CN113736454A - Organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with heterovalent ions and preparation method thereof - Google Patents

Organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with heterovalent ions and preparation method thereof Download PDF

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CN113736454A
CN113736454A CN202111031891.3A CN202111031891A CN113736454A CN 113736454 A CN113736454 A CN 113736454A CN 202111031891 A CN202111031891 A CN 202111031891A CN 113736454 A CN113736454 A CN 113736454A
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常海欣
叶港
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Huazhong University of Science and Technology
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Abstract

The invention discloses an organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with aliovalent ions and a preparation method thereof, belonging to the field of photoelectric materials. Reacting ZnX2And BXnDissolving in a volatile polar solvent, wherein B is a monovalent or trivalent metal ion, and X is a halogen ion, to obtain a first premixed solution; dissolving organic amine in a polar solvent with the same volatility to obtain a second premixed solution; mixing the pre-mixed solution, and adding halogen acid to make organic amine protonAnd reacting with all metal ions and halogen ions to obtain a third premixed solution, and volatilizing the solvent to separate out the organic-inorganic hybrid zinc-based two-dimensional perovskite crystal doped with the aliovalent ions. The high-fluorescence quantum yield aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material provided by the invention has high purity and large half-peak width of emission spectrum (>100nm) with larger Stokes shift, the photoluminescence quantum yield is high and can reach 98 percent at most, and the stability is good.

Description

Organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with heterovalent ions and preparation method thereof
Technical Field
The invention belongs to the field of photoelectric materials, and particularly relates to an organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with aliovalent ions and a preparation method thereof, in particular to an organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with aliovalent ions with high fluorescence quantum yield and a preparation method thereof.
Background
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 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 hybrid perovskite greatly increases the diversity of perovskite by replacing A site with long-chain organic cations, so that the electronic structure dimension 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 perovskites have a large exciton binding energy, and therefore the number of excitons dominates over the free charge, even at lower excitation densities. The special exciton properties of the two-dimensional perovskite make its photophysical characteristics much different from those of the 3D perovskite, which shows extremely broad spectrum and large stokes shift in photoluminescence spectrum. The two-dimensional perovskite not only has the characteristics of solution-soluble processing, molecular scale self-assembly, excellent film-forming property and the like of a two-dimensional material, but also retains the advantages of excellent luminescence property, higher quantum yield, higher color purity and the like of the perovskite, and the advantages enable the perovskite to become a new generation candidate material for electronic and photoelectric integrated devices such as light emitting diodes, field effect transistors, lasers and the like.
However, the toxicity of lead, which is currently the major constituent of perovskites, greatly limits its use in the photovoltaic field, and it is therefore desirable to replace lead with elements that are non-toxic or less toxic. There have been many reports demonstrating that toxic Pb elements can be effectively replaced with non-toxic metal elements such as Sn, Ge, Sb, and Bi, resulting in green lead-free perovskite materials. However, the lead-free perovskites obtained after substitution of these elements often have significantly reduced photoluminescence quantum yields, much lower than those of lead-based perovskite materials, and even have compromised stability. On the other hand, doping is an effective way to control the electronic structure and physical properties of metal halide perovskites significantly, and even to induce new functions.
Disclosure of Invention
The organic and inorganic hybridization zinc-based two-dimensional perovskite material doped with the heterovalent ions has high purity, green and nontoxic zinc ions are used for replacing heavy metal lead ions, the electronic structure and the physical properties of the zinc-based perovskite material are further regulated and controlled by doping the heterovalent ions, the half-peak width of an emission spectrum is large (>100nm), the photoluminescence quantum yield is high along with larger Stokes shift and can reach 80 percent at most, the stability is good, the preparation process is simple, the cost is low, the repeatability is high, the preparation period is short, the environment is friendly, and the organic and inorganic hybridization zinc-based two-dimensional perovskite material doped with the heterovalent ions can be effectively applied to the field of solid-state lighting.
According to the first aspect of the invention, the preparation method of the organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with the aliovalent ions is provided, and comprises the following steps:
(1) reacting ZnX2And BXnDissolving in a volatile polar solvent, wherein B is monovalent and/or trivalent aliovalent metal ions, and X is halogen ions, to obtain a first premix; dissolving organic amine in a volatile polar solvent to obtain a second premixed solution;
(2) mixing the first premixed solution and the second premixed solution obtained in the step (1), then dropwise adding halogen acid to protonate organic amine to form organic amine ions, and reacting the organic amine ions with all kinds of metal ions and halogen ions to obtain a third premixed solution;
(3) and (3) volatilizing the solvent in the third premixed solution obtained in the step (2) to separate out an organic-inorganic hybrid zinc-based two-dimensional perovskite crystal doped with the aliovalent ions.
Preferably, B is Cu+、Bi3+、In3+、Fe3+And Sb3+At least one of (1).
Preferably, the first premix liquid further comprises manganese halide.
Preferably, the organic amine is an aromatic amine;
preferably, the aromatic amine is benzylamine, phenylethylamine, amphetamine, p-methylphenylethylamine, o-fluorophenylmethylamine, m-fluorophenylmethylamine, o-fluorophenylethylamine, m-fluorophenylethylamine, or p-fluorophenylethylamine.
Preferably, the X is fluoride, chloride or bromide, and the hydrohalic acid is at least one of hydrofluoric acid, hydrochloric acid and hydrobromic acid.
Preferably, the volatile polar solvent is at least one of methanol, absolute ethanol, isopropanol, and acetone.
Preferably, the concentration ratio of the organic amine ions in the third premix to the sum of the concentrations of all kinds of metal ions is (0.1-10): 1.
Preferably, the concentration of the organic amine ions in the third premixed liquid is 0.05mol/L-10mol/L, and the total concentration of the metal ions is 0.05mol/L-10 mol/L.
According to another aspect of the invention, the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by any one of the methods is provided.
Preferably, the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material has a general formula A2Zn1- xBxX4Wherein A is aromatic amine cation, X is halogen element, and B is Cu+、Bi3+、In3+、Fe3+And Sb3+At least one of;
preferably, the aromatic amine cation is a benzylamine ion, phenethylamine ion, amphetamine ion, p-methylphenethylamine ion, o-fluorophenylmethylamine ion, m-fluorophenylmethylamine ion, o-fluorophenylethylamine ion, m-fluorophenylethylamine ion, or p-fluorophenylethylamine ion.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by the invention has high purity, the emission spectrum is wide spectrum, the wide spectrum luminescence is from self-trapping exciton composite luminescence caused by strong phonon-electron coupling effect in low-dimensional perovskite, the luminescence center wavelength is 475-495nm, the half peak width is 75-105nm, and the photoluminescence quantum yield is 40-98%. Through the doping of the heterovalent ions, the photoluminescence quantum yield of the material can be greatly improved, and can reach about 80 percent at most, which is far higher than the quantum yield of the existing organic-inorganic non-lead two-dimensional perovskite, and the stability of the material is good.
(2) The organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with the aliovalent ions prepared by the invention can effectively inhibit a non-radiative recombination approach caused by lattice intrinsic defects by introducing the aliovalent ions, thereby greatly improving the photoluminescence quantum yield of the organic-inorganic hybrid zinc-based two-dimensional perovskite material.
(3) The invention utilizes the principle of an evaporative crystallization method, uses volatile polar liquid as a solvent, slowly evaporates a solution containing a solute with a stoichiometric ratio under an environmental condition, and prepares the heterovalent ion-doped organic-inorganic zinc-based two-dimensional perovskite material with high fluorescence quantum yield through the steps of filtering, washing, vacuum drying and the like.
(4) Compared with the organic and inorganic hybrid zinc-based two-dimensional perovskite material obtained by a hydrothermal method, the organic and inorganic hybrid zinc-based two-dimensional perovskite material prepared by the method is prepared by adopting an evaporative crystallization method, and the fluorescence quenching caused by the generation of a non-fluorescent perovskite complex can be avoided because the system belongs to an anhydrous system.
(5) The organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with the aliovalent ions, prepared by the invention, has excellent thermal stability, and is particularly characterized in that the photoluminescent intensity of the perovskite material is 80-98% of the original intensity after continuously heating for 1000 hours at 100 ℃.
(6) The aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by the invention has excellent light stability, and is particularly characterized in that the photoluminescent intensity of the material is still 50-75% of the original intensity after the material is continuously irradiated for 240 minutes by an LED with the rated power of 6-10W and the wavelength of 302 nm.
(7) The aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by the invention has excellent storage stability, and is particularly characterized in that the photoluminescent intensity is almost unchanged when the material is stored for 3 months under the environmental conditions that the temperature is 20-25 ℃ and the humidity is 50-70%.
(8) The organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with the aliovalent ions prepared by the method disclosed by the invention is green, environment-friendly and environment-friendly because no toxic raw materials or reagents are used in the whole preparation process.
(9) The preparation method disclosed by the invention is simple in preparation process, mild in production condition, low in cost, high in repeatability and short in preparation period, and can be effectively applied to the field of solid-state lighting.
Drawings
Fig. 1 is an XRD pattern of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of comparative example 1 and examples 1-6.
Fig. 2 is the uv-vis absorption spectra of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite materials of comparative example 1 and examples 1-6.
FIG. 3 is a fluorescence spectrum of an aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of comparative example 1 and examples 1-6.
Fig. 4 is an EDS spectrum of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of comparative example 1 and examples 1-6.
FIG. 5 is a thermogravimetric plot of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite materials of comparative example 1 and examples 1-6.
Fig. 6 is a microscopic map and an EDS elemental surface distribution diagram of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3.
FIG. 7 is excitation spectra of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3 at different emission wavelengths.
Fig. 8 is a two-dimensional profile of fluorescence of the heterovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3 at different excitation wavelengths.
FIG. 9 is a graph of the dependence of fluorescence intensity of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3 on excitation light power.
Fig. 10 is a photoluminescence quantum efficiency graph of an aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3.
Fig. 11 is a graph of fluorescence lifetime of the organic-inorganic hybrid zinc-based two-dimensional perovskite material of comparative example 1.
Fig. 12 is a graph of fluorescence lifetime of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention relates to an organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with high-fluorescence quantum yield aliovalent ions, which mainly comprises the following steps:
(1) weighing mixed metal halide ZnX with a certain molar ratio in inert atmosphere2And BXnDissolving the pre-mixed solution in a volatile polar solvent, and stirring until the solution is clear to obtain a pre-mixed solution X;
(2) dissolving organic amine A in a stoichiometric ratio in the same volatile polar solvent, and stirring until the solution is clear to obtain a premixed solution Y;
(3) mixing the premixed solution X and the premixed solution Y, then dropwise adding halogen acid with corresponding molar volume, and stirring until the solution is clear to obtain a premixed solution Z;
(4) sealing the premixed solution Z obtained in the step (3) by using a sealing film, pricking a plurality of small holes to control the volatilization rate of the solvent, slowly evaporating for a plurality of days at room temperature, and separating out the organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with the aliovalent ions with high fluorescence quantum yield from the bottom of the container;
(5) and (4) 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 the temperature of 60 ℃.
Preferably, in the step (1), the volatile solvent is at least one of methanol, absolute ethanol, isopropanol and acetone.
Preferably, in the step (3), the hydrohalic 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 isopropanol, acetone, diethyl ether and ethyl acetate.
Preferably, the molar ratio of the organic amine A to the total metal ions in the premix Z is (0.1-10): 1.
Preferably, the concentration of the organic amine A in the premix Z is 0.05 to 10mol/L, and the total metal ion concentration is 0.05 to 10 mol/L.
The high-fluorescence quantum yield aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by the preparation method meets the general formula A2Zn1-xBxX4Wherein A is a benzylamine ion (C)6H5CH2NH3 +，BA+) Phenylethylamine ion (C)6H5C2H4NH3 +，PEA+) Phenylpropionamine ion (C)6H5C3H6NH3 +，PPA+) P-methylphenylethylamine ion (CH)3C6H5C2H4NH3 +，4-MPEA+) O-fluorobenzylamine ion (FC)6H4CH2NH3 +,2-FBA+) M-fluorobenzylamine ion (FC)6H4CH2NH3 +,3-FBA+) O-fluorophenylethylamine ion (FC)6H4C2H4NH3 +，2-FPEA+) M-fluorophenylethylamine ion (FC)6H4C2H4NH3 +，3-FPEA+) P-fluorophenylethylamine ion (FC)6H4C2H4NH3 +，4-FPEA+) Octylamine ion (C)8H17NH3 +，OA+) B is Cu+、Bi3+、In3+、Fe3+、Sb3+、Mn2+One or more of metal ions are mixed, and X is one or more of halogen elements F, Cl and Br.
Furthermore, the luminescence center wavelength is 475-495nm, the half-peak width is 75-105nm, and the photoluminescence quantum yield is 40-98%.
Further, the broad spectrum luminescence is derived from self-trapping exciton recombination luminescence caused by strong phonon-electron coupling effect in low-dimensional perovskite.
Further, it has excellent thermal stability. The specific expression is that the photoluminescence intensity of the material is still 80 to 98 percent of the original intensity after continuously heating for 1000 hours at 80 ℃.
Further, it has excellent light stability. It is characterized by that when the LED whose nominal power is 6-10W and whose wavelength is 302nm is continuously irradiated for 240 min, its photoluminescence intensity still retains 50-75% of original intensity.
Further, it has excellent storage stability. Specifically, the photoluminescence intensity of the material is almost unchanged when the material is stored for 3 months under the environmental conditions that the temperature is 20-25 ℃ and the humidity is 50-70%.
Comparative example 1
Respectively adding 4mmol of zinc bromide (ZnBr)2) And 8mmol of phenethylamine (C)6H5C2H4NH2) Dissolving in 5ml of methanol, uniformly mixing the two premixed liquids, adding 940 mu l of hydrobromic acid, and vigorously stirring for 4h at room temperature at the rotation speed of 800-. Sealing the solution with sealing film with small holes, slowly evaporating at room temperature for several days, and separating out colorless crystal at the bottom of the container. Washing the obtained crystal with isopropanol for three times, and placing the crystal in a vacuum drying oven at 60 DEG CDrying for one day to obtain the organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA2ZnBr4. The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 1.7%, the luminescence center is 475nm, and the half-peak width is 180 nm.
Example 1
Respectively adding 3.92mmol of zinc bromide (ZnBr)2) 0.08mmol cuprous bromide (CuBr) and 8mmol phenethylamine (C)6H5C2H4NH2) Dissolving in 5ml of methanol, uniformly mixing the two premixed liquids, adding 250 mu l of hypophosphorous acid and 940 mu l of hydrobromic acid, and vigorously stirring for 4 hours at room temperature at the rotation speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution with sealing film with small holes, slowly evaporating at room temperature for several days, and separating out colorless crystal at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60 deg.C for one day to obtain the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA2Zn0.98Cu0.02Br3.98. The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 60.2%, the luminescence center is 481nm, and the half-peak width is 84 nm.
Example 2
Respectively adding 3.86mmol of zinc bromide (ZnBr)2) 0.14mmol cuprous bromide (CuBr) and 8mmol phenethylamine (C)6H5C2H4NH2) Dissolving in 5ml of methanol, uniformly mixing the two premixed liquids, adding 250 mu l of hypophosphorous acid and 940 mu l of hydrobromic acid, and vigorously stirring for 4 hours at room temperature at the rotation speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution with sealing film with small holes, slowly evaporating at room temperature for several days, and separating out colorless crystal at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60 deg.C for one day to obtain the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA2Zn0.965Cu0.035Br3.965. The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 71.8 percent, and the luminescent center is positioned at 475nmThe half-peak width was 94 nm.
Example 3
Respectively adding 3.80mmol of zinc bromide (ZnBr)2) 0.20mmol cuprous bromide (CuBr) and 8mmol phenethylamine (C)6H5C2H4NH2) Dissolving in 5ml of methanol, uniformly mixing the two premixed liquids, adding 250 mu l of hypophosphorous acid and 940 mu l of hydrobromic acid, and vigorously stirring for 4 hours at room temperature at the rotation speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution with sealing film with small holes, slowly evaporating at room temperature for several days, and separating out colorless crystal at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60 deg.C for one day to obtain the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA2Zn0.95Cu0.05Br3.95. The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 79.1%, the luminescence center is 477nm, and the half-peak width is 94 nm.
Example 4
Respectively adding 3.70mmol of zinc bromide (ZnBr)2) 0.30mmol cuprous bromide (CuBr) and 8mmol phenethylamine (C)6H5C2H4NH2) Dissolving in 5ml of methanol, uniformly mixing the two premixed liquids, adding 250 mu l of hypophosphorous acid and 940 mu l of hydrobromic acid, and vigorously stirring for 4 hours at room temperature at the rotation speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution with sealing film with small holes, slowly evaporating at room temperature for several days, and separating out colorless crystal at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60 deg.C for one day to obtain the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA2Zn0.925Cu0.075Br3.925. The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 65.7%, the luminescent center is 477nm, and the half-peak width is 93 nm.
Example 5
Respectively adding 3.60mmol of zinc bromide (ZnBr)2) 0.40mmol cuprous bromide (CuBr) and 8mmol phenethylamine (C)6H5C2H4NH2) Dissolving in 5ml of methanol, uniformly mixing the two premixed liquids, adding 250 mu l of hypophosphorous acid and 940 mu l of hydrobromic acid, and vigorously stirring for 4 hours at room temperature at the rotation speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution with sealing film with small holes, slowly evaporating at room temperature for several days, and separating out colorless crystal at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60 deg.C for one day to obtain the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA2Zn0.9Cu0.1Br3.9. The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 65.0%, the luminescence center is 478nm, and the half-peak width is 92 nm.
Example 6
Respectively adding 3.20mmol of zinc bromide (ZnBr)2) 0.80mmol cuprous bromide (CuBr) and 8mmol phenethylamine (C)6H5C2H4NH2) Dissolving in 5ml of methanol, uniformly mixing the two premixed liquids, adding 250 mu l of hypophosphorous acid and 940 mu l of hydrobromic acid, and vigorously stirring for 4 hours at room temperature at the rotation speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution with sealing film with small holes, slowly evaporating at room temperature for several days, and separating out colorless crystal at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60 deg.C for one day to obtain the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA2Zn0.8Cu0.2Br3.8. The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 45.7%, the luminescence center is located at 482nm, and the half-peak width is 92 nm.
Example 7
Respectively adding 3.60mmol of zinc bromide (ZnBr)2) 0.20mmol cuprous bromide (CuBr), 0.20mmol ferric bromide (FeBr)3) And 8mmol of phenethylamine (C)6H5C2H4NH2) Dissolving in 5ml of absolute ethanol, mixing the two premixes uniformly, adding 250. mu.l of hypophosphorous acid and 940. mu.l of hydrobromic acid, and standing at room temperatureStirring vigorously for 4h under the condition, wherein the rotating speed is 800-. Sealing the solution with sealing film with small holes, slowly evaporating at room temperature for several days, and separating out colorless crystal at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60 deg.C for one day to obtain the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA2Zn0.90Cu0.05Fe0.05Br4. The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 42.6%, the luminescence center is 485nm, and the half-peak width is 93 nm.
Example 8
Respectively adding 3.60mmol of zinc bromide (ZnBr)2) 0.20mmol cuprous bromide (CuBr), 0.20mmol indium bromide (InBr)3) And 8mmol of phenethylamine (C)6H5C2H4NH2) Dissolving in 5ml of isopropanol, uniformly mixing the two premixed liquids, adding 250 mu l of hypophosphorous acid and 940 mu l of hydrobromic acid, and vigorously stirring for 4 hours at room temperature at the rotation speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution with sealing film with small holes, slowly evaporating at room temperature for several days, and separating out colorless crystal at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60 deg.C for one day to obtain the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA2Zn0.90Cu0.05In0.05Br4. The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 76.4%, the luminescent center is 477nm, and the half-peak width is 87 nm.
Example 9
Respectively adding 3.60mmol of zinc bromide (ZnBr)2) 0.20mmol of cuprous bromide (CuBr), 0.20mmol of antimony bromide (SbBr)3) And 8mmol of phenethylamine (C)6H5C2H4NH2) Dissolving in 5ml acetone, mixing the two pre-mixed solutions uniformly, adding 250 μ l hypophosphorous acid and 940 μ l hydrobromic acid, and stirring vigorously at room temperature for 4h at the rotation speed of 800-. The use stamp has a plurality of smallThe solution is sealed by a sealing film of the hole, is slowly evaporated for a plurality of days at room temperature, and colorless crystals are separated out from the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60 deg.C for one day to obtain the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA2Zn0.90Cu0.05Sb0.05Br4. The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 46.8%, the luminescence center is 472nm, and the half-peak width is 73 nm.
Example 10
Respectively adding 3.60mmol of zinc bromide (ZnBr)2) 0.20mmol cuprous bromide (CuBr), 0.20mmol manganese bromide (MnBr)2) And 8mmol of phenethylamine (C)6H5C2H4NH2) Dissolving the two premixed liquids in 5ml of mixed solution of methanol and absolute ethanol, uniformly mixing the two premixed liquids, then adding 250 mu l of hypophosphorous acid and 940 mu l of hydrobromic acid, and violently stirring for 4h at room temperature at the rotation speed of 800-1000rpm/min to obtain clear and transparent solution. Sealing the solution with sealing film with small holes, slowly evaporating at room temperature for several days, and separating out colorless crystal at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60 deg.C for one day to obtain the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA2Zn0.90Cu0.05Mn0.05Br3.95. The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 76.9%, the luminescence center is 478.5nm, and the half-peak width is 89 nm.
Example 11
Respectively adding 3.40mmol of zinc bromide (ZnBr)2) 0.20mmol cuprous bromide (CuBr), 0.40mmol manganese bromide (MnBr)2) And 8mmol of phenethylamine (C)6H5C2H4NH2) Dissolving the mixture in 5ml of mixed solution of methanol and isopropanol, uniformly mixing the two premixed solutions, then adding 250 mu l of hypophosphorous acid and 940 mu l of hydrobromic acid, and vigorously stirring for 4h at room temperature at the rotation speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution with sealing film with small holes, and placing in a chamberSlowly evaporating for several days under warm condition, and precipitating colorless crystals at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60 deg.C for one day to obtain the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA2Zn0.85Cu0.05Mn0.10Br3.95. The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 82.0%, the luminescence center is 476.5nm, and the half-peak width is 93 nm.
Example 12
Respectively adding 3.20mmol of zinc bromide (ZnBr)2) 0.20mmol cuprous bromide (CuBr), 0.60mmol manganese bromide (MnBr)2) And 8mmol of phenethylamine (C)6H5C2H4NH2) Dissolving the two premixed liquids in 5ml of mixed solution of methanol and acetone, uniformly mixing the two premixed liquids, then adding 250 mu l of hypophosphorous acid and 940 mu l of hydrobromic acid, and violently stirring for 4h at the room temperature at the rotation speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution with sealing film with small holes, slowly evaporating at room temperature for several days, and separating out colorless crystal at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60 deg.C for one day to obtain the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA2Zn0.80Cu0.05Mn0.15Br3.95. The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 94.1%, the luminescence center is 478.5nm, and the half-peak width is 94 nm.
Example 13
Respectively adding 3.00mmol of zinc bromide (ZnBr)2) 0.20mmol cuprous bromide (CuBr), 0.80mmol manganese bromide (MnBr)2) And 8mmol of phenethylamine (C)6H5C2H4NH2) Dissolving in 5ml of methanol, uniformly mixing the two premixed liquids, adding 250 mu l of hypophosphorous acid and 940 mu l of hydrobromic acid, and vigorously stirring for 4 hours at room temperature at the rotation speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution with sealing film with small holes, slowly evaporating at room temperature for several days, and separating out colorless crystal at the bottom of the container.Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60 deg.C for one day to obtain the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA2Zn0.65Cu0.05Mn0.20Br3.95. The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 98.0%, the luminescence center is 477.5nm, and the half-peak width is 93 nm.
Example 14
Respectively adding 2.80mmol of zinc bromide (ZnBr)2) 0.20mmol cuprous bromide (CuBr), 1.00mmol manganese bromide (MnBr)2) And 8mmol of phenethylamine (C)6H5C2H4NH2) Dissolving in 5ml of methanol, uniformly mixing the two premixed liquids, adding 250 mu l of hypophosphorous acid and 940 mu l of hydrobromic acid, and vigorously stirring for 4 hours at room temperature at the rotation speed of 800-1000rpm/min to obtain a clear and transparent solution. Sealing the solution with sealing film with small holes, slowly evaporating at room temperature for several days, and separating out colorless crystal at the bottom of the container. Washing the obtained crystal with isopropanol three times, and drying in a vacuum drying oven at 60 deg.C for one day to obtain the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material PEA2Zn0.60Cu0.05Mn0.25Br3.95. The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 90.0%, the luminescence center is 473.5nm, and the half-peak width is 94 nm.
Fig. 1 is an XRD pattern of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of comparative example 1 and examples 1-6. From the figure, it can be seen that Cu is doped+Then, the XRD characteristic peak has little change, which indicates that Cu+The crystal form of the organic-inorganic hybrid zinc-based two-dimensional perovskite is not changed by the introduction of the (A). And with Cu+The increase of the doping amount and the gradual shift of the diffraction peak of the low-angle area to a large angle prove that the Cu+Enters into the crystal lattice of organic-inorganic hybrid zinc-based two-dimensional perovskite and Cu+The introduction of (2) can reduce the lattice constant of the organic-inorganic hybrid zinc-based two-dimensional perovskite.
Fig. 2 is the uv-vis absorption spectra of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite materials of comparative example 1 and examples 1-6. It can be seen from the figure that, compared with comparative example 1, examples 1 to 6 have an extra shoulder at 300 nm, corresponding to the exciton absorption peak, indicating that the doping of the aliovalent ion causes the exciton absorption to be enhanced, thereby forming a stable exciton, which is beneficial to improving the quantum efficiency of photoluminescence.
FIG. 3 is a fluorescence spectrum of an aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of comparative example 1 and examples 1-6. It can be seen from the figure that the luminescence intensity of comparative example 1 is extremely low compared with that of examples 1-6, which shows that the luminescence property of the organic-inorganic hybrid zinc-based two-dimensional perovskite material can be greatly improved by doping a small amount of aliovalent ions.
Fig. 4 is an EDS spectrum of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of comparative example 1 and examples 1-6. Characteristic peaks of C, N, Zn, Cu and Br elements can be clearly observed from the graph, and further, the successful entering of Cu + into the crystal lattice of the organic-inorganic hybrid zinc-based two-dimensional perovskite is confirmed.
FIG. 5 is a thermogravimetric plot of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite materials of comparative example 1 and examples 1-6. The figure shows that the thermal decomposition temperature of the organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with the aliovalent ions is about 320 ℃, and the organic-inorganic hybrid zinc-based two-dimensional perovskite material has excellent thermal stability.
Fig. 6 is a microscopic map and an EDS elemental surface distribution diagram of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3. It can be seen from the figure that Cu + is uniformly distributed in the crystal lattice of the perovskite.
FIG. 7 is excitation spectra of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3 at different emission wavelengths. It can be seen from the figure that the excitation spectra of example 3 all maintain the same pattern at different emission wavelengths from 420 nm to 600 nm, indicating that the fluorescence emissions all come from the same excited state.
Fig. 8 is a two-dimensional profile of fluorescence of the heterovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3 at different excitation wavelengths. It can be seen from the figure that both the photoluminescence peak position and the half-peak width of example 3 remain substantially unchanged at different excitation wavelengths from 240 nm to 380 nm, indicating the presence of only one emission center.
FIG. 9 is a graph of the dependence of fluorescence intensity of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3 on excitation light power. The figure shows that the fluorescence intensity of the organic-inorganic hybrid zinc-based two-dimensional perovskite material and the exciting light power are in a super-linear relation, and the fact that the luminescence is from strong exciton recombination rather than from permanent defects is proved.
Fig. 10 is a photoluminescence quantum efficiency graph of an aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3. It is seen from the figure that example 3 exhibits a high photoluminescence quantum yield of 79.10%.
Fig. 11 is a graph of fluorescence lifetime of the organic-inorganic hybrid zinc-based two-dimensional perovskite material of comparative example 1. It is known from the figure that the organic-inorganic hybrid zinc-based two-dimensional perovskite material of comparative example 1 exhibits a double exponential lifetime, wherein the short lifetime is 47 microseconds and the long lifetime is 342 microseconds. Wherein the short lifetime results from exciton recombination and the long lifetime results from defect recombination.
Fig. 12 is a graph of fluorescence lifetime of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3. It is known from the figure that the heterovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of the example 3 has single index and the fluorescence lifetime of 63 microseconds. Indicating that the defects can be effectively passivated by aliovalent metal ions, resulting in luminescence originating entirely from exciton recombination, resulting in high photoluminescence quantum yields.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of an organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with aliovalent ions is characterized by comprising the following steps:
(1) reacting ZnX2And BXnDissolving in a volatile polar solvent, wherein B is monovalent and/or trivalent aliovalent metal ions, and X is halogen ions, to obtain a first premix; dissolving organic amine in a volatile polar solvent to obtain a second premixed solution;
(2) mixing the first premixed solution and the second premixed solution obtained in the step (1), then dropwise adding halogen acid to protonate organic amine to form organic amine ions, and reacting the organic amine ions with all kinds of metal ions and halogen ions to obtain a third premixed solution;
(3) and (3) volatilizing the solvent in the third premixed solution obtained in the step (2) to separate out an organic-inorganic hybrid zinc-based two-dimensional perovskite crystal doped with the aliovalent ions.
2. The method for preparing an aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material as claimed in claim 1, wherein B is Cu+、Bi3+、In3+、Fe3+And Sb3+At least one of (1).
3. The method for preparing an aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material as claimed in claim 2, wherein the first pre-mixed liquid further comprises a manganese halide.
4. The method for preparing the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material as claimed in any one of claims 1 to 3, wherein the organic amine is aromatic amine;
preferably, the aromatic amine is benzylamine, phenylethylamine, amphetamine, p-methylphenylethylamine, o-fluorophenylmethylamine, m-fluorophenylmethylamine, o-fluorophenylethylamine, m-fluorophenylethylamine, or p-fluorophenylethylamine.
5. The method for preparing the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material as claimed in any one of claims 1 to 3, wherein X is fluoride ion, chloride ion or bromide ion, and the hydrohalic acid is at least one of hydrofluoric acid, hydrochloric acid and hydrobromic acid.
6. The method for preparing an aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material as claimed in claim 1, wherein the volatile polar solvent is at least one of methanol, absolute ethanol, isopropanol and acetone.
7. The method for preparing an aliovalent ion-doped organic-inorganic hybrid zinc-based two-dimensional perovskite material as claimed in claim 1, wherein the concentration ratio of the organic amine ions in the third pre-mixed liquid to the concentration of all kinds of metal ions is (0.1-10): 1.
8. The method for preparing an aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material as claimed in claim 7, wherein the concentration of organic amine ions in the third pre-mixed liquid is 0.05mol/L-10mol/L, and the total metal ion concentration is 0.05mol/L-10 mol/L.
9. An aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material prepared by the method as claimed in any one of claims 1 to 8.
10. The aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material as claimed in claim 9, wherein the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material has a general formula A2Zn1-xBxX4Wherein A is aromatic amine cation, X is halogen element, and B is Cu+、Bi3+、In3+、Fe3+And Sb3+At least one of;
preferably, the aromatic amine cation is a benzylamine ion, phenethylamine ion, amphetamine ion, p-methylphenethylamine ion, o-fluorophenylmethylamine ion, m-fluorophenylmethylamine ion, o-fluorophenylethylamine ion, m-fluorophenylethylamine ion, or p-fluorophenylethylamine ion.
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