CN116675608B - Method for preparing blue perovskite quantum dots in situ by single crystal powder - Google Patents
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 64
- 239000013078 crystal Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000843 powder Substances 0.000 title claims abstract description 19
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 36
- IRAGENYJMTVCCV-UHFFFAOYSA-N 2-phenylethanamine;hydrobromide Chemical compound [Br-].[NH3+]CCC1=CC=CC=C1 IRAGENYJMTVCCV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012296 anti-solvent Substances 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000005525 hole transport Effects 0.000 claims description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- -1 amine salt cations Chemical class 0.000 abstract description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 150000003608 titanium Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 31
- 239000011259 mixed solution Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Natural products NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 8
- 229940117803 phenethylamine Drugs 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- SKHIBNDAFWIOPB-UHFFFAOYSA-N hydron;2-phenylethanamine;chloride Chemical compound Cl.NCCC1=CC=CC=C1 SKHIBNDAFWIOPB-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940048346 phenethylamine hydrochloride Drugs 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
- C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
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Abstract
The invention provides a method for preparing blue perovskite quantum dots by single crystal powder in situ, which comprises the steps of firstly mixing two-dimensional perovskite single crystal powder, bromide, chloride, phenethylamine hydrobromide and an organic solvent, performing heat treatment in an inert atmosphere to obtain a precursor solution, coating the precursor solution on a substrate in the inert atmosphere, and sequentially performing dropwise adding reaction solvent and annealing treatment to obtain the blue perovskite quantum dots. According to the invention, the coulomb effect provided by organic amine salt cations in phenethylamine hydrobromide and halogen in bromide and chloride is utilized to cut open an octahedral network connected with perovskite corners, the three-dimensional network structure of perovskite octahedron is prevented from continuing to grow, the grain size is controlled, single crystal powder is added to regulate and control perovskite phase distribution, non-radiative recombination caused by low-dimensional layered perovskite phase is inhibited, the energy transmission efficiency is improved, the film crystallinity formed by blue perovskite quantum dots is improved, and the luminous performance of the Lan Guanggai titanium quantum dots is remarkably improved.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a method for preparing blue perovskite quantum dots in situ by single crystal powder.
Background
The perovskite light emitting diode (PELED) structure mainly comprises an anode, a hole injection layer, a hole transport layer, a quantum dot light emitting layer, an electron transport layer, a metal cathode and the like, wherein the quantum dot light emitting layer is a perovskite light emitting layer film. The perovskite quantum dot has the advantages of good photoelectric property, low cost and simple synthesis process, and compared with the traditional quantum dot material, the perovskite quantum dot has the advantages of high fluorescence quantum yield and narrow half-peak width, so that the perovskite quantum dot becomes a research hot spot.
At present, the External Quantum Efficiency (EQE) of red and green perovskite quantum dot light emitting diodes (PeLEDs) breaks through 20%, and the EQE of blue light PeLEDs is only 18%, which severely restricts the full-color display application of the PeLEDs. The traditional method for synthesizing perovskite quantum dots is very rapid in the process of quantum dot nucleation and crystallization, and has more surface defects of the quantum dots, so that the method is not beneficial to carrier injection and transmission. Compared with the colloidal perovskite quantum dots, perovskite grows into a uniform and compact film directly on a transmission layer, so that defects at crystals and grain boundaries can be effectively inhibited, fluorescence quantum yield attenuation caused by self absorption can be avoided, and the perovskite thin film is an effective way of high-efficiency blue light PeLEDs. However, because of the effect of the antisolvent, the supersaturation degree of crystal nucleus in the perovskite precursor liquid film is changed, the liquid film is induced to quickly form nucleus crystallization, and perovskite phases with smaller n values are easy to form in the perovskite film prepared in situ due to the influence of lower formation energy and quick crystallization, the perovskite phases with different n values in the film exist when the perovskite phases with smaller n values are the same, the non-radiative recombination in the perovskite phases with smaller n values is very serious, the energy transfer efficiency is low, and the luminous performance of the blue light perovskite quantum dot light-emitting diode is severely limited. Therefore, how to purify perovskite phase distribution and improve the luminescence performance of blue perovskite quantum dots (i.e., blue perovskite thin films) is a technical problem that needs to be solved in the prior art.
Disclosure of Invention
The invention aims to provide a method for preparing blue perovskite quantum dots in situ by single crystal powder.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing blue perovskite quantum dots by single crystal powder in situ, which comprises the following steps:
(1) Mixing two-dimensional perovskite single crystal powder, bromide, chloride, phenethylamine hydrobromide and an organic solvent, and performing heat treatment in an inert atmosphere to obtain a precursor solution;
(2) And (3) coating the precursor solution obtained in the step (1) on a substrate in an inert atmosphere, and then sequentially dripping a reaction solvent and carrying out annealing treatment to obtain the blue perovskite quantum dot.
Preferably, the two-dimensional perovskite single crystal powder in the step (1) includes (PEA) 2 PbBr 4 Single crystal, (PEA) 2 FAPb 2 Br 7 Single crystal, (PEA) 2 FA 2 Pb 3 Br 10 One or more of the single crystals.
Preferably, the bromide in the step (1) is CsBr, pbBr 2 One or more of FABr.
Preferably, the temperature of the heat treatment in the step (1) is 55-65 ℃; the heat treatment time is 3-6h.
Preferably, the concentration of phenethylamine hydrobromide in the precursor solution in the step (1) is 0.1-0.3mol/L.
Preferably, pb in the precursor solution in the step (1) 2+ The concentration of (C) is 0.1-0.3mol/L
Preferably, in the step (2), the substrate is a hole transport layer.
Preferably, the time for dropping the anti-solvent in the step (2) is 18-22s after coating.
Preferably, the antisolvent in step (2) is one or more of chlorobenzene, toluene, acetone, methyl acetate and ethyl acetate.
Preferably, the temperature of the annealing treatment in the step (2) is 65-75 ℃; the annealing treatment time is 7-14min.
The invention provides a method for preparing blue perovskite quantum dots (namely blue perovskite thin films) by single crystal powder in situ. According to the invention, an octahedral network connected with the corners of perovskite is cut through utilizing coulomb action provided by organic amine salt cations (namely phenethylamine cations) in phenethylamine hydrobromide and halogen in bromide and chloride, the continuous growth of a three-dimensional network structure of the perovskite octahedron is hindered, the grain size is controlled, and single crystal powder is added into a precursor solution to regulate and control the distribution of perovskite phases, so that the distribution of purified perovskite phases is realized, the non-radiative recombination caused by low-dimensional layered perovskite phases is inhibited, the energy transmission efficiency is improved, the crystallinity of a film formed by blue perovskite quantum dots is improved, and the luminous performance (electroluminescence and photoluminescence) of the Lan Guanggai perovskite quantum dots is remarkably improved. The results of the examples show that the blue perovskite quantum dots prepared in the example 1 have the strongest crystallinity, and the quantum dots prepared in the example 1 are used as the light-emitting layer, so that the prepared quantum dot light-emitting diode device has the highest external quantum efficiency and brightness and excellent light-emitting performance.
Drawings
FIG. 1 is an XRD pattern of blue perovskite quantum dots prepared according to example 1, comparative example 1 and comparative example 2 of the present invention;
FIG. 2 is a TEM image of blue perovskite quantum dots prepared according to example 1 of the present invention;
fig. 3 is a graph showing the light emission performance of the quantum dot light emitting diode according to application examples 1 to 3, wherein a is the external quantum efficiency, b is the luminance, and c is the current density.
Detailed Description
The invention provides a method for preparing blue perovskite quantum dots by single crystal powder in situ, which comprises the following steps:
(1) Mixing two-dimensional perovskite single crystal powder, bromide, chloride, phenethylamine hydrobromide and an organic solvent, and performing heat treatment in an inert atmosphere to obtain a precursor solution;
(2) And (3) coating the precursor solution obtained in the step (1) on a substrate in an inert atmosphere, and then sequentially dripping a reaction solvent and carrying out annealing treatment to obtain the blue perovskite quantum dot.
In the present invention, the raw materials used are all conventional commercial products in the art unless otherwise specified.
The invention mixes two-dimensional perovskite monocrystal powder, bromide, chloride, phenethylamine hydrobromide and organic solvent, and then carries out heat treatment in inert atmosphere to obtain precursor solution.
In the present invention, the two-dimensional perovskite single crystal powder preferably includes (PEA) 2 PbBr 4 Single crystal, (PEA) 2 FAPb 2 Br 7 Single crystal, (PEA) 2 FA 2 Pb 3 Br 10 One or more of the single crystals, more Preferably (PEA) 2 PbBr 4 And (3) single crystals.
In the present invention, the (PEA) 2 PbBr 4 The method for producing a single crystal preferably comprises the steps of:
(S1) PbBr 2 Mixing phenethylamine hydrobromide and a solvent to obtain a mixed solution;
(S2) stirring, heat treating and cooling the mixed solution obtained in the step (S1) in sequence to obtain (PEA) 2 PbBr 4 And (3) single crystals.
In the present invention, the solvent is preferably at least one of N, N-dimethylformamide and dimethyl sulfoxide. In the present invention, pb in the mixed solution 2+ The concentration of the phenethylamine cation in the mixed solution is preferably 1.8mol/L, and in the present invention, the concentration of the phenethylamine cation in the mixed solution is preferably 3.6mol/L. In the invention, phenethylamine cations and Pb in the mixed solution 2+ The molar ratio of (2) to (1) is preferred.
In the present invention, the temperature of the stirring heat treatment is preferably 65 to 75 ℃, more preferably 68 to 73 ℃. In the present invention, the time of the stirring heat treatment is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours. The invention controls the temperature and time of the stirring heat treatment in the above range to promote the full dissolution of each component. In the present invention, the cooling means is preferably cooling to room temperature at a rate of 0.5 to 1.5 ℃/h, more preferably 0.8 to 1.2 ℃/h. According to the invention, through the cooling mode, the cooling rate is controlled to control the crystallization speed, so that the quality of crystals is ensured.
In the present invention, theThe bromide is preferably CsBr, pbBr 2 One or more of FABr (phenethylamine hydrobromic acid salt). In the present invention, the concentration of bromide in the precursor solution is preferably 0.4 to 0.6mol/L, more preferably 0.47mol/L.
In the present invention, the chloride is preferably CsCl, pbCl 2 One or more of phenethylamine hydrochloride. In the present invention, the concentration of the chloride in the precursor solution is preferably 0.08 to 0.25mol/L, more preferably 0.1 to 0.2mol/L.
In the present invention, the organic solvent is preferably one or more of dimethyl sulfoxide and N, N-dimethylformamide.
In the present invention, the inert atmosphere is preferably argon.
In the present invention, the heat treatment is preferably performed under stirring. The stirring method of the present invention is not particularly limited, and stirring methods well known in the art may be employed. In the present invention, the temperature of the heat treatment is preferably 55 to 65 ℃, more preferably 58 to 63 ℃. In the present invention, the time of the heat treatment is preferably 3 to 6 hours, more preferably 3.5 to 5 hours. The present invention controls the temperature and time of the heat treatment within the above-mentioned ranges to promote sufficient dissolution of the components.
In the present invention, the concentration of phenethylamine hydrobromide in the precursor solution is preferably 0.1 to 0.3mol/L, more preferably 0.16mol/L. The concentration of phenethylamine hydrobromide in the precursor solution is in the range, so that the coulomb effect provided by phenethylamine cations in the phenethylamine hydrobromide is utilized to cut open the octahedral network connected with the perovskite corners, the three-dimensional network structure of the perovskite octahedron is prevented from continuing to grow, and the grain size is controlled.
In the present invention, pb in the precursor solution 2+ The concentration of (C) is preferably 0.1 to 0.3mol/L, more preferably 0.2mol/L. The invention controls Pb in the precursor solution 2+ The concentration of (2) is in the above range to control the number of octahedral layers in the film.
After the precursor solution is obtained, the precursor solution is coated on a substrate in inert atmosphere, and then the reaction solvent is dripped and the annealing treatment is sequentially carried out, so that the blue perovskite quantum dot is obtained.
In the present invention, the precursor solution is preferably filtered using an organic cartridge filter prior to the coating. The precursor solution is filtered through an organic needle core filter to filter out undissolved medicines and impurities. In the present invention, the coating means is preferably spin coating.
In the present invention, the substrate is preferably a hole transport layer.
In the present invention, the time for dropping the antisolvent is preferably 18 to 22 seconds after coating, more preferably 20 seconds after coating. The present invention controls the time of dropping the antisolvent within the above range to control the rate of perovskite nucleation and crystallization.
In the present invention, the antisolvent is one or more of chlorobenzene, toluene, acetone, methyl acetate and ethyl acetate.
In the present invention, the temperature of the annealing treatment is preferably 65 to 75 ℃, more preferably 68 to 72 ℃, and even more preferably 70 ℃. In the present invention, the time of the annealing treatment is preferably 7 to 14 minutes, more preferably 8 to 12 minutes, and still more preferably 10 minutes. The invention controls the temperature and time of the annealing treatment in the above range to control the size of perovskite grains.
The method for preparing the blue perovskite quantum dots by the single crystal powder in situ provided by the invention is simple to operate, mild in reaction condition and suitable for large-scale production.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. 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.
Example 1
The method for preparing the blue perovskite quantum dots by the single crystal powder in situ comprises the following steps:
(1) Will (PEA) 2 PbBr 4 Single crystal, csBr,PbBr 2 、PbCl 2 Dissolving phenethylamine hydrobromide in dimethyl sulfoxide, mixing, and performing heat treatment for 4h in an argon environment at 60 ℃ under stirring to obtain a precursor solution;
said (PEA) 2 PbBr 4 The preparation method of the single crystal comprises the following steps:
(S1) PbBr 2 Mixing phenethylamine hydrobromide and N, N-dimethylformamide to obtain a mixed solution;
pb in the mixed solution 2+ The concentration of phenethylamine cations in the mixed solution is 1.8mol/L, the concentration of phenethylamine cations in the mixed solution is 3.6mol/L, and the concentration of phenethylamine cations and Pb in the mixed solution is 1.8mol/L 2+ The concentration ratio of (2) to (1);
(S2) subjecting the mixed solution obtained in the step (S1) to stirring heat treatment at 70 ℃ for 2 hours, stopping stirring after complete dissolution, and then cooling to room temperature at a speed of 1 ℃/h to obtain (PEA) 2 PbBr 4 A single crystal;
the concentration of CsBr in the precursor solution is 0.21mol/L; pbBr in the precursor solution 2 The concentration of (2) is 0.1mol/L; pbCl in the precursor solution 2 The concentration of (2) is 0.1mol/L; the concentration of phenethylamine hydrobromide in the precursor solution is 0.16mol/L; pb in the precursor solution 2+ The concentration of (C) was 0.2mol/L.
(2) And (3) filtering the precursor solution obtained in the step (1) by using an organic needle core filter, spin-coating the filtered precursor solution on a hole transport layer, and annealing at 70 ℃ for 10min to form the blue perovskite quantum dot.
Application example 1
Blue perovskite quantum dots were prepared according to the method of example 1, and quantum dot light emitting diodes were further prepared using the Lan Guanggai titanium quantum dots as light emitting layers, as follows:
(1) Spin coating PEDOT: PSS is arranged on the anode ITO to form a hole injection layer;
(2) Mixing chlorobenzene and PVK polyvinylcarbazole to obtain PVK dispersion; spin-coating the PVK dispersion liquid on the surface of the hole injection layer obtained in the step (1), and annealing at 140 ℃ for 15min for forming to form a hole transport layer;
(3) Preparing blue perovskite quantum dots on the surface of the hole transport layer (namely, as a substrate) obtained in the step (2) according to the method of the embodiment 1 to form a light-emitting layer;
(4) Evaporating the surface of the light-emitting layer obtained in the step (3) by using TPBi as a raw material to form an evaporating electron transport layer; vacuum degree of 6×10 during vapor deposition -4 pa；
(5) Evaporating the surface of the evaporated electron transport layer obtained in the step (4) by using LiF as a raw material to form an electron injection layer; vacuum degree of 6×10 during vapor deposition -4 pa；
(6) Evaporating the surface of the electron injection layer obtained in the step (4) by using aluminum as a raw material to form a cathode, thereby obtaining a quantum dot light-emitting diode; vacuum degree of 6×10 during vapor deposition -4 pa, guarantee the stability of evaporation rate.
Comparative example 1
Blue perovskite quantum dots were prepared according to the method of example 1, differing from example 1 in that: in preparing the precursor solution, 50% by mass of the precursor solution (PEA) 2 PbBr 4 Equivalent PbBr for single crystal 2 And phenethylamine hydrobromide.
Application example 2
The quantum dot light emitting diode was prepared according to the method of application example 1, which is different from application example 1 in that: blue perovskite quantum dots were prepared according to the method of comparative example 1.
Comparative example 2
Blue perovskite quantum dots were prepared according to the method of example 1, differing from example 1 in that: when preparing the precursor solution, no addition (PEA) was made 2 PbBr 4 Single crystal is used as raw material, and equivalent PbBr is fully adopted 2 And phenethylamine hydrobromide instead (PEA) 2 PbBr 4 And (3) single crystals.
Application example 3
The quantum dot light emitting diode was prepared according to the method of application example 1, which is different from application example 1 in that: blue perovskite quantum dots were prepared according to the method of comparative example 2.
The blue perovskite quantum dots prepared in example 1, comparative example 1 and comparative example 2 were observed and detected by an X-ray diffractometer, and XRD patterns were obtained as shown in FIG. 1. It is understood from FIG. 1 that the crystallinity of the blue perovskite quantum dots prepared in example 1 is strongest, which means that the crystallinity of the prepared blue perovskite quantum dot luminescent layer film is enhanced when the single crystal content is increased.
The blue perovskite quantum dots prepared in example 1 were observed and detected by a transmission electron microscope to obtain a TEM image as shown in fig. 2, and as can be seen from fig. 2, the perovskite with the cubic phase of the blue perovskite quantum dots prepared in example 1.
Luminescence performance detection
Tests under nitrogen environment by using a Keithley2400 source meter and a ChromaMeterCS-2000 show that the quantum dot light-emitting diode prepared by taking the blue perovskite quantum dots prepared in example 1 as a light-emitting layer and the quantum dot light-emitting diode prepared by taking the blue perovskite quantum dots prepared in comparative example 2 as a light-emitting layer are tested, and the light-emitting performance is shown in a graph in FIG. 3, wherein a in FIG. 3 is external quantum efficiency, b in FIG. 3 is brightness, c in FIG. 3 is current density, and it can be seen that the addition of single crystals leads to significant improvement of the external quantum efficiency and brightness of the quantum dot light-emitting diode prepared by taking the blue perovskite quantum dots prepared in example 1 as the light-emitting layer because the addition of single crystals improves the crystallinity of the blue perovskite quantum dot light-emitting layer film prepared in example 1 and realizes regulation of n-value distribution of the perovskite film, so that energy transmission is more effective.
In conclusion, the crystallinity of the blue perovskite quantum dots prepared in the embodiment 1 of the invention is strongest, and the blue perovskite quantum dots prepared in the embodiment 1 are used as the light-emitting layer, so that the external quantum efficiency and the brightness of the prepared quantum dot light-emitting diode device are highest, and the light-emitting performance is excellent.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A method for preparing blue perovskite quantum dots by single crystal powder in situ comprises the following steps:
(1) Will (PEA) 2 PbBr 4 Single crystal, csBr, pbBr 2 、PbCl 2 Mixing phenethylamine hydrobromide and an organic solvent, and performing heat treatment in an inert atmosphere to obtain a precursor solution;
(2) And (3) coating the precursor solution obtained in the step (1) on a substrate in an inert atmosphere, and then sequentially dripping a reaction solvent and carrying out annealing treatment to obtain the blue perovskite quantum dot.
2. The method according to claim 1, wherein the temperature of the heat treatment in step (1) is 55 to 65 ℃; the heat treatment time is 3-6h.
3. The method according to claim 2, wherein the concentration of phenethylamine hydrobromide in the precursor solution in step (1) is 0.1 to 0.3mol/L.
4. The method according to claim 3, wherein Pb in the precursor solution in the step (1) 2+ The concentration of (C) is 0.1-0.3mol/L
5. The method of claim 4, wherein the substrate in step (2) is a hole transport layer.
6. The method of claim 5, wherein the time for dropping the antisolvent in step (2) is 18-22s after coating.
7. The method of claim 6, wherein the antisolvent in step (2) is one or more of chlorobenzene, toluene, acetone, methyl acetate, and ethyl acetate.
8. The method of claim 7, wherein the temperature of the annealing treatment in step (2) is 65-75 ℃; the annealing treatment time is 7-14min.
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