine, o-fluorobenzylamine, m-fluorobenzylamine, o-fluorophenylethylamine, m-fluorophenylethylamine or p-fluorophenylethylamine.
5. The method for preparing an organic-inorganic hybrid zinc-based two-dimensional perovskite material according to claim 4, wherein the volatile polar solvent is at least one of methanol, absolute ethanol, isopropanol and acetone.
6. The method for preparing an organic-inorganic hybrid zinc-based two-dimensional perovskite material according to claim 1, wherein the ratio of the concentration of organic amine ions to the concentration of zinc ions in the premix Z is (0.1-10): 1.
7. The method for preparing the organic-inorganic hybrid zinc-based two-dimensional perovskite material according to claim 6, wherein the concentration of organic amine ions in the premix Z is 0.05mol/L-10mol/L, and the concentration of zinc ions is 0.05mol/L-10mol/L.
8. The organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by the method according to any one of claims 1 to 7.
9. The organic-inorganic hybrid zinc-based two-dimensional perovskite material according to claim 8, wherein the organic-inorganic hybrid zinc-based two-dimensional perovskite material has a general formula of A 2 ZnX 4 Wherein A is aromatic amine cation and X is halogenThe elements F and Cl, or F and Br.
10. The organic-inorganic hybrid zinc-based two-dimensional perovskite material according to claim 9, wherein the aromatic amine cation is a benzylamine ion, a phenethylamine ion, an amphetamine ion, a p-methylphenylethylamine ion, an o-fluorobenzylamine ion, a m-fluorobenzylamine ion, an o-fluorophenylethylamine ion, a m-fluorophenylethylamine ion, or a p-fluorophenylethylamine ion.
11. A white LED device comprising an organic-inorganic hybrid zinc-based two-dimensional perovskite material according to any one of claims 8 to 10.
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