CN115093442B - Perovskite nanocrystalline with high fluorescence quantum yield and preparation method thereof - Google Patents
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Abstract
The invention discloses a perovskite nanocrystalline with high fluorescence quantum yield and a preparation method thereof, organic cation long-chain BABr, PEABr,4-FPEABr are introduced into a perovskite precursor solution to passivate surface defects of crystal grains, and quantum confinement is realized under the assistance of an SBA-15 template, so that the fluorescence quantum yield of the perovskite nanocrystalline is improved, and the highest fluorescence quantum yield can reach 98.5%. The excellent photoelectric property of the perovskite nano-crystal can help to promote the mass production and commercial application of the perovskite nano-crystal with high fluorescence quantum yield.
Description
Technical Field
The invention belongs to the field of photoelectrons, and particularly relates to a perovskite nanocrystal with high fluorescence quantum yield and a preparation method thereof.
Background
The metal halide perovskite nanocrystals have attracted considerable attention in recent years in the optoelectronic field due to their excellent optoelectronic properties, with commercial potential in terms of display, illumination, and radiation scintillation. However, due to the instability and tendency to blend into the bulk phase of perovskite solid films, it remains challenging to actually implement their optoelectronic devices by virtue of preserving the quantum confinement state. Furthermore, conventional methods of precipitation by solvent-induced co-precipitation strategies and ligand-assisted re-precipitation have difficulty in obtaining large amounts of high fluorescence quantum yield perovskite nanocrystalline materials by simple and scalable precipitation, and thus materials are difficult to obtain, which limits mass production of high fluorescence quantum yield perovskite nanocrystals.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a perovskite nanocrystalline with high fluorescence quantum yield and a preparation method thereof, wherein Ruddlesden-Popper (RP) perovskite NCs directly grown in a mesoporous silica template realize bright and stable emission. The perovskite nanocrystalline with high fluorescence quantum yield and the preparation method thereof are provided, and the quantitative preparation of the perovskite nanocrystalline is realized by controlling the quantity of the porous template SBA-15 and the quantity of the corresponding perovskite precursor solution, so that the problem that the perovskite nanocrystalline with high fluorescence quantum yield is difficult to synthesize in a large quantity in the prior art is solved.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
a method for preparing perovskite nanocrystalline with fluorescence quantum yield, which comprises the following steps:
Step 1, mixing SBA-15 powder and perovskite precursor solution to obtain mixed solution C; the SBA-15 is an inert mesoporous template, the solute of the perovskite precursor solution is a mixture of PbBr 2、CH3NH3 Br and organic cation long-chain substances, and the solvent is DMF; the organic cation long-chain substance is BABr, or PEABr or 4-FPEABr;
Step 2, carrying out ultrasonic treatment on the mixed solution C to obtain a mixed solution D;
Step 3, separating the mixed solution D by a decompression suction filtration method to obtain SBA-15 filled with perovskite precursor solution;
And 4, annealing and crystallizing the SBA-15 filled with the perovskite precursor solution until the mixture is completely discolored from white, and emitting green light under the irradiation of an ultraviolet lamp to generate perovskite nanocrystalline in the SBA-15.
The invention further improves that:
Preferably, in step 1, the concentration of the perovskite precursor solution is 0.05-0.2M.
Preferably, in step 1, the perovskite precursor solution is prepared by the following steps: according to the molar ratio n: n-1:2, mixing PbBr 2、CH3NH3 Br and organic cation long-chain substances, wherein n is a natural number of 2-5, forming a mixed solute A, and dissolving the mixed solute A in DMF to obtain a mixed solution B; and (3) oscillating the mixed solution B for more than 5 hours, and filtering the mixed solution by an organic filtering membrane to obtain a clear perovskite precursor solution.
Preferably, in step 1, the mixing ratio of SBA-15 powder and perovskite precursor solution is 0.05g:300uL.
Preferably, in step 2, the ultrasound time is 10-30 minutes.
Preferably, in step 4, the annealing temperature is 100 ℃.
Preferably, in step 1, the preparation method of the SBA-15 powder comprises the following steps: adding P123 into a hydrochloric acid solution, stirring, adding TEOS, continuously stirring to obtain a mixed solution, filtering the mixed solution to obtain a solid product, drying the solid product, redispersing the dried solid in a hydrochloric acid-ethanol solution, stirring, filtering, drying the filtered product, and calcining the dried product in air to generate SBA-15 powder.
Preferably, the mass ratio of the P123 to the hydrochloric acid in the hydrochloric acid solution is 3.46:4.5; p123 was added to the hydrochloric acid solution and stirred at 45 ℃ for 6 hours, and after the addition of TEOS, stirred at 45 ℃ for 24 hours.
Preferably, in step 4, the annealing temperature is 100 ℃.
A fluorescence quantum yield perovskite nanocrystal prepared by the above preparation method, wherein the size of the nanocrystal is 5±2nm.
Compared with the prior art, the invention has the following beneficial effects:
The invention discloses a preparation method of perovskite nanocrystalline with high fluorescence quantum yield, which uses BABr, PEABr and 4-FPEABr as additives to prepare perovskite precursor solution, and prepares perovskite nanocrystalline with high fluorescence quantum yield by regulating precursor solute components. This will provide a new idea and method for pushing perovskite fluorescent materials towards commercial applications. Therefore, by regulating and controlling the components of the precursor liquid, an additive with excellent performance is searched for to obtain a high-standard perovskite precursor liquid, and a solution method is used for preparing perovskite nanocrystals with high fluorescence quantum yield.
In the preparation process of the perovskite nanocrystalline, organic cation long-chain BABr, PEABr and 4-FPEABr are introduced into MAPbBr 3 solution, and NCs are formed in SBA-15 mesoporous silica in order to benefit from physical limitation; NC is 5+ -2 nanometers in size, which is smaller than the Bohr radius. Efficient energy funnels are formed between RP layers tuned for different quantum sizes in NCs. The combined exciton confinement and efficient energy funneling between the electron separated quantum wells ensures that radiative recombination is successful over non-radiative recombination, yielding PLQYs% or more. The excellent photoelectric property of the perovskite nano-crystal can help to promote the mass production and commercial application of the perovskite nano-crystal with high fluorescence quantum yield.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) of organic cationic long chain 4-FPEA (n=2) perovskite nanocrystals in SBA-15 introduced by the method described in the examples of the invention.
FIG. 2 is a graph comparing the fluorescence quantum yield (PLQY) of perovskite nanocrystals without organic cation long chains introduced by the method described in the examples of the present invention. (a) The graph shows the fluorescence quantum yield of perovskite nanocrystals without the organic cation long chain incorporated therein, and (b) the graph shows the fluorescence quantum yield of perovskite nanocrystals with the organic cation long chain incorporated therein of 4-FPEA.
Fig. 3 is a graph comparing ultraviolet absorption of perovskite nanocrystals prepared without the introduction of organic cation long chain 4-FPEA (n=2) by the method described in the examples of the present invention.
Fig. 4 is a graph of steady-state fluorescence comparison of perovskite nanocrystals prepared without the introduction of organic cation long chains 4-FPEA (n=2) according to the method described in the examples of the present invention.
Detailed Description
The invention is described in further detail below with reference to the attached drawing figures:
The invention relates to a preparation method of perovskite nanocrystalline with high fluorescence quantum yield, which comprises the following steps:
Step 1, preparation of perovskite precursor solution
Mixing PbBr 2、CH3NH3 Br and organic cation long-chain substances according to a molar ratio (A) 2(MA)n-1PbnBr3n+1 (n=1-5, +%) (A=BABr, PEABr, 4-FPEABr), wherein the molar ratio is (n: n-1:2, n=2-5, n is a natural number), and the organic cation long-chain substances are BABr, PEABr or 4-FPEABr, forming a mixed solute A, dissolving the mixed solute A in DMF solvent to form a mixed solution B with a concentration of 0.05-0.2M, oscillating the mixed solution B for more than 5 hours, and filtering the mixed solution B by an organic filter membrane with a pore diameter of 0.45 mu M to obtain a clear perovskite precursor solution.
Step 2, synthesizing an SBA-15 template: 4.5 g of concentrated hydrochloric acid was added to 21.6 g of deionized water to form a homogeneous hydrochloric acid solution A. 3.46 g of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer) were introduced into the above solution A and stirred vigorously at 45℃for 6 hours. Subsequently, 5ml of TEOS (tetraethoxysilane) was added to the solution and the whole mixture was kept stirring at 45 ℃ for 24 hours. The solid product was obtained by filtration and dried at 100 ℃ for 12 hours. Finally, the solid was redispersed in a hydrochloric acid-ethanol (volume ratio=1:4) solution so that the hydrochloric acid-ethanol solution could completely cover the solid, stirred for 4 hours after the dispersion, then filtered, the filtered product was dried overnight at 100 ℃ and calcined in air at 550 ℃ for 6 hours to finally synthesize highly ordered inert mesoporous template SBA-15.
And 3, mixing the SBA-15 powder and the perovskite precursor solution to obtain a mixed solution C, wherein the mixed proportion of the SBA-15 and the perovskite precursor solution is that about 300uL of the perovskite precursor solution is added into each 0.05g of SBA-15 powder.
And 4, ultrasonically treating a mixed solution C of SBA-15 and perovskite nanocrystalline, and ultrasonically treating a mixture of SBA-15 and perovskite precursor solution in an ultrasonic cleaning agent for about 10-30 minutes, so that the perovskite precursor solution fully impregnates pore channels of the SBA-15 template.
Step 5: separating SBA-15 from excess perovskite precursor solution: and separating the excessive perovskite precursor solution from the SBA-15 by adopting a decompression suction filtration method to finally obtain the SBA-15 filled with the perovskite precursor solution, wherein the SBA-15 is the SBA-15 filled with the perovskite precursor solution.
Step 6, annealing and crystallizing the mixture with the perovskite precursor solution filled with SBA-15 pore canals: SBA-15 filled with perovskite precursor solution was annealed to the mixture powder at 100 ℃ from white all to pale yellow with Nanocrystalline (NC) size of 5±2 nanometers, less than the bohr radius. The fluorescent quantum yield of nearly 100% can be achieved by strong green light emission under irradiation of ultraviolet lamp (365 nm). In the crystallization process, perovskite crystal grains are nucleated and grown, and pore channels in the SBA-15 template in the growth process are limited domains with space sizes for growing perovskite nanocrystals.
Example 1
The preparation method of the perovskite nanocrystalline with high fluorescence quantum yield, disclosed by the invention, comprises the following preparation steps of:
Preparing perovskite precursor liquid: the preparation concentration was 0.1M, and PbBr 2 was weighed according to (4-FPEA) 2(MA)n-1PbnBr3n+1 (n=2): MABr:4-FPEABr = 2:1:2 solute dissolved in DMF solvent to give 1mL perovskite precursor solution.
Synthesizing an SBA-15 template: 4.5 grams of concentrated hydrochloric acid was added to 21.6 grams of deionized water to form a homogeneous solution. 3.46 g of P123 were introduced into the above solution and stirred vigorously at 45℃for 6 hours. Subsequently, TEOS was added to the solution and the whole mixture was kept stirring at 45 ℃ for 24 hours. The solid product was obtained by filtration and dried overnight at 100 ℃. Finally, the solid was redispersed in a hydrochloric acid-ethanol (volume ratio=1:4) solution and stirred for 4 hours, then filtered, dried overnight at 100 ℃, and calcined in air at 550 ℃ for 6 hours to remove the template.
Mixing SBA-15 powder and perovskite precursor solution: the ratio of SBA-15 to perovskite precursor solution was such that 300uL of perovskite precursor solution was added per 0.05g of SBA-15 powder.
Mixture of ultrasonic SBA-15 powder and perovskite nanocrystals: the mixture of SBA-15 and perovskite precursor solution was sonicated in an ultrasonic cleaner for 30 minutes.
Separating SBA-15 from excess perovskite precursor solution: and separating the mixture of the SBA-15 and the perovskite precursor solution after ultrasonic treatment by adopting a decompression suction filtration method to finally obtain a mixture of the perovskite precursor solution filled in the SBA-15 pore canal.
Annealing and crystallizing the mixture with the perovskite precursor solution filled with SBA-15 pore canals: SBA-15 impregnated with perovskite precursor solution was annealed to the mixture at 100 ℃ to fully color change from white.
The characterization analysis of the perovskite nanocrystalline with high fluorescence quantum yield comprises the following contents:
FIG. 1 shows that perovskite nanocrystals are limited in an SBA-15 template after long chains are introduced, so that the effect of space limitation is achieved, and the size is about 5nm (FIG. 1).
Fig. 2: a fluorescence quantum yield test Pattern (PLQY) of perovskite nanocrystals. The perovskite nanocrystalline with high fluorescence quantum yield prepared by the invention has obviously improved fluorescence quantum yield after long-chain 4-FPEA, PEA and BA are introduced. The optimized sample had a fluorescence quantum yield of 98.5% (fig. 2 a), while the reference sample had a fluorescence quantum yield of 16.4% (fig. 2 b).
Fig. 3: ultraviolet visible light absorption diagram (UV-Vis) of perovskite nanocrystals. As can be seen from fig. 3: there is a slight blue shift after long chain incorporation compared to perovskite nanocrystals without long chain incorporation. The band gap of the perovskite nanocrystalline without introducing a long chain is 2.26eV, the band gap is gradually increased after introducing a long chain, and the perovskite nanocrystalline band gap is calculated to be 2.54 eV when n=2.
Fig. 4: fluorescence emission spectrum (PL) of perovskite thin film. As can be seen from fig. 4: there is a slight blue shift after long chain incorporation, which is consistent with the ultraviolet absorbance pattern, compared to perovskite nanocrystals without long chain incorporation.
Example 2
The preparation method of the high fluorescence quantum yield comprises the following preparation steps:
preparing perovskite precursor liquid: the preparation concentration was 0.1M, and PbBr 2 was weighed according to (4-FPEA) 2(MA)n-1PbnBr3n+1 (n=3): MABr:4-FPEABr = 1.5:1:1 solute dissolved in DMF solvent to give 1mL perovskite precursor solution.
The other steps were the same as in example 1.
Example 3
The preparation method of the high fluorescence quantum yield comprises the following preparation steps:
Preparing perovskite precursor liquid: the preparation concentration was 0.1M, and PbBr 2 was weighed according to (4-FPEA) 2(MA)n-1PbnBr3n+1 (n=4): MABr:4-FPEABr = 4:3:2 solute dissolved in DMF solvent to give 1mL perovskite precursor solution.
The other steps were the same as in example 1.
Example 4
The preparation method of the high fluorescence quantum yield comprises the following preparation steps:
Preparing perovskite precursor liquid: the preparation concentration was 0.1M, and PbBr 2 was weighed according to (4-FPEA) 2(MA)n-1PbnBr3n+1 (n=5): MABr:4-FPEABr = 5:4:2 solute dissolved in DMF solvent to give 1mL perovskite precursor solution.
The other steps were the same as in example 1.
Example 5
The preparation method of the high fluorescence quantum yield comprises the following preparation steps:
preparing perovskite precursor liquid: the concentration was formulated at 0.1M and PbBr 2 was weighed according to (PEA) 2(MA)n-1PbnBr3n+1 (n=2): MABr: PEABr = 2:1:2 solute, dissolved in DMF solvent to give 1mL of perovskite precursor solution.
The other steps were the same as in example 1.
Example 6
The preparation method of the high fluorescence quantum yield comprises the following preparation steps:
Preparing perovskite precursor liquid: the concentration was formulated at 0.1M and PbBr 2 was weighed according to (PEA) 2(MA)n-1PbnBr3n+1 (n=3): MABr: PEABr = 1.5:1:1 solute, dissolved in DMF solvent to give 1mL of perovskite precursor solution.
The other steps were the same as in example 1.
Example 7
The preparation method of the high fluorescence quantum yield comprises the following preparation steps:
Preparing perovskite precursor liquid: the concentration was formulated at 0.1M and PbBr 2 was weighed according to (PEA) 2(MA)n-1PbnBr3n+1 (n=4): MABr: PEABr = 4:3:2 solute dissolved in DMF solvent to give 1mL of perovskite precursor solution.
The other steps were the same as in example 1.
Example 8
The preparation method of the high fluorescence quantum yield comprises the following preparation steps:
Preparing perovskite precursor liquid: the concentration was formulated at 0.1M and PbBr 2 was weighed according to (PEA) 2(MA)n-1PbnBr3n+1 (n=5): MABr: PEABr = 5:4:2 solute, dissolved in DMF solvent to give 1mL of perovskite precursor solution.
The other steps were the same as in example 1.
Example 9
The preparation method of the high fluorescence quantum yield comprises the following preparation steps:
Preparing perovskite precursor liquid: the concentration was 0.1M, and PbBr 2 was weighed according to (BA) 2(MA)n-1PbnBr3n+1 (n=2): MABr: BABr = 2:1:2 solute, dissolved in DMF solvent to give 1mL of perovskite precursor solution.
The other steps were the same as in example 1.
Example 10
The preparation method of the high fluorescence quantum yield comprises the following preparation steps:
Preparing perovskite precursor liquid: the concentration was 0.1M, and PbBr 2 was weighed according to (BA) 2(MA)n-1PbnBr3n+1 (n=3): MABr: BABr = 1.5:1:1 solute, dissolved in DMF solvent to give 1mL of perovskite precursor solution.
The other steps were the same as in example 1.
Example 11
The preparation method of the high fluorescence quantum yield comprises the following preparation steps:
Preparing perovskite precursor liquid: the concentration was 0.1M, and PbBr 2 was weighed according to (BA) 2(MA)n-1PbnBr3n+1 (n=4): MABr: BABr = 4:3:2 solute dissolved in DMF solvent to give 1mL of perovskite precursor solution.
The other steps were the same as in example 1.
Example 12
The preparation method of the high fluorescence quantum yield comprises the following preparation steps:
Preparing perovskite precursor liquid: the concentration was 0.1M, and PbBr 2 was weighed according to (BA) 2(MA)n-1PbnBr3n+1 (n=5): MABr: BABr = 5:4:2 solute, dissolved in DMF solvent to give 1mL of perovskite precursor solution.
The other steps were the same as in example 1.
Comparative example 1
The preparation method of the high fluorescence quantum yield comprises the following preparation steps:
Preparing perovskite precursor liquid: the preparation concentration is 0.1M, and the weight molar ratio is PbBr 2: MABr = 1:1 solute, dissolved in DMF solvent to give 1mL perovskite precursor solution.
The other steps were the same as in example 1.
Comparative example 2
The preparation method of the perovskite nanocrystalline with high fluorescence quantum yield comprises the following preparation steps:
Preparing perovskite precursor liquid: the preparation concentration is 0.2M, and the weight molar ratio is PbBr 2: MABr = 1:1 solute, dissolved in DMF solvent to give 1mL perovskite precursor solution.
The other steps were the same as in example 1.
The results of the fluorescence quantum yield test on (a) 2(MA)n-1PbnBr3n+1 (n=2-5) (a=4-FPEA, PEA, BA) perovskite nanocrystals prepared in examples 1-12 and comparative examples 1-2, respectively, were tested in a room temperature environment under an excitation wavelength of 365nm using a quantum yield measurement system of model C9920-02G of pinus koraiensis, as shown in table 1 below.
List one
Example 13
The concentration of the perovskite precursor solution in this example was 0.05M, and the rest of the procedure was the same as in example 1.
Example 14
The concentration of the perovskite precursor solution in this example was 0.08M, and the rest of the procedure was the same as in the example.
Example 15
The concentration of the perovskite precursor solution in this example was 0.12M, and the rest of the procedure was the same as in the example.
Example 16
The concentration of the perovskite precursor solution in this example was 0.15M, and the rest of the procedure was the same as in the example.
Example 17
The concentration of the perovskite precursor solution in this example was 0.18M, and the rest of the procedure was the same as in the example.
Example 18
The concentration of the perovskite precursor solution in this example was 0.20M, and the rest of the procedure was the same as in the example.
The invention relates to a perovskite luminescent material, in particular to a preparation method of perovskite nanocrystalline with high fluorescence quantum yield. Step 1: preparing perovskite precursor liquid; step 2: synthesizing an SBA-15 template; step 3: the SBA-15 powder and perovskite precursor solution were mixed. Step 4, putting the mixture of SBA-15 and perovskite precursor solution into an ultrasonic cleaning agent for ultrasonic treatment; step 5, separating the mixture of the SBA-15 and the perovskite precursor solution after ultrasonic treatment under a low-pressure atmosphere to obtain a mixture of the perovskite precursor solution filled in the SBA-15 pore canal; step 6: the perovskite precursor solution fills the mixture of SBA-15 pore canals for annealing and crystallization. Step 7: testing of fluorescence quantum yield.
The invention discloses a preparation method of perovskite nanocrystalline with high fluorescence quantum yield, which comprises the steps of introducing organic cation long chains such as BABr, PEABr,4-FPEABr and the like into perovskite precursor solution, and preparing perovskite nanocrystalline with high fluorescence quantum yield by regulating precursor solute components. This will provide a new idea and method for pushing perovskite fluorescent materials towards commercial applications.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (1)
1. The preparation method of the perovskite nanocrystalline with fluorescence quantum yield is characterized by comprising the following steps:
Step 1, mixing SBA-15 powder and perovskite precursor solution to obtain mixed solution C; the SBA-15 is an inert mesoporous template, the solute of the perovskite precursor solution is a mixture of PbBr 2 、CH3NH3 Br and organic cation long-chain substances, and the solvent is DMF; the organic cation long-chain substance is BABr, or PEABr or 4-FPEABr;
the concentration of the perovskite precursor solution is 0.05-0.2M;
the preparation process of the perovskite precursor solution comprises the following steps: according to the molar ratio n: n-1:2, mixing PbBr 2 、CH3NH3 Br and organic cation long-chain substances, wherein n is a natural number of 2-5, forming a mixed solute A, and dissolving the mixed solute A in DMF to obtain a mixed solution B; oscillating the mixed solution B for more than 5 hours, and filtering by an organic filtering membrane to obtain a clear perovskite precursor solution;
The mixing ratio of SBA-15 powder and perovskite precursor solution was 0.05g:300uL;
Step 2, carrying out ultrasonic treatment on the mixed solution C to obtain a mixed solution D;
The ultrasonic time is 10-30 minutes;
Step 3, separating the mixed solution D by a decompression suction filtration method to obtain SBA-15 filled with perovskite precursor solution;
step 4, annealing and crystallizing the SBA-15 filled with the perovskite precursor solution until the mixture is completely discolored from white, and emitting green light under the irradiation of an ultraviolet lamp to generate perovskite nanocrystalline in the SBA-15;
The annealing temperature is 100 ℃;
The preparation method of the SBA-15 powder comprises the following steps: adding P123 into a hydrochloric acid solution, stirring, adding TEOS, continuously stirring to obtain a mixed solution, filtering the mixed solution to obtain a solid product, drying the solid product, re-dispersing the dried solid in a hydrochloric acid-ethanol solution, stirring, filtering, drying the filtered product, and calcining the dried product in air to generate SBA-15 powder;
The mass ratio of the P123 to the hydrochloric acid in the hydrochloric acid solution is 3.46:4.5; p123 was added to the hydrochloric acid solution and stirred at 45 ℃ for 6 hours, and after the addition of TEOS, stirred at 45 ℃ for 24 hours.
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