CN115521561B - Ligand modified high-stability MAPbBr 3 Perovskite quantum dot@polymer optical film - Google Patents
Ligand modified high-stability MAPbBr 3 Perovskite quantum dot@polymer optical film Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 63
- 239000012788 optical film Substances 0.000 title claims abstract description 40
- 239000003446 ligand Substances 0.000 title claims abstract description 34
- 229920000642 polymer Polymers 0.000 title claims abstract description 26
- KISZTEOELCMZPY-UHFFFAOYSA-N 3,3-diphenylpropylamine Chemical compound C=1C=CC=CC=1C(CCN)C1=CC=CC=C1 KISZTEOELCMZPY-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000010408 film Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- GIDDQKKGAYONOU-UHFFFAOYSA-N octylazanium;bromide Chemical compound Br.CCCCCCCCN GIDDQKKGAYONOU-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 238000004020 luminiscence type Methods 0.000 claims description 6
- 239000005357 flat glass Substances 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000003517 fume Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000009423 ventilation Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 238000002791 soaking Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 238000007792 addition Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- -1 n-octylamine bromine Chemical compound 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005424 photoluminescence Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000005538 encapsulation Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- C08J5/18—Manufacture of films or sheets
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
The invention relates to a ligand modified high-stability MAPbBr 3 Perovskite quantum dot@polymer optical film belongs to optical film technical field. The invention discloses a ligand modified high-stability MAPbBr 3 Perovskite quantum dot @ polymer optical film, the highly stable MAPbBr 3 Perovskite quantum dot @ polymer optical films were ligand modified by adding 3, 3-Diphenylpropylamine (DPPA), n-Xin Anxiu (OABr) to the precursor solution.
Description
Technical Field
The invention belongs to the technical field of optical films, and relates to a ligand modified high-stability MAPbBr 3 Perovskite quantum dot @ polymer optical film.
Background
The perovskite quantum dot has the advantages of high quantum efficiency, accurate and controllable fluorescence color, narrow half-peak width of a luminescence spectrum, good solution processing characteristics and the like, and has wide application prospect in liquid crystal backlight application. The organic-inorganic hybrid perovskite quantum dots combine the synthesis capability of organic molecules and the excellent photoelectric performance of inorganic solid materials, but the ionic nature of the crystal structure enables the organic-inorganic hybrid perovskite quantum dot film to be easily damaged in water, heat and other environments, and inherent instability becomes the biggest obstacle for the practical application of the organic-inorganic hybrid perovskite quantum dot film. In particular, perovskite quantum dot thin film devices typically operate at high temperatures, and thermal stability is an unavoidable issue for practical applications. Poor thermal stability will lead to thermal quenching of the perovskite quantum dot emitter and even to decomposition of the perovskite quantum dots and loss of part of the organic components at high temperatures, leading to rapid degradation of device performance. Thus, there is a need for improved stability in the environment by specific techniques.
And the current perovskite quantum dot film device generally adopts polymer to wrap perovskite quantum dots, and the MAPbBr is disclosed in document 1 (Advanced Materials,2016,28 (41): 9163-9168.) 3 The PVDF composite film has 94.6% of PL QY in the green light wave band, but the composite film has no ligand modification, so that the surface ligand of the quantum dot is easy to fall off and easily agglomerate and regrow at high temperature, and the optical performance is rapidly deteriorated. Researchers have therefore begun to prepare red-emitting MAPbI using the addition of 3, 3-diphenylpropylamine as a precursor solubility modulator, as in document 2 (nanoscales, 2019, 11:4942-4947) 3 When DPPA is added, MAI and PbI are reduced 2 Solubility difference of (2) and increase compatibility between polymer and precursor, realizes MAPbI with PL QY as high as 91% 3 Preparing red film quantum dots; chinese patent application texts (publication No. CN114525129A, CN114479560A, CN114437710A, CN 110387227A) all disclose that the prepared film has better performance by adopting 3, 3-diphenylpropylamine as an amine ligand; chinese patent application text (publication No. CN 110387227A) uses octylamine bromide and/or brominated 3, 3-diphenylpropylamine as amine ligands,the brominated 3, 3-diphenylpropylamine is adopted, and the film has good stability in air by combining amine with Pb ions exposed on the surface; and after the quantum dot film is prepared, adding a ligand to passivate the surface of the quantum dot film.
Disclosure of Invention
The present invention has been made in view of the above problems occurring in the prior art, and it is an object of the present invention to provide ligand-modified highly stable MAPbBr having both thermal and water stability 3 Perovskite quantum dot @ polymer optical film.
The aim of the invention can be achieved by the following technical scheme:
ligand modified high-stability MAPbBr 3 Perovskite quantum dot @ polymer optical film, the highly stable MAPbBr 3 Perovskite quantum dot @ polymer optical films were ligand modified by adding 3, 3-Diphenylpropylamine (DPPA), n-Xin Anxiu (OABr) to the precursor solution.
The 3, 3-diphenylpropylamine added in the invention can be used as an organic amine ligand to passivate MAPbBr 3 The surface defect of the quantum dot simultaneously inhibits the performance degradation caused by the agglomeration and regrowth of the quantum dot at high temperature due to the large steric hindrance, thereby greatly improving MAPbBr 3 Photoluminescent quantum efficiency and thermal stability of the quantum dot optical film. And the n-octylamine bromine ligand is used for assisting in modification, and bromine ions are used for passivating halogen vacancies on the surface of the quantum dot, so that MAPbBr is greatly improved 3 Thermal stability of quantum dot optical films. According to the invention, 3-diphenylpropylamine and n-octylamine bromine are added simultaneously to carry out ligand modification, and the surface halogen vacancies, other passivation for coordination ions and the space isolation among quantum dots are properly and cooperatively realized by adjusting the proportion of the 3, 3-diphenylpropylamine and n-octylamine bromine, so that the quantum dot fluorescent lamp has higher luminous quantum efficiency and better stability.
Preferably, the mass ratio of the 3, 3-diphenylpropylamine to the n-octylamine bromide is (1-50): 1.
further preferably, the mass ratio of the 3, 3-diphenylpropylamine to the n-octylamine bromide is (7-35): 1.
preferably, the 3, 3-diphenylpropylamine is added to the precursor solution in an amount of 0.5-3.5mg/100ml.
Preferably, the precursor solution comprises the following components in percentage by mass (10-20): (50-70): MABr (methyl Ammonia bromide), pbBr of 1 2 、PVDF。
Preferably, the mass of the 3, 3-diphenylpropylamine and n-octylamine bromine is PbBr in the precursor respectively 2 10-50% and 1-5% of the weight of the composition.
The content of the ligand in the precursor solution needs to be controlled, and if too much ligand causes the luminescence peak position to deviate from the application optimum value (530-540 nm) and half-width to become wider (causing negative influence of lowering color purity), too little results in poor performance improvement effect.
Preferably, the mixed solution modified by the ligand is subjected to ultrasonic treatment, centrifugal defoaming, filtering and dripping on the surface of the flat glass, and a transparent precursor layer is formed by a blade knife coating technology.
Preferably, the rotational speed of the centrifugal defoaming process is 4000-7000rpm, and the time is 1-5 minutes.
Preferably, the filtration process uses a microporous membrane filter with a pore size of 0.22 μm or less.
Preferably, the blade coating is performed on a plate glass, and the thickness of the transparent coating obtained after the blade coating is 100-500 μm.
Preferably, the transparent precursor layer is also required to be dried.
Preferably, the drying process comprises vacuumizing and ventilating at normal temperature.
Further preferably, the vacuuming process vacuumizes at 20-50 ℃ for 3-8 minutes.
The purpose of the vacuum pumping is to accelerate the volatilization of the solvent and form a film.
Further preferably, the ambient temperature ventilation is allowed to stand in a fume hood for 24-48 hours.
The purpose of normal temperature ventilation and standing is to wait for quantum dot formation, and too short a time leads to less formed quantum dots.
Preferably, the highly stable MAPbBr 3 The thickness of the perovskite quantum dot@polymer optical film is 5-100 μm; the particle size of the quantum dots is 8-12nm; the luminescence peak position is adjustable at 525-540 nm.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the passivation of surface halogen vacancies and other position coordination ions and the space isolation among quantum dots are cooperatively realized by controlling the addition amount and the proportion of 3, 3-diphenylpropylamine and n-octylamine bromide, so that the prepared optical film keeps a better application value at the luminescence peak position, and has higher luminescence quantum efficiency and better stability.
2. The invention can passivate MAPbBr by adding 3, 3-diphenylpropylamine ligand for modification 3 The surface defect of the quantum dot simultaneously inhibits the performance degradation caused by the agglomeration and regrowth of the quantum dot at high temperature due to the large steric hindrance, thereby greatly improving MAPbBr 3 Photoluminescent quantum efficiency and thermal stability of the quantum dot optical film.
3. The invention greatly improves MAPbBr by adding n-octylamine bromine ligand for modification 3 Thermal stability of quantum dot optical films.
4. MAPbBr prepared by the invention 3 The quantum dot optical film has better heat stability and water stability, and can still keep more than 75% of the original photoluminescence quantum efficiency after being continuously heated on a hot plate at 60 ℃ for 7 days; the product can keep 80% of the original photoluminescence quantum efficiency after being soaked in water for 7 days.
5. The invention has the advantages of easily obtained raw materials and simple and controllable preparation process.
Drawings
FIG. 1 shows MAPbBr prepared in example 1 of the present invention 3 Quantum dot optical thin film scanning Transmission Electron Microscopy (TEM) images.
FIG. 2 shows MAPbBr prepared in example 1 of the present invention 3 Quantum dot optical thin film Scanning Electron Microscope (SEM) images.
FIG. 3 shows MAPbBr prepared in comparative example 2 and examples 1 to 4 according to the present invention 3 Thermal stability diagram of quantum dot optical film.
FIG. 4 shows MAPbBr prepared in example 1, comparative example 1 and comparative example 5 of the present invention 3 Water stability profile of quantum dot optical films.
FIG. 5 shows the present inventionMAPbBr prepared in Ming comparative examples 3-6 3 Thermal stability diagram of quantum dot optical film.
FIG. 6 shows MAPbBr prepared in example 1, comparative examples 3-6 of the present invention 3 Photoluminescence quantum efficiency map of quantum dot optical films.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described, but the present invention is not limited to these examples.
Example 1
57.3mg MABr, 220.2mg PbBr 2 4.2g PVDF was added to 30mL DMF solvent and stirred for 12 hours to prepare a precursor solution. 76.1mg of 3, 3-diphenylpropylamine (DPPA: pbBr at this time) 2 The molar ratio of (2) is 0.6:1, noted 0.6DPPA, supra), 7.6mg of positive Xin Anxiu (OABr at this time: pbBr 2 The molar ratio of (2) is 0.06:1, noted as 0.06OABr, the same applies below) was added to the precursor solution, mixed well and sonicated for 2 hours, followed by centrifugation at 5000rpm for 3 minutes. The solution was then filtered using a microporous membrane filter with a pore size of 0.22 μm to obtain a transparent and uniform solution. The precursor solution was dropped onto the surface of a plate glass, and a transparent precursor layer having a uniform thickness of 200 μm was formed by a blade coating technique. Vacuum-pumping the plate glass with the precursor coating at 30 ℃ for 5 minutes to volatilize the solvent to form MAPbBr 3 A film. The film was then placed in a chemical fume hood for 24 hours to give a film thickness of 8 μm, a luminescence peak position of 525nm and a half-width of 28nm.
FIG. 1 is MAPbBr 3 High resolution transmission electron microscopy of quantum dot optical films shows a compact arrangement of quantum dots with an average diameter of about 10nm. FIG. 2 shows MAPbBr 3 The back-scattered SEM image of the quantum dot optical film shows that the quantum dots are well dispersed in the polymer.
Then, performing performance test on the prepared film; FIG. 3 is a graph showing the thermal stability of the resulting film, after heating on a hot plate at 60℃for 7 days, the performance is reduced by only 22.1%; FIG. 4 is a graph showing the water stability of the resulting film, which was immersed in water for 7 days, and the performance was reduced by 18.7% after immersion.
Example 2
The difference compared with example 1 is that the amount of n-octylamine bromide added is 2.5mg (0.02 OABr). Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 27.6% after heating; the performance is reduced by 16.9% after soaking in water for 7 days continuously.
Example 3
The difference compared with example 1 is that the amount of n-octylamine bromide added is 5.0mg (0.04 OABr). Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 25.4% after heating; the performance is reduced by 18.9% after soaking in water for 7 days continuously.
Example 4
The difference compared with example 1 is that the amount of n-octylamine bromide added is 10mg (0.08 OABr). Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 28.9% after heating; the performance is reduced by 17.2% after soaking in water for 7 days continuously.
Example 5
The difference compared with example 1 is that the amount of n-octylamine bromide added is 2mg. Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 44.1% after heating; the performance is reduced by 24.2% after soaking in water for 7 days continuously.
Example 6
The difference compared with example 1 is that the amount of n-octylamine bromide added is 12mg. Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 48.6% after heating; the performance is reduced by 19.2% after soaking in water for 7 days continuously.
Example 7
The difference compared to example 1 is that the amount of 3, 3-diphenylpropylamine added is 25.36mg (0.2 DPPA). Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 29.5% after heating; the performance is reduced by 17.9% after soaking in water for 7 days continuously.
Example 8
The difference compared to example 1 is that the amount of 3, 3-diphenylpropylamine added is 50.7mg (0.4 DPPA). Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 26.8% after heating; the performance is reduced by 18.2% after soaking in water for 7 days continuously.
Example 9
The difference compared to example 1 is that the amount of 3, 3-diphenylpropylamine added is 101.4mg (0.8 DPPA). Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 29.9% after heating; the performance is reduced by 18.5% after soaking in water for 7 days continuously.
Example 10
The difference compared to example 1 is that a transparent precursor layer having a uniform thickness of 1000 μm is formed by the blade coating technique. Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 29.7% after heating; the performance is reduced by 16.8% after soaking in water for 7 days continuously. The thicker film enables the quantum dots to be better coated in the polymer, and has better stability; however, in the application of the liquid crystal display backlight source, the too thick quantum dot film can cause the green light proportion to be too high, so that the color coordinates of the panel are difficult to meet the commercial requirement.
Example 11
The difference compared to example 1 is that the film is placed in a chemical fume hood for 12 hours. Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 31.4 percent after heating; the performance is reduced by 18.7% after soaking in water for 7 days continuously.
Comparative example 1
In comparison with example 1, the difference is that 3, 3-diphenylpropylamine and n-octylamine bromide are not added. Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 93.2% after heating; the performance is reduced by 31.7 percent after the continuous soaking in water for 7 days; PL QY was 42.1%.
Comparative example 2
In comparison with example 1, the difference is that n-octylamine bromide is not added. Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 56.2% after heating; the performance is reduced by 24.2 percent after the continuous soaking in water for 7 days; PL QY was 65.1%.
Comparative example 3
The difference compared to example 1 is that only 25.36mg of 3, 3-diphenylpropylamine (0.2 DPPA) was added to the precursor solution. Fig. 5 is a thermal stability diagram of the fabricated quantum dot optical film, and fig. 6 is a photoluminescence quantum efficiency diagram of the fabricated quantum dot optical film. Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 61% after heating; the performance is reduced by 27.2 percent after the continuous soaking in water for 7 days; PL QY was 47%.
Comparative example 4
The difference compared to example 1 is that only 50.7mg of 3, 3-diphenylpropylamine (0.4 DPPA) was added to the precursor solution. Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 59.3% after heating; the performance is reduced by 25.0% after the continuous soaking in water for 7 days; PL QY was 60.6%.
Comparative example 5
The difference compared to example 1 is that only 76.1mg of 3, 3-diphenylpropylamine (0.6 DPPA) was added to the precursor solution. Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 56.2% after heating; the performance is reduced by 24.2 percent after the continuous soaking in water for 7 days; PL QY was 65.1%.
Comparative example 6
The difference compared to example 1 is that only 101.4mg of 3, 3-diphenylpropylamine (0.8 DPPA) was added to the precursor solution. Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 57.7% after heating; the performance is reduced by 26.4 percent after the continuous soaking in water for 7 days; PL QY was 60.4%.
Comparative example 7
The difference compared with example 1 is that the precursor solution was prepared according to the method of document 1 (Zhou Q, et al Advanced Materials,2016,28 (41): 9163-9168.). Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 41.5% after heating; the performance is reduced by 34.9 percent after the continuous soaking in water for 7 days; PL QY was 51.4%.
Comparative example 8
The difference compared to example 1 is that the ligands added are n-octylamine and brominated 3, 3-diphenylpropylamine. Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 37.1% after heating; the performance is reduced by 40.6% after the continuous soaking in water for 7 days; PL QY was 48.5%.
Comparative example 9
The difference compared to example 1 is that the ligands added are octylamine bromide, brominated 3, 3-diphenylpropylamine. Heating on a hot plate at 60 ℃ for 7 days continuously, wherein the performance is reduced by 38.1% after heating; the performance is reduced by 39.4 percent after the continuous soaking in water for 7 days; PL QY was 49.1%.
As can be seen from FIGS. 1-6, the ligand-modified highly stable MAPbBr of the present invention 3 The perovskite quantum dot@polymer optical film has good thermal stability and water stability. And fig. 3 shows that the thermal stability can be further improved by adding ligand n Xin Anxiu on the basis of a certain amount of 3, 3-diphenylpropylamine ligand, because n Xin Anxiu can passivate the surface defects of perovskite quantum dots more effectively than comparative examples 3-6 using only 3, 3-diphenylpropylamine ligand. Fig. 4 shows the change in water stability after addition of different ligands, it can be seen that ligand addition has little effect on improving water stability, and that the better water stability of the sample is more due to the effect of polymer encapsulation. FIG. 5 shows that the PL QY of samples with different 3, 3-diphenylpropylamine content increases with increasing 3, 3-diphenylpropylamine content over a range, and the sample of comparative example 5 reaches a maximum of 85.9% and then decreases slightly with further increase in content, since too much 3, 3-diphenylpropylamine ligand causes large steric hindrance, resulting in 3, 3-diphenylpropylamine vs Pb 2+ The ion coordination is insufficient. FIG. 6 shows that after heating at 60℃for 7 days for all samples, PL QY was reduced, but the addition of the ligand 3, 3-diphenylpropylamine improved the thermal stability to some extent, probably due to defects formed by continuous growth of perovskite quantum dots formed at high temperature, due to Pb surface 2+ The effective coordination of the ions and the large steric resistance to the regeneration of the perovskite quantum dots formed, additional 3, 3-diphenylpropylamine ligands may partially inhibit this phenomenon.
In conclusion, the ligand-modified highly stable MAPbBr of the present invention 3 The perovskite quantum dot@polymer optical film has good thermal stability and water stability.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (10)
1. Ligand modified high-stability MAPbBr 3 The perovskite quantum dot@polymer optical film is characterized in that the high-stability MAPbBr 3 The perovskite quantum dot optical film is prepared by adding 3, 3-diphenylpropylamine and n-octylamine bromide into a precursor solution for ligand modification.
2. The highly stable MAPbBr of claim 1 3 The perovskite quantum dot@polymer optical film is characterized in that the mass ratio of 3, 3-diphenylpropylamine to n-octylamine bromide is (1-50): 1.
3. the highly stable MAPbBr of claim 1 3 The perovskite quantum dot@polymer optical film is characterized in that the addition amount of 3, 3-diphenylpropylamine in a precursor solution is 0.5-3.5mg/100ml.
4. The highly stable MAPbBr of claim 1 3 The perovskite quantum dot@polymer optical film is characterized in that the precursor solution comprises the following components in percentage by mass (10-20): (50-70): MABr, pbBr of 1 2 、PVDF。
5. The highly stable MAPbBr of claim 1 3 The perovskite quantum dot@polymer optical film is characterized in that the mass of 3, 3-diphenylpropylamine and n-octylamine bromide is PbBr in a precursor respectively 2 10-50% and 1-5% of the weight of the composition.
6. The highly stable MAPbBr of claim 1 3 The perovskite quantum dot@polymer optical film is characterized in that a mixed solution modified by a ligand is subjected to ultrasonic treatment, centrifugal defoaming, filtering and dripping on the surface of flat glass, and a transparent precursor layer is formed by a blade knife coating technology.
7. The highly stable MAPbBr of claim 6 3 Perovskite quantum dot @ polymersAn optical film, characterized in that the transparent precursor layer has a thickness of 100-500 μm.
8. The highly stable MAPbBr of claim 6 3 The perovskite quantum dot@polymer optical film is characterized in that a microporous film filter with the pore diameter less than or equal to 0.22 mu m is adopted in the filtering process.
9. The highly stable MAPbBr of claim 6 3 The perovskite quantum dot@polymer optical film is characterized in that the transparent precursor layer is required to be dried, and the drying process comprises vacuumizing and normal-temperature ventilation; vacuumizing at 20-50deg.C for 3-8 min; and (3) standing for 24-48 hours in a fume hood through normal-temperature ventilation.
10. The highly stable MAPbBr of any one of claims 1 to 9 3 The perovskite quantum dot@polymer optical film is characterized in that the thickness of the optical film is 5-100 mu m; the particle size of the quantum dots is 8-12nm; the luminescence peak position is adjustable at 525-540 nm.
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