CN113736454B - Organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with aliovalent ions and preparation method thereof - Google Patents
Organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with aliovalent ions and preparation method thereof Download PDFInfo
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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. ZnX is to 2 And BX n Dissolving in a volatile polar solvent, wherein B is a monovalent or trivalent metal ion, and X is a halogen ion, so as to obtain a first premix; dissolving organic amine in the same volatile polar solvent to obtain a second premix; mixing the premix, adding halogen acid to protonate the organic amine to form organic amine ions, reacting with all metal ions and halogen ions to obtain a third premix, and volatilizing the solvent to separate out the aliovalent ion doped organic and inorganic hybrid zinc-based two-dimensional perovskite crystal. The organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with the alien ions and having high fluorescence quantum yield has high purity and large half-peak width of an emission spectrum>100 nm), with a large stokes shift, the photoluminescence quantum yield is high and can reach 98% at most, and the stability is good.
Description
Technical Field
The invention belongs to the field of photoelectric materials, and particularly relates to an organic and inorganic hybrid zinc-based two-dimensional perovskite material doped with aliovalent ions and a preparation method thereof, in particular to an organic and inorganic hybrid zinc-based two-dimensional perovskite material doped with aliovalent ions and high in 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 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, lead is currently the main component of perovskite, the toxicity of which greatly limits its application in the photovoltaic field, and therefore it is necessary to replace lead with an element that is non-toxic or less toxic. 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. Doping, on the other hand, is an effective way to significantly control the electronic structure and physical properties of metal halide perovskite and even to induce new functions.
Disclosure of Invention
The invention aims to provide an organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with aliovalent ions and high in fluorescence quantum yield and a preparation method thereof, and the organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with aliovalent ions is high in purity, green and nontoxic zinc ions are used for replacing heavy metal lead ions, aliovalent ion doping is used for further regulating and controlling the electronic structure and physical properties of the zinc-based perovskite material, the half-peak width of an emission spectrum is large (> 100 nm), and along with larger Stokes displacement, the photoluminescence quantum yield is high and can reach 80% at most, the stability is good, the preparation process is simple, the cost is low, the repeatability is high, the preparation period is short, and the material is environment-friendly and can be effectively applied to the field of solid-state lighting.
According to a first aspect of the present invention, there is provided a method for preparing an aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material, comprising the steps of:
(1) ZnX is to 2 And BX n Dissolving in a volatile polar solvent, wherein B is monovalent and/or trivalent heterovalent metal ions, and X is halogen ions, so as to obtain a first premix; dissolving organic amine in a volatile polar solvent to obtain a second premix;
(2) Mixing the first premix liquid and the second premix liquid obtained in the step (1), then dropwise adding halogen acid to enable the organic amine to be protonated to form organic amine ions, and reacting with all kinds of metal ions and halogen ions to obtain a third premix liquid;
(3) And (3) volatilizing the solvent in the third premix liquid obtained in the step (2), and separating out the aliovalent ion doped organic and inorganic hybrid zinc-based two-dimensional perovskite crystal.
Preferably, B is Cu + 、Bi 3+ 、In 3+ 、Fe 3+ And Sb (Sb) 3+ At least one of them.
Preferably, the first premix solution further comprises a manganese halide.
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 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 sum of the concentration of the organic amine ions in the third premix solution and the concentration of all kinds of metal ions is (0.1-10): 1.
Preferably, the concentration of the organic amine ions in the third premix is 0.05mol/L-10mol/L, and the concentration of the total metal ions is 0.05mol/L-10mol/L.
According to another aspect of the invention, an organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with aliovalent ions and prepared by any one of the methods is provided.
Preferably, the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material has the general formula A 2 Zn 1- x B x X 4 Wherein A is aromatic amine cation, X is halogen element, B is Cu + 、Bi 3+ 、In 3+ 、Fe 3+ And Sb (Sb) 3+ At least one of (a) and (b);
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.
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 doped with the aliovalent ions, which is prepared by the invention, has high purity, the emission spectrum is wide, the wide-spectrum luminescence is derived from self-trapping exciton composite luminescence caused by strong phonon-electron coupling 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%. The photoluminescence quantum yield of the material can be greatly improved by doping with aliovalent ions, the maximum is about 80 percent, the quantum yield is far higher than that 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 can effectively inhibit a non-radiative composite path caused by lattice intrinsic defects through introduction of aliovalent ions, so that the photoluminescence quantum yield of the organic-inorganic hybrid zinc-based two-dimensional perovskite material is greatly improved.
(3) 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 under the environmental condition, and prepares the organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with aliovalent ions and having high fluorescence quantum yield through the steps of filtering, washing, vacuum drying and the like.
(4) The organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with the aliovalent ions is crystallized by adopting an evaporation crystallization method, and 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 is prepared by adopting a system which belongs to an anhydrous system, so that fluorescence quenching caused by the generation of non-fluorescent perovskite complex can be avoided.
(5) The organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with the aliovalent ions has excellent thermal stability, and is characterized in that the photoluminescent intensity of the material still keeps 80-98% of the original intensity after the material is continuously heated for 1000 hours at 100 ℃.
(6) The organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with the aliovalent ions has excellent light stability, and is characterized in that the photoluminescence intensity of the material still keeps 50-75% of the original intensity after the LED with the rated power of 6-10W and the wavelength of 302nm is continuously irradiated for 240 minutes.
(7) The organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with the aliovalent ions has excellent storage stability, and is characterized in that the material is stored for 3 months under the environmental conditions of 20-25 ℃ and 50-70% of humidity, and the photoluminescence intensity of the material is almost unchanged.
(8) In the whole preparation process of the organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with the aliovalent ions, no toxic raw materials or reagents are used, and the material is environment-friendly and environment-friendly.
(9) The invention has simple preparation process, mild production condition, low cost, high repeatability and short 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 an ultraviolet visible absorption spectrum of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of comparative example 1 and examples 1-6.
FIG. 3 is a fluorescence spectrum of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of comparative example 1 and examples 1 to 6.
FIG. 4 is an EDS pattern 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 material of comparative example 1 and examples 1-6.
FIG. 6 is a microscopic map and EDS elemental surface profile of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3.
Fig. 7 is an excitation spectrum 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 at different excitation wavelengths for the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3.
FIG. 9 is a graph showing the dependence of fluorescence intensity on excitation light power of the hetero-valence ion-doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3.
Fig. 10 is a photoluminescence quantum efficiency plot of the 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
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 an organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with aliovalent ions and having high fluorescence quantum yield, which mainly comprises the following steps:
(1) Weighing mixed metal halide ZnX with a certain molar ratio under inert atmosphere 2 And BX n Dissolving the mixture in a volatile polar solvent, and stirring until the solution is clear to obtain a premix solution X;
(2) Dissolving organic amine A with 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 the aliovalent ion doped organic and inorganic hybrid zinc-based two-dimensional perovskite material with high fluorescence quantum yield from the bottom of the 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 at least one of methanol, absolute ethanol, isopropanol and acetone.
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 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 0.05-10mol/L, and the total metal ion concentration is 0.05-10mol/L.
The organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with the aliovalent ions and having high fluorescence quantum yield and prepared by the preparation method meets the general formula A 2 Zn 1-x B x X 4 Wherein A is 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 + ) Octylamine ion (C) 8 H 17 NH 3 + ，OA + ) One or a mixture of more than one of the components, B is Cu + 、Bi 3+ 、In 3+ 、Fe 3+ 、Sb 3+ 、Mn 2+ The metal ions are mixed by one or more of halogen elements F, cl and Br.
Further, 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 results from self-trapping exciton recombination luminescence due to strong phonon-electron coupling in the low-dimensional perovskite.
Further, it has excellent thermal stability. The specific expression is that the photoluminescent intensity of the material still keeps 80-98% of the original intensity after the material is heated continuously for 1000 hours at 80 ℃.
Further, it has excellent light stability. The method is characterized in that the photoluminescence intensity of the LED is still 50-75% of the original intensity after the LED with the rated power of 6-10W and the wavelength of 302nm is continuously irradiated for 240 minutes.
Further, it has excellent storage stability. The specific expression is that the photoluminescent intensity is almost unchanged when the product is stored for 3 months under the environmental conditions that the temperature is 20-25 ℃ and the humidity is 50-70%.
Comparative example 1
4mmol of zinc bromide (ZnBr) 2 ) And 8mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 5ml of methanol, uniformly mixing the two premix solutions, adding 940. 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 PEA 2 ZnBr 4 . 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 180nm.
Example 1
3.92mmol of zinc bromide (ZnBr) 2 ) 0.08mmol of cuprous bromide (CuBr) and 8mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 5ml of methanol, uniformly mixing the two premix solutions, adding 250 μl of hypophosphorous acid and 940 μl of 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 with sealing film with small holes, slowly evaporating at room temperature for several days to separate 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 doped with aliovalent ions 2 Zn 0.98 Cu 0.02 Br 3.98 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 60.2%, the luminescence center is located at 481nm, and the half-peak width is 84nm.
Example 2
3.86mmol of zinc bromide (ZnBr) 2 ) 0.14mmol of cuprous bromide (CuBr) and 8mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 5ml of methanol, uniformly mixing the two premix solutions, adding 250 μl of hypophosphorous acid and 940 μl of 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 PEA doped with aliovalent ions 2 Zn 0.965 Cu 0.035 Br 3.965 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 71.8%, the luminescence center is 475nm, and the half-peak width is 94nm.
Example 3
3.80mmol of zinc bromide (ZnBr) were each reacted 2 ) 0.20mmol of cuprous bromide (CuBr) and 8mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 5ml of methanol, uniformly mixing the two premix solutions, adding 250 μl of hypophosphorous acid and 940 μl of 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 PEA doped with aliovalent ions 2 Zn 0.95 Cu 0.05 Br 3.95 . 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 94nm.
Example 4
3.70mmol of zinc bromide (ZnBr) were each reacted 2 ) 0.30mmol of cuprous bromide (CuBr) and 8mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 5ml of methanol, uniformly mixing the two premix solutions, adding 250 μl of hypophosphorous acid and 940 μl of 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 PEA doped with aliovalent ions 2 Zn 0.925 Cu 0.075 Br 3.925 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 65.7%, the luminescence center is 477nm, and the half-peak width is 93nm.
Example 5
3.60mmol of zinc bromide (ZnBr) were each reacted 2 ) 0.40mmol of cuprous bromide (CuBr) and 8mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 5ml of methanol, uniformly mixing the two premix solutions, adding 250 μl of hypophosphorous acid and 940 μl of 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 PEA doped with aliovalent ions 2 Zn 0.9 Cu 0.1 Br 3.9 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 65.0%, the luminescence center is located at 478nm, and the half-peak width is 92nm.
Example 6
3.20mmol of zinc bromide (ZnBr) were each reacted 2 ) 0.80mmol of cuprous bromide (CuBr) and 8mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 5ml of methanol, uniformly mixing the two premix solutions, adding 250 μl of hypophosphorous acid and 940 μl of 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 PEA doped with aliovalent ions 2 Zn 0.8 Cu 0.2 Br 3.8 . 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 92nm.
Example 7
3.60mmol of zinc bromide (ZnBr) were each reacted 2 ) 0.20mmol of cuprous bromide (CuBr), 0.20mmol of ferric bromide (FeBr) 3 ) And 8mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 5ml of absolute ethanol, uniformly mixing the two premix solutions, then adding 250 μl of hypophosphorous acid and 940 μl of 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 PEA doped with aliovalent ions 2 Zn 0.90 Cu 0.05 Fe 0.05 Br 4 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 42.6%, the luminescence center is positioned at 485nm, and the half-peak width is 93nm.
Example 8
3.60mmol of zinc bromide (ZnBr) were each reacted 2 ) 0.20mmol of cuprous bromide (CuBr), 0.20mmol of indium bromide (InBr) 3 ) And 8mmol of phenethylamine(C 6 H 5 C 2 H 4 NH 2 ) Dissolving in 5ml of isopropanol, uniformly mixing the two premix solutions, then adding 250 μl of hypophosphorous acid and 940 μl of 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 PEA doped with aliovalent ions 2 Zn 0.90 Cu 0.05 In 0.05 Br 4 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 76.4%, the luminescence center is 477nm, and the half-peak width is 87nm.
Example 9
3.60mmol of zinc bromide (ZnBr) were each reacted 2 ) 0.20mmol of cuprous bromide (CuBr), 0.20mmol of antimony bromide (SbBr) 3 ) And 8mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 5ml of acetone, uniformly mixing the two premix solutions, adding 250 μl of hypophosphorous acid and 940 μl of 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 PEA doped with aliovalent ions 2 Zn 0.90 Cu 0.05 Sb 0.05 Br 4 . 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 73nm.
Example 10
3.60mmol of zinc bromide (ZnBr) were each reacted 2 ) 0.20mmol of cuprous bromide (CuBr), 0.20mmol of manganese bromide (MnBr) 2 ) And 8mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolved in 5ml of methanol and absolute ethanolThe two premix solutions were mixed homogeneously, followed by addition of 250. Mu.l of hypophosphorous acid and 940. Mu.l of hydrobromic acid, and vigorously stirred at room temperature for 4 hours at a speed of 800-1000rpm/min, to give 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 doped with aliovalent ions 2 Zn 0.90 Cu 0.05 Mn 0.05 Br 3.95 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 76.9%, the luminescence center is located at 478.5nm, and the half-peak width is 89nm.
Example 11
3.40mmol of zinc bromide (ZnBr) were each reacted 2 ) 0.20mmol of cuprous bromide (CuBr), 0.40mmol of manganese bromide (MnBr) 2 ) And 8mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 5ml of mixed solution of methanol and isopropanol, uniformly mixing the two premix solutions, then adding 250 μl of hypophosphorous acid and 940 μl of 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 PEA doped with aliovalent ions 2 Zn 0.85 Cu 0.05 Mn 0.10 Br 3.95 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 82.0%, the luminescence center is located at 476.5nm, and the half-peak width is 93nm.
Example 12
3.20mmol of zinc bromide (ZnBr) were each reacted 2 ) 0.20mmol of cuprous bromide (CuBr), 0.60mmol of manganese bromide (MnBr) 2 ) And 8mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 5ml of mixed solution of methanol and acetone, and mixing the two pre-mixed solutionsAfter mixing, 250. Mu.l of hypophosphorous acid and 940. Mu.l of hydrobromic acid were added and stirred vigorously at room temperature for 4 hours at 800-1000rpm/min to give 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 doped with aliovalent ions 2 Zn 0.80 Cu 0.05 Mn 0.15 Br 3.95 . The quantum yield of the obtained organic-inorganic hybrid zinc-based two-dimensional perovskite material is 94.1%, the luminescence center is located at 478.5nm, and the half-peak width is 94nm.
Example 13
3.00mmol of zinc bromide (ZnBr) 2 ) 0.20mmol of cuprous bromide (CuBr), 0.80mmol of manganese bromide (MnBr) 2 ) And 8mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 5ml of methanol, uniformly mixing the two premix solutions, adding 250 μl of hypophosphorous acid and 940 μl of 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 PEA doped with aliovalent ions 2 Zn 0.65 Cu 0.05 Mn 0.20 Br 3.95 . 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 93nm.
Example 14
2.80mmol of zinc bromide (ZnBr) were each reacted 2 ) 0.20mmol of cuprous bromide (CuBr), 1.00mmol of manganese bromide (MnBr) 2 ) And 8mmol of phenethylamine (C) 6 H 5 C 2 H 4 NH 2 ) Dissolving in 5ml methanol, mixing the two pre-mixed solutions uniformly, adding 250 μl hypophosphorous acid and 940 μl hydrobromic acid, and stirring vigorously at room temperature for 4 hrThe rotational speed is 800-1000rpm/min, and clear and transparent solution is 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 PEA doped with aliovalent ions 2 Zn 0.60 Cu 0.05 Mn 0.25 Br 3.95 . 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 94nm.
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 incorporated + After that, XRD characteristic peak changes very little, indicating Cu + The introduction of (3) does not change the crystal form of the organic-inorganic hybrid zinc-based two-dimensional perovskite. And with Cu + The increase of doping amount, the diffraction peak of the low angle area gradually shifts to a large angle, which proves that Cu + Into the lattice of the organic-inorganic hybrid zinc-based two-dimensional perovskite, and Cu + The introduction of (3) reduces the lattice constant of the organic-inorganic hybrid zinc-based two-dimensional perovskite.
FIG. 2 is an ultraviolet visible absorption spectrum of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of comparative example 1 and examples 1-6. As can be seen from the graph, examples 1 to 6 have a shoulder at 300 nm more than comparative example 1, which corresponds to the exciton absorption peak, indicating that the doping of the hetero-valence ions causes the enhancement of the exciton absorption, thereby forming stable excitons, which is advantageous for improving the photoluminescence quantum efficiency.
FIG. 3 is a fluorescence spectrum of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of comparative example 1 and examples 1 to 6. From the graph, the light-emitting intensity of comparative example 1 is extremely low compared with that of examples 1 to 6, which indicates that the light-emitting performance of the organic-inorganic hybrid zinc-based two-dimensional perovskite material can be greatly improved through a small amount of aliovalent ion doping.
FIG. 4 is an EDS pattern 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 Cu+ is further proved to successfully enter the crystal lattice of the organic-inorganic hybrid zinc-based two-dimensional perovskite.
FIG. 5 is a thermogravimetric plot of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of comparative example 1 and examples 1-6. From the graph, the thermal decomposition temperature of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material is about 320 ℃, and the material has excellent thermal stability.
FIG. 6 is a microscopic map and EDS elemental surface profile 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 lattice of the perovskite.
Fig. 7 is an excitation spectrum of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3 at different emission wavelengths. From the figure, it is clear that the excitation spectrum of example 3 maintains the same pattern at different emission wavelengths from 420 nm to 600 nm, indicating that the fluorescence emissions are all from the same excited state.
FIG. 8 is a two-dimensional profile of fluorescence at different excitation wavelengths for the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3. From the graph, it is known that the photoluminescence peak position and half-width of example 3 remain substantially unchanged at different excitation wavelengths of 240 nm to 380 nm, indicating that only one emission center exists.
FIG. 9 is a graph showing the dependence of fluorescence intensity on excitation light power of the hetero-valence ion-doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3. From the graph, the fluorescence intensity and the excitation light power of the organic-inorganic hybrid zinc-based two-dimensional perovskite material are in a super-linear relation, and the luminescence is proved to be derived from strong exciton recombination rather than permanent defects.
Fig. 10 is a photoluminescence quantum efficiency plot of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3. From the figure it is known 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. From the graph, it is known that the organic-inorganic hybrid zinc-based two-dimensional perovskite material of comparative example 1 exhibits a double exponential lifetime, in which the short lifetime is 47 microseconds and the long lifetime is 342 microseconds. Wherein short lifetime results from exciton recombination and 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. From the graph, it is known that the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material of example 3 exhibits a single index with a fluorescence lifetime of 63 microseconds. It is demonstrated that defects can be effectively passivated by aliovalent metal ions, resulting in luminescence derived entirely from exciton recombination, resulting in high photoluminescence quantum yields.
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 (8)
1. The preparation method of the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material is characterized by comprising the following steps of:
(1) ZnX is to 2 And BX n Dissolving in a volatile polar solvent, wherein B is monovalent and/or trivalent heterovalent metal ions, and X is halogen ions, so as to obtain a first premix; dissolving organic amine in a volatile polar solvent to obtain a second premix;
b is Cu + 、Bi 3+ And Fe (Fe) 3+ At least one of (a) and (b);
the first premix solution also comprises manganese halide;
(2) Mixing the first premix liquid and the second premix liquid obtained in the step (1), then dropwise adding halogen acid to enable the organic amine to be protonated to form organic amine ions, and reacting with all kinds of metal ions and halogen ions to obtain a third premix liquid;
(3) And (3) volatilizing the solvent in the third premix liquid obtained in the step (2), and separating out the aliovalent ion doped organic and inorganic hybrid zinc-based two-dimensional perovskite crystal.
2. The method for preparing a heterovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material according to claim 1, wherein the organic amine is aromatic amine.
3. The method for preparing the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material according to claim 2, wherein the aromatic amine is benzyl amine, phenethyl amine, amphetamine, p-methylphenylethylamine, o-fluorobenzene methylamine, m-fluorobenzene methylamine, o-fluorobenzene ethylamine, m-fluorobenzene ethylamine or p-fluorobenzene ethylamine.
4. A method for preparing an aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material according to 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.
5. The method for preparing an isovalent ion doped organic and inorganic hybrid zinc-based two-dimensional perovskite material according to claim 1, wherein the volatile polar solvent is at least one of methanol, absolute ethanol, isopropanol and acetone.
6. The method for preparing the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material according to claim 1, wherein the sum of the concentration of organic amine ions in the third premix solution and the concentration of all kinds of metal ions is (0.1-10): 1.
7. The method for preparing the aliovalent ion doped organic-inorganic hybrid zinc-based two-dimensional perovskite material according to claim 6, wherein the concentration of organic amine ions in the third premix solution is 0.05mol/L-10mol/L, and the concentration of total metal ions is 0.05mol/L-10mol/L.
8. The organic-inorganic hybrid zinc-based two-dimensional perovskite material doped with aliovalent ions prepared by the method of any one of claims 1 to 7.
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