CN117925230A - Perovskite film with high luminous efficiency and stability and preparation method thereof - Google Patents
Perovskite film with high luminous efficiency and stability and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002096 quantum dot Substances 0.000 claims abstract description 76
- 239000002135 nanosheet Substances 0.000 claims abstract description 43
- 239000011521 glass Substances 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 238000000137 annealing Methods 0.000 claims abstract description 26
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 24
- 238000004528 spin coating Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 13
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- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 74
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 40
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 36
- 239000010408 film Substances 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 239000010409 thin film Substances 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 20
- 235000019260 propionic acid Nutrition 0.000 claims description 20
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 18
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- 239000011159 matrix material Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
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- 229920002223 polystyrene Polymers 0.000 description 2
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- 229910052682 stishovite Inorganic materials 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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Abstract
The invention belongs to the technical field of luminescent materials, and discloses a perovskite film with high luminous efficiency and stability and a preparation method thereof. The method comprises the following steps: and uniformly mixing CsPbBr 3 quantum dots and p-MSB solution to obtain CsPbBr 3 quantum dots/p-MSB nanosheet solution, spin-coating the mixed nanosheet solution on the surface of the treated SiO 2 glass substrate to form a nanosheet film, annealing at 80 ℃, repeating spin-coating and annealing for 3-5 times, and annealing to obtain the perovskite film. According to the invention, the p-MSB and CsPbBr 3 form a type II heterostructure, so that the fluorescence quantum yield is remarkably improved, and the hydrophobic p-MSB is attached to the surface of CsPbBr 3, so that the corrosion of water to CsPbBr 3 quantum dots can be effectively prevented, and excellent humidity stability is obtained.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a perovskite thin film with high luminous efficiency and stability and a preparation method thereof.
Background
In recent years, metal halide perovskite has been used as a luminescent material of a light emitting diode and a gain medium in a semiconductor laser, and is a very promising photoelectric material, by virtue of its extremely high fluorescence quantum yield, a relatively narrow emission bandwidth, excellent exciton binding energy, a large absorption coefficient and the like.
As a typical metal halide perovskite, csPbBr 3 quantum dots can emit green light with extremely high color purity, and the fluorescence quantum yield of CsPbBr 3 quantum dot solution is close to 100%. However, the agglomeration of nanocrystals reduces the fluorescence quantum yield of the CsPbBr 3 quantum dot film to 18%, which is associated with loss of quantum confinement. At the same time, perovskite is often susceptible to humidity due to the low formation energy and the large number of surface traps, which prevents further use of perovskite in underwater environments. Therefore, how to improve the humidity stability of the CsPbBr 3 quantum dot film while maintaining the higher fluorescence quantum yield is still an important subject.
At present, more and more researches try to explore a method capable of effectively improving the stability of CsPbBr 3 quantum dots. One conventional approach is to build a relatively inert shell or barrier matrix over the quantum dots to prevent undesirable attack by moisture. The CsPbBr 3 @CdS core-shell structure effectively improves the stability, but reduces the fluorescence quantum yield. Using SiO 2 as a shell, the fluorescence quantum yield is improved, but the CsPbBr 3@SiO2 surface is porous due to lattice mismatch and still subject to moisture attack. To solve the lattice mismatch problem, a CsPbBr 3 @ CsPbBrx structure was proposed, which successfully improved the fluorescence quantum yield, but the instability of CsPbBr x remains a pending problem. CsPbBr 3 quantum dots can also be filled into crosslinked polystyrene beads, thus exhibiting extraordinary water resistance. However, since an organic matrix such as polystyrene itself cannot emit light, the effective light emitting area is sacrificed, and thus radiation is attenuated.
Through the above analysis, the problems and defects existing in the prior art are as follows: the CsPbBr 3 quantum dot film cannot simultaneously have high fluorescence quantum yield and high stability.
Disclosure of Invention
The invention aims to provide a perovskite film with high luminous efficiency and stability and a preparation method thereof, aiming at the problem that the traditional CsPbBr 3 quantum dot film can not have high fluorescence quantum yield and high stability.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
The first object of the present invention is to provide a method for producing a perovskite thin film having both high luminous efficiency and stability, comprising the steps of: and uniformly mixing the CsPbBr 3 quantum dots and the p-MSB solution to obtain CsPbBr 3 quantum dots/p-MSB nanosheet solution, spin-coating the nanosheet solution on the surface of the treated SiO 2 glass substrate to form a nanosheet film, annealing at 80 ℃, and repeating spin-coating and annealing for 3-5 times to obtain the perovskite film.
Preferably, the CsPbBr 3 quantum dot is prepared according to the following steps:
S1, dissolving PbBr 2 powder in a first solvent to obtain PbBr 2 solution; dissolving Cs 2CO3 powder in propionic acid, and performing ultrasonic treatment to obtain a Cs + precursor solution;
s2, adding the Cs + precursor solution into a second solvent, stirring, injecting the solution into PbBr 2, and centrifuging at 1500r/min and 2000r/min respectively to remove the supernatant to obtain the CsPbBr 3 quantum dot.
Preferably, the mass-volume ratio of the PbBr 2 to the first solvent is 0.9175 g/5 mL, the first solvent is a mixed solution formed by butylamine, isopropanol and propionic acid in a volume ratio of 1:1:1, and the mass-volume ratio of the Cs 2CO3 to the propionic acid is 0.5868 g/1 mL.
Preferably, the volume ratio of the Cs + precursor solution to the second solvent to the PbBr 2 solution is 25 mu L, 15mL is 0.27mL, and the second solvent is a mixed solution formed by isopropanol and n-hexane in a volume ratio of 1:2.
Preferably, the mass-volume ratio of PbBr 2 and p-MSB solution in the CsPbBr 3 quantum dot is 0.9175g:8mL.
Preferably, the p-MSB solution is p-MSB toluene solution, and the concentration of the p-MSB is 0.025-2mg/mL.
Preferably, the volume of the nano-sheet solution spin-coating is 120-200 mu L.
Preferably, the spin coating method is to rotate the nano-sheet solution at 500r/min for 20s on the SiO 2 glass substrate, then continue to rotate at 2000r/min for 40s, the annealing time is 1min, and the final annealing time is 5min.
Preferably, the SiO 2 glass substrate is processed in the following manner: firstly removing oil stains on the surface of SiO 2 glass by using a cleaning agent, then sequentially carrying out ultrasonic treatment by using water, ethanol and acetone for 10min, and finally drying by using nitrogen for later use.
The second object of the present invention is to provide a perovskite thin film having both high luminous efficiency and stability, which is prepared by the above-mentioned preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) The perovskite film with high luminous efficiency and stability is provided by the invention, the zero-dimensional-two-dimensional CsPbBr 3 quantum dot/p-MSB nanosheet film has higher fluorescence quantum yield and excellent humidity stability, the p-MSB and CsPbBr 3 form a typical II-type heterostructure, the electron migration rate of the p-MSB is far greater than the hole migration rate of CsPbBr 3, and the radiation recombination of a large number of extra electrons transferred to CsPbBr 3,CsPbBr3 is enhanced, so that the fluorescence quantum yield is remarkably improved. Meanwhile, the hydrophobic p-MSB is attached to the surface of the CsPbBr 3, so that a firm barrier is formed, and the corrosion of moisture to CsPbBr 3 quantum dots can be effectively prevented, so that excellent humidity stability is obtained.
(2) The perovskite thin film with high luminous efficiency and stability provided by the invention has the advantages of simple manufacturing process and strong repeatability; can be prepared in air environment.
Drawings
FIG. 1 is a flow chart of a perovskite thin film process of the invention having both high luminous efficiency and stability;
FIG. 2 is a normalized photoluminescence spectrum of perovskite thin films prepared by examples 1 to 6 and comparative example 1 of the invention;
FIG. 3 is a graph showing the change in fluorescence quantum yield of perovskite thin films of examples 1 to 6 and comparative example 1 according to the present invention;
FIG. 4 shows the photoluminescent intensity variation at 30%, 75% and 84% relative humidity of the perovskite thin films as prepared by example 2 and comparative example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the data in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that the technical terms used in the present invention are only for describing specific examples, and are not intended to limit the scope of the present invention, and various raw materials, reagents, instruments and equipment used in the following examples of the present invention are commercially available or prepared by the existing method, and the p-MSB used in the present invention is 1, 4-bis (4-methylstyrene) benzene, unless otherwise specifically indicated.
Example 1
A preparation method of a perovskite film with high luminous efficiency and stability comprises the following steps:
s1, cleaning a SiO 2 glass substrate: cleaning oil stains on the surface of SiO 2 glass by using detergent, sequentially carrying out ultrasonic treatment by using deionized water, ethanol and acetone for 10min, and finally drying by using nitrogen for later use;
S2, preparing CsPbBr 3 quantum dots: 0.9175g of PbBr 2 powder is dissolved in 5mL of a mixed solution of butylamine, isopropanol and propionic acid with the volume ratio of 1:1:1, so as to obtain a PbBr 2 solution; 0.5868g of Cs 2CO3 powder is dissolved in 1mL of propionic acid, and then is subjected to ultrasonic treatment to obtain a Cs + precursor solution;
Injecting 25 mu L of Cs + precursor into a mixture of 5mL of isopropanol and 10mL of n-hexane, vigorously stirring for 2min, rapidly injecting 0.27mL of PbBr 2 solution into the mixture, respectively centrifuging for two minutes at the rotating speeds of 1500r/min and 2000r/min, and removing the supernatant to obtain the CsPbBr 3 quantum dot;
S3, preparing CsPbBr 3 quantum dot/p-MSB nano sheet solution: the synthesized CsPbBr 3 quantum dot is dissolved in p-MSB toluene solution with the concentration of 8mLp-MSB of 2 mg/mL;
S4, preparing a CsPbBr 3 quantum dot/p-MSB nano sheet film: placing a glass substrate on a spin coater, dripping the mixed CsPbBr 3 quantum dot/p-MSB nanosheet solution on the surface of the glass substrate, rotating for 20s at a rotating speed of 500r/min, then rotating for 40s at 2000r/min, annealing for 1min at 80 ℃ after spin coating is finished, repeating the steps for 3 times, and annealing for 5min at 80 ℃ after the last spin coating is finished.
The CsPbBr 3 quantum dot/p-MSB nano sheet film prepared in example 1 is tested, the excitation wavelength is 350nm, and the result shows that the fluorescence quantum yield is 38.82%.
Example 2
A preparation method of a perovskite film with high luminous efficiency and stability comprises the following steps:
s1, cleaning a SiO 2 glass substrate: cleaning oil stains on the surface of SiO 2 glass by using detergent, sequentially carrying out ultrasonic treatment by using deionized water, ethanol and acetone for 10min, and finally drying by using nitrogen for later use;
S2, preparing CsPbBr 3 quantum dots: 0.9175g PbBr 2 powder was dissolved in 5mL volume ratio of 1:1:1, mixing butylamine, isopropanol and propionic acid to obtain PbBr 2 solution; 0.5868g of Cs 2CO3 powder is dissolved in 1mL of propionic acid, and then is subjected to ultrasonic treatment to obtain a Cs + precursor solution;
Injecting 25 mu L of Cs + precursor into a mixture of 5mL of isopropanol and 10mL of n-hexane, vigorously stirring for 2min, rapidly injecting 0.27mL of PbBr 2 solution into the mixture, respectively centrifuging for two minutes at the rotating speeds of 1500r/min and 2000r/min, and removing the supernatant to obtain the CsPbBr 3 quantum dot;
S3, preparing CsPbBr3 quantum dot/p-MSB nano sheet solution: the synthesized CsPbBr 3 quantum dot is dissolved in 8 mLp-p-MSB toluene solution with the MSB concentration of 1 mg/mL;
S4, preparing a CsPbBr 3 quantum dot/p-MSB nano sheet film: placing a glass substrate on a spin coater, dripping the mixed CsPbBr 3 quantum dot/p-MSB nanosheet solution on the surface of the glass substrate, rotating for 20s at a rotating speed of 500r/min, then rotating for 40s at 2000r/min, annealing for 1min at 80 ℃ after spin coating is finished, repeating the steps for 3 times, and annealing for 5min at 80 ℃ after the last spin coating is finished.
The CsPbBr 3 quantum dot/p-MSB nano sheet film prepared in example 2 is tested, the excitation wavelength is 350nm, and the result shows that the fluorescence quantum yield is 39.79%.
Example 3
A preparation method of a perovskite film with high luminous efficiency and stability comprises the following steps:
s1, cleaning a SiO 2 glass substrate: cleaning oil stains on the surface of SiO 2 glass by using detergent, sequentially carrying out ultrasonic treatment by using deionized water, ethanol and acetone for 10min, and finally drying by using nitrogen for later use;
S2, preparing CsPbBr 3 quantum dots: 0.9175g PbBr 2 powder was dissolved in 5mL volume ratio of 1:1:1, mixing butylamine, isopropanol and propionic acid to obtain PbBr 2 solution; 0.5868g of Cs 2CO3 powder is dissolved in 1mL of propionic acid, and then is subjected to ultrasonic treatment to obtain a Cs + precursor solution;
Injecting 25 mu L of Cs + precursor into a mixture of 5mL of isopropanol and 10mL of n-hexane, vigorously stirring for 2min, rapidly injecting 0.27mL of PbBr 2 solution into the mixture, respectively centrifuging for two minutes at the rotating speeds of 1500r/min and 2000r/min, and removing the supernatant to obtain the CsPbBr 3 quantum dot;
S3, preparing CsPbBr 3 quantum dot/p-MSB nano sheet solution: the synthesized CsPbBr 3 quantum dot is dissolved in p-MSB toluene solution with the concentration of 8mLp-MSB of 0.5 mg/mL;
S4, preparing a CsPbBr 3 quantum dot/p-MSB nano sheet film: placing a glass substrate on a spin coater, dripping the mixed CsPbBr 3 quantum dot/p-MSB nanosheet solution on the surface of the glass substrate, rotating for 20s at a rotating speed of 500r/min, then rotating for 40s at 2000r/min, annealing for 1min at 80 ℃ after spin coating is finished, repeating the steps for 3 times, and annealing for 5min at 80 ℃ after the last spin coating is finished.
The CsPbBr 3 quantum dot/p-MSB nano-sheet film prepared in example 3 is tested, the excitation wavelength is 350nm, and the result shows that the fluorescence quantum yield is 29.68%.
Example 4
A preparation method of a perovskite film with high luminous efficiency and stability comprises the following steps:
s1, cleaning a SiO 2 glass substrate: cleaning oil stains on the surface of SiO 2 glass by using detergent, sequentially carrying out ultrasonic treatment by using deionized water, ethanol and acetone for 10min, and finally drying by using nitrogen for later use;
S2, preparing CsPbBr 3 quantum dots: 0.9175g PbBr 2 powder was dissolved in 5mL volume ratio of 1:1:1, mixing butylamine, isopropanol and propionic acid to obtain PbBr 2 solution; 0.5868g of Cs 2CO3 powder is dissolved in 1mL of propionic acid, and then is subjected to ultrasonic treatment to obtain a Cs + precursor solution;
Injecting 25 mu L of Cs + precursor into a mixture of 5mL of isopropanol and 10mL of n-hexane, vigorously stirring for 2min, rapidly injecting 0.27mL of PbBr 2 solution into the mixture, respectively centrifuging for two minutes at the rotating speeds of 1500r/min and 2000r/min, and removing the supernatant to obtain the CsPbBr 3 quantum dot;
S3, preparing CsPbBr 3 quantum dot/p-MSB nano sheet solution: the synthesized CsPbBr 3 quantum dot is dissolved in p-MSB toluene solution with the concentration of 8mLp-MSB of 0.1 mg/mL;
S4, preparing a CsPbBr 3 quantum dot/p-MSB nano sheet film: placing a glass substrate on a spin coater, dripping the mixed CsPbBr 3 quantum dot/p-MSB nanosheet solution on the surface of the glass substrate, rotating for 20s at a rotating speed of 500r/min, then rotating for 40s at 2000r/min, annealing for 1min at 80 ℃ after spin coating is finished, repeating the steps for 3 times, and annealing for 5min at 80 ℃ after the last spin coating is finished.
The CsPbBr 3 quantum dot/p-MSB nanosheet film prepared in example 4 was tested, and the excitation wavelength was 350nm, which showed a fluorescence quantum yield of 27.82%.
Example 5
A preparation method of a perovskite film with high luminous efficiency and stability comprises the following steps:
s1, cleaning a SiO 2 glass substrate: cleaning oil stains on the surface of SiO 2 glass by using detergent, sequentially carrying out ultrasonic treatment by using deionized water, ethanol and acetone for 10min, and finally drying by using nitrogen for later use;
S2, preparing CsPbBr 3 quantum dots: 0.9175g PbBr 2 powder was dissolved in 5mL volume ratio of 1:1:1, mixing butylamine, isopropanol and propionic acid to obtain PbBr 2 solution; 0.5868g of Cs 2CO3 powder is dissolved in 1mL of propionic acid, and then is subjected to ultrasonic treatment to obtain a Cs + precursor solution;
Injecting 25 mu L of Cs + precursor into a mixture of 5mL of isopropanol and 10mL of n-hexane, vigorously stirring for 2min, rapidly injecting 0.27mL of PbBr 2 solution into the mixture, respectively centrifuging for two minutes at the rotating speeds of 1500r/min and 2000r/min, and removing the supernatant to obtain the CsPbBr 3 quantum dot;
S3, preparing CsPbBr 3 quantum dot/p-MSB nano sheet solution: the synthesized CsPbBr 3 quantum dot is dissolved in p-MSB toluene solution with the concentration of 8mLp-MSB of 0.05 mg/mL;
S4, preparing a CsPbBr 3 quantum dot/p-MSB nano sheet film: placing a glass substrate on a spin coater, dripping the mixed CsPbBr 3 quantum dot/p-MSB nanosheet solution on the surface of the glass substrate, rotating for 20s at a rotating speed of 500r/min, then rotating for 40s at 2000r/min, annealing for 1min at 80 ℃ after spin coating is finished, repeating the steps for 3 times, and annealing for 5min at 80 ℃ after the last spin coating is finished.
The CsPbBr 3 quantum dot/p-MSB nanosheet film prepared in example 5 is tested, the excitation wavelength is 350nm, and the result shows that the fluorescence quantum yield is 24.40%.
Example 6
A preparation method of a perovskite film with high luminous efficiency and stability comprises the following steps:
s1, cleaning a SiO 2 glass substrate: cleaning oil stains on the surface of SiO 2 glass by using detergent, sequentially carrying out ultrasonic treatment by using deionized water, ethanol and acetone for 10min, and finally drying by using nitrogen for later use;
S2, preparing CsPbBr 3 quantum dots: 0.9175g PbBr 2 powder was dissolved in 5mL volume ratio of 1:1:1, mixing butylamine, isopropanol and propionic acid to obtain PbBr 2 solution; 0.5868g of Cs 2CO3 powder is dissolved in 1mL of propionic acid, and then is subjected to ultrasonic treatment to obtain a Cs + precursor solution;
Injecting 25 mu L of Cs + precursor into a mixture of 5mL of isopropanol and 10mL of n-hexane, vigorously stirring for 2min, rapidly injecting 0.27mL of PbBr 2 solution into the mixture, respectively centrifuging for two minutes at the rotating speeds of 1500r/min and 2000r/min, and removing the supernatant to obtain the CsPbBr 3 quantum dot;
s3, preparing CsPbBr 3 quantum dot/p-MSB nano sheet solution: the synthesized CsPbBr 3 quantum dot is dissolved in p-MSB toluene solution with the concentration of 8mLp-MSB of 0.025 mg/mL;
S4, preparing a CsPbBr 3 quantum dot/p-MSB nano sheet film: placing a glass substrate on a spin coater, dripping the mixed CsPbBr 3 quantum dot/p-MSB nanosheet solution on the surface of the glass substrate, rotating for 20s at a rotating speed of 500r/min, then rotating for 40s at 2000r/min, annealing for 1min at 80 ℃ after spin coating is finished, repeating the steps for 3 times, and annealing for 5min at 80 ℃ after the last spin coating is finished.
The CsPbBr 3 quantum dot/p-MSB nano sheet film prepared in example 6 is tested, the excitation wavelength is 350nm, and the result shows that the fluorescence quantum yield is 23.55%.
Comparative example 1
A method for preparing a perovskite thin film, comprising the following steps:
s1, cleaning a SiO 2 glass substrate: cleaning oil stains on the surface of SiO 2 glass by using detergent, sequentially carrying out ultrasonic treatment by using deionized water, ethanol and acetone for 10min, and finally drying by using nitrogen for later use;
S2, preparing CsPbBr 3 quantum dots: 0.9175g PbBr 2 powder was dissolved in 5mL volume ratio of 1:1:1, mixing butylamine, isopropanol and propionic acid to obtain PbBr 2 solution; 0.5868g of Cs 2CO3 powder is dissolved in 1mL of propionic acid, and then is subjected to ultrasonic treatment to obtain a Cs + precursor solution;
Injecting 25 mu L of Cs + precursor into a mixture of 5mL of isopropanol and 10mL of n-hexane, vigorously stirring for 2min, rapidly injecting 0.27mL of PbBr 2 solution into the mixture, respectively centrifuging for two minutes at the rotating speeds of 1500r/min and 2000r/min, and removing the supernatant to obtain the CsPbBr 3 quantum dot;
S3, preparing CsPbBr 3 quantum dot/p-MSB nano sheet solution: the synthesized CsPbBr 3 quantum dot is dissolved in p-MSB toluene solution with the concentration of 8mLp-MSB of 0 mg/mL;
S4, preparing a CsPbBr 3 quantum dot/p-MSB nano sheet film: placing a glass substrate on a spin coater, dripping the mixed CsPbBr 3 quantum dot/p-MSB nanosheet solution on the surface of the glass substrate, rotating for 20s at a rotating speed of 500r/min, then rotating for 40s at 2000r/min, annealing for 1min at 80 ℃ after spin coating is finished, repeating the steps for 3 times, and annealing for 5min at 80 ℃ after the last spin coating is finished.
The CsPbBr 3 quantum dot/p-MSB nano sheet film prepared in comparative example 1 is tested, the excitation wavelength is 350nm, and the result shows that the fluorescence quantum yield is 18.58%.
The perovskite thin films prepared in examples 1 to 6 and comparative example 1 were tested for luminous efficiency and stability properties.
FIG. 2 is a graph of normalized fluorescence emission spectra (PL) of perovskite thin films prepared in example 2 and comparative example 1 of the present invention. As shown in FIG. 2, the PL intensity was higher when doped with 1mg/mLp-MSB (example 2) than when undoped with p-MSB (comparative example 1) at an annealing temperature of 80 ℃.
FIG. 3 shows the variation of the fluorescence quantum yield (PLQY) of perovskite thin films prepared according to examples 1 to 6 and comparative example 1 of the present invention. As shown in FIG. 3, the fluorescence quantum yield (PLQY) of the p-MSB doped quantum dot film (comparative example 1) was 23.55%, PLQY increased with increasing p-MSB doping concentration, PLQY increased by up to 39.79% when doped with 1mg/mL of p-MSB toluene solution (example 2), and increased by two times compared to undoped (comparative example 1). As the doping concentration was further increased (example 1), PLQY decreased. Indicating that 1mg/mL is the optimal doping concentration.
After the perovskite thin film prepared in example 2 is placed in an atmospheric environment for 1 month, PL is hardly attenuated, which indicates that the CsPbBr 3 quantum dot/p-MSB nano sheet thin film prepared in the invention has excellent time stability.
The films prepared in example 2 and comparative example 1 were exposed to environments having relative humidities of 30%, 75% and 84%, respectively, for 12 hours, and their PL intensity changes are shown in fig. 4, and fig. 4 shows the photoluminescence intensity changes at relative humidities of 30%, 75% and 84% for the perovskite films prepared in example 2 and comparative example 1 according to the present invention. As shown in fig. 4, the CsPbBr 3 quantum dot/p-MSB nanoplatelet film (example 2) produced by doping 1mg/mL of p-MSB toluene solution has excellent humidity stability compared to the undoped p-MSB (comparative example 1).
It should be noted that, when numerical ranges are referred to in the present invention, it should be understood that two endpoints of each numerical range and any numerical value between the two endpoints are optional, and because the adopted step method is the same as the embodiment, in order to prevent redundancy, the present invention describes a preferred embodiment. While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. The preparation method of the perovskite thin film with high luminous efficiency and stability is characterized by comprising the following steps: and uniformly mixing the CsPbBr 3 quantum dots and the p-MSB solution to obtain CsPbBr 3 quantum dots/p-MSB nanosheet solution, spin-coating the nanosheet solution on the surface of the treated SiO 2 glass substrate to form a nanosheet film, annealing at 80 ℃, and repeating spin-coating and annealing for 3-5 times to obtain the perovskite film.
2. The preparation method of the perovskite thin film with high luminous efficiency and stability according to claim 1, wherein the CsPbBr 3 quantum dots are prepared according to the following steps:
S1, dissolving PbBr 2 powder in a first solvent to obtain PbBr 2 solution; dissolving Cs 2CO3 powder in propionic acid, and performing ultrasonic treatment to obtain a Cs + precursor solution;
s2, adding the Cs + precursor solution into a second solvent, stirring, injecting the solution into PbBr 2, and centrifuging at 1500r/min and 2000r/min respectively to remove the supernatant to obtain the CsPbBr 3 quantum dot.
3. The method for preparing a perovskite thin film having both high luminous efficiency and high stability according to claim 2, wherein the mass-volume ratio of PbBr 2 to the first solvent is 0.9175 g/5 ml, the first solvent is a mixed solution of butylamine, isopropanol and propionic acid in a volume ratio of 1:1:1, and the mass-volume ratio of Cs 2CO3 to propionic acid is 0.5868 g/1 ml.
4. The method for producing a perovskite thin film having both high light-emitting efficiency and stability according to claim 3, wherein the volume ratio of the Cs + precursor solution, the second solvent and the PbBr 2 solution is 25 μl:15ml:0.27ml, and the second solvent is a mixed solution of isopropanol and n-hexane in a volume ratio of 1:2.
5. The method for preparing a perovskite thin film having both high luminous efficiency and high stability according to claim 4, wherein the mass-volume ratio of PbBr 2 and p-MSB solution in the CsPbBr 3 quantum dot is 0.9175g:8mL.
6. The method for producing a perovskite thin film having both high luminous efficiency and stability as claimed in claim 5, wherein said p-MSB solution is p-MSB toluene solution, and the concentration of p-MSB is 0.025-2mg/mL.
7. The method for preparing a perovskite thin film having both high luminous efficiency and stability according to claim 1, wherein the volume of the nanosheet solution spin-coating is 120-200 μl.
8. The method for preparing a perovskite thin film with high luminous efficiency and stability according to claim 1, wherein the spin coating method is to continuously rotate a nano-sheet solution at 500r/min for 40s after a SiO 2 glass substrate rotates for 20s instead of 2000r/min, the annealing time is 1min, and the final annealing time is 5min.
9. The method for preparing a perovskite thin film with high luminous efficiency and stability according to claim 1, wherein the treatment mode of the SiO 2 glass substrate is as follows: firstly removing oil stains on the surface of SiO 2 glass by using a cleaning agent, then sequentially carrying out ultrasonic treatment by using water, ethanol and acetone for 10min, and finally drying by using nitrogen for later use.
10. A perovskite thin film having both high luminous efficiency and stability, prepared by the preparation method as claimed in any one of claims 1 to 9.
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| KR20130111483A (en) * | 2012-03-30 | 2013-10-10 | 주식회사 엘지화학 | Organic light emitting device |
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