CN113845898A - Multifunctional ligand-modified mixed halogen perovskite quantum dot and application thereof - Google Patents
Multifunctional ligand-modified mixed halogen perovskite quantum dot and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of perovskite quantum dots, and particularly relates to a multifunctional ligand-modified mixed halogen perovskite quantum dot and application thereof. The multifunctional ligand has a structure containing carboxyl and amino groups capable of passivating the surface defects of the mixed halogen perovskite quantum dots and also containing functional groups capable of forming hydrogen bonds with halogen in the mixed halogen perovskite quantum dots, and experiments prove that the multifunctional ligand interacts with the mixed halogen perovskite quantum dots, can passivate the defects of the mixed halogen perovskite quantum dots, and can inhibit phase separation possibly occurring under an electric field. The light-emitting diode prepared by using the mixed halogen perovskite quantum dots modified by the mixed halogen perovskite quantum dot solution modified by the multifunctional ligand passivation has the efficiency of more than 18 percent and has better spectral stability.
Description
Technical Field
The invention belongs to the technical field of preparation of perovskite quantum dots, and particularly relates to a multifunctional ligand-modified mixed halogen perovskite quantum dot and application thereof.
Background
The perovskite quantum dot has the advantages of simple synthesis method, wide color gamut range, adjustable band gap and the like, and has great potential application value in the fields of light emitting diodes, solar cells, photoelectric detectors and the like.
Through the development of recent years, the research on pure halogen perovskite quantum dot light emitting diodes has been greatly advanced, but the research on mixed halogen perovskite quantum dot light emitting diodes is still slow. The reason is that the mixed halogen perovskite quantum dots have many surface defects, and are phase-separated when applied to a light-emitting diode, so that the spectrum is shifted, and the performance of the device is reduced.
Chinese patent CN109796976B discloses a method for preparing copper-doped red perovskite quantum dots, which adopts copper-doped mixed halogen red perovskite quantum dots to improve the structural stability of materials, but the electroluminescent diode has poor performance [ Nano Energy 2019,62,434-441 ], which indicates that the surface of the metal ion-doped mixed halogen perovskite quantum dots still has more defects. In addition, phase separation is the biggest obstacle in practical application of the mixed-halogen perovskite quantum dot, and at present, no effective strategy can simultaneously passivate the surface defect of the mixed-halogen perovskite quantum dot and inhibit the phase separation. Related reports previously propose passivation and repair of quantum dot surfaces by using different ligands, but these methods still cannot inhibit phase separation of mixed halogen perovskite quantum dots, and spectral shift still occurs when the method is applied to light-emitting diodes. The prior art usually only focuses on one point, and is difficult to simultaneously satisfy the synergistic effect of passivating defects and inhibiting the phase separation of mixed halogen quantum dots. Therefore, there is a need to develop more effective strategies while passivating the defects and inhibiting mixed-halogen perovskite phase separation, improving its light emitting diode performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a mixed halogen perovskite quantum dot modified by multifunctional ligand passivation and application thereof.
In order to achieve the above object, the present invention provides a mixed-halogen perovskite quantum dot modified with a multifunctional ligand, wherein the multifunctional ligand has a structure containing carboxyl groups and amino groups capable of passivating surface defects of the mixed-halogen perovskite quantum dot, and further contains a functional group capable of forming a hydrogen bond with a halogen in the mixed-halogen perovskite quantum dot.
Preferably, the preparation method of the perovskite quantum dot comprises the following steps: and mixing and stirring the multifunctional ligand and the mixed halogen perovskite quantum dot solution, and performing solid-liquid separation to obtain a liquid phase, namely the multifunctional ligand modified mixed halogen perovskite quantum dot.
Preferably, the preparation of the mixed halogen perovskite quantum dot solution comprises the following steps: centrifuging the mixed halogen perovskite quantum dot solution by using an anti-solvent to obtain quantum dot precipitate; and dissolving the quantum dot precipitate by using a nonpolar solvent to obtain a mixed halogen perovskite quantum dot solution.
Preferably, the mixed halogen perovskite quantum dot structure is CsPbBrxCl3-x、CsPbBrxI3-x、MAPbBrxCl3-x、MAPbBrxI3-x、FAPbBrxCl3-x、FAPbBrxI3-xWherein 0 is<x<3。
Preferably, the antisolvent is one or more of methyl acetate, ethyl acetate, butyl acetate, isopropanol, n-butanol, acetonitrile, acetone.
Preferably, the volume ratio of the anti-solvent to the quantum dot solution is 1: 1-4: 1.
Preferably, the nonpolar solvent is any one of toluene, n-hexane, n-octane and cyclohexane.
Preferably, the functional group capable of forming a hydrogen bond with the halogen in the mixed-halogen perovskite quantum dot, which is contained in the structure of the multifunctional ligand, is one or more of amino, imino, hydroxyl and sulfhydryl.
Preferably, the multifunctional ligand is a neutral amino acid.
Preferably, the multifunctional ligand is one or more of tryptophan, glutamine, threonine, serine, asparagine, cysteine, and tyrosine.
Further preferably, the multifunctional ligand is tryptophan.
Preferably, the molar ratio of the multifunctional ligand to the quantum dots is 0.1: 1-1: 1.
Preferably, the multifunctional ligand and the mixed halogen perovskite quantum dot solution are mixed and stirred, and a filtrate is obtained after solid-liquid separation, wherein the filtrate specifically comprises the following components: mixing the multifunctional ligand and the mixed halogen perovskite quantum dot solution, stirring at 300-600rpm for 15-30 minutes, centrifuging at 10000-15000rpm for 5-10 minutes, and taking the supernatant to obtain the mixed halogen perovskite quantum dot modified by the multifunctional ligand passivation.
According to another aspect of the invention, there is provided a use of the perovskite quantum dot in the preparation of a light emitting diode, a photodetector or a solar cell.
Preferably, the perovskite quantum dots are used as a light emitting layer material of a light emitting diode or a light absorbing layer material of a photoelectric detector or a solar cell.
According to another aspect of the present invention, there is provided a light emitting diode whose light emitting layer material contains the perovskite quantum dots.
According to another aspect of the present invention, there is provided a photodetector, wherein the light absorbing layer material comprises said perovskite quantum dots.
According to another aspect of the present invention, there is provided a solar cell having a light absorbing layer material comprising said perovskite quantum dots.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) the multifunctional ligand modified mixed halogen perovskite quantum dot provided by the invention has the structure containing carboxyl and amino which can passivate surface defects of the mixed halogen perovskite quantum dot, and also contains a functional group which can form a hydrogen bond with halogen in the mixed halogen perovskite quantum dot.
(2) According to the invention, different multifunctional ligands are utilized to modify the surface defects of the mixed halogen perovskite quantum dots, and based on the synergistic effect of metal coordination bonds and hydrogen bonds between the multifunctional ligands and the quantum dots, the coordination bonds can passivate the defects, so that the perovskite quantum dots have better luminous efficiency, and the hydrogen bonds can stabilize the perovskite quantum dots and cannot be separated under the action of an electric field. Meanwhile, the multifunctional ligand enables the quantum dots to be more stable, improves charge extraction and injection of the quantum dots, and improves luminous efficiency.
(3) The External Quantum Efficiency (EQE), brightness, current efficiency and the like of the high-performance and high-efficiency light-emitting diode prepared by using the mixed halogen perovskite quantum dot solution modified by multifunctional ligand passivation are greatly improved. The efficiency of a light-emitting diode prepared by using the mixed halogen perovskite quantum dot modified by the multifunctional ligand is over 18 percent, the spectral stability is good, and the performance is greatly improved compared with that of a perovskite quantum dot light-emitting diode not modified by a short-chain ligand.
(4) In order to improve the performances of the mixed halogen perovskite quantum dot such as light efficiency, stability and the like and expand the application of the perovskite quantum dot in a photoelectric device, the invention provides a method for modifying the mixed halogen perovskite quantum dot by a multifunctional ligand, wherein the multifunctional ligand has the synergistic effect of passivating defects and forming hydrogen bonds, and can simultaneously reduce the surface defects of the perovskite quantum dot and inhibit the phase separation of the mixed halogen quantum dot under the action of an electric field. And the prepared quantum dots are applied to electroluminescent devices, so that the device performance is greatly improved. The method has the following advantages: 1. the method is simple to operate, and the perovskite quantum dot solution and the multifunctional ligand are mixed and stirred. 2. Low cost, low price, and the needed multifunctional ligand is an industrial common raw material.
Drawings
Fig. 1 shows transmission electron microscope images of the halogen-mixed perovskite quantum dots obtained in comparative example 1 and example 1.
FIG. 2 is a comparison graph of fluorescence spectrum and PLQY of the mixed-halogen perovskite quantum dots obtained in example 1 and comparative example 1.
FIG. 3 is a graph comparing the stability of the mixed-halogen perovskite quantum dots obtained in example 1 and comparative example 1.
FIG. 4 is a graph comparing the efficiency of light emitting diodes prepared with different multifunctional ligand treated perovskite quantum dots.
Content a and content b of fig. 5 are graphs showing the changes of electroluminescence spectra of the light-emitting diode prepared by the mixed halogen perovskite quantum dots obtained in comparative example 1 and example 1 respectively along with the current.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a multifunctional ligand-modified mixed halogen perovskite quantum dot, which is a multifunctional ligand passivation-modified mixed halogen perovskite quantum dot, wherein the structure of the multifunctional ligand contains carboxyl and amino which can passivate surface defects of the mixed halogen perovskite quantum dot, the carboxyl can passivate B-site defects (halogen defects), and the amino can passivate A-site defects (cesium, methylamine or formamidine); and the functional group can form hydrogen bond with halogen in the mixed halogen perovskite quantum dot.
In some embodiments, the method for preparing the mixed-halogen perovskite quantum dot comprises the following steps: and mixing and stirring the multifunctional ligand and the mixed halogen perovskite quantum dot solution, and carrying out solid-liquid separation to obtain a liquid phase, namely the multifunctional ligand passivation modified mixed halogen perovskite quantum dot.
In some embodiments, the preparation of the mixed-halogen perovskite quantum dot solution comprises the following steps: centrifuging the mixed halogen perovskite quantum dot solution by using an anti-solvent to obtain quantum dot precipitate; and dissolving the quantum dot precipitate by using a nonpolar solvent to obtain a mixed halogen perovskite quantum dot solution.
In some embodiments, the mixed halogen perovskite quantum dot solution is prepared by a conventional quantum dot preparation method such as a thermal injection method or an anion exchange method.
In some embodiments of the invention, the performance of the mixed-halogen perovskite quantum dots is improved by multifunctional ligands, including filling in surface vacancies of the quantum dots to passivate defects, and forming hydrogen bonds with halogens to inhibit quantum dot phase separation. Firstly, synthesizing a quantum dot stock solution by using a hot injection method, then purifying by using an anti-solvent, then dissolving in a non-polar solvent, and modifying by using a multifunctional ligand to obtain the nearly perfect mixed halogen perovskite quantum dot.
The mixed halogen perovskite quantum dot structure comprises but is not limited to CsPbBrxCl3-x、CsPbBrxI3-x、MAPbBrxCl3-x、MAPbBrxI3-x、FAPbBrxCl3-x、FAPbBrxI3-xWherein 0 is<x<3。
In some embodiments, the anti-solvent is one or more of methyl acetate, ethyl acetate, butyl acetate, isopropanol, n-butanol, acetonitrile, acetone.
In some embodiments, the volume ratio of the anti-solvent to the quantum dot solution is 1:1 to 4: 1.
In some embodiments, the non-polar solvent is any one of toluene, n-hexane, n-octane, and cyclohexane.
In some embodiments, the functional group contained in the structure of the multifunctional ligand capable of forming a hydrogen bond with the halogen in the mixed-halogen perovskite quantum dot is one or more of an amino group, an imino group, a hydroxyl group, and a thiol group.
The amino acids are classified into neutral amino acids, acidic amino acids and basic amino acids, and it is found in experiments that, in a preferred embodiment, the multifunctional ligand is a neutral amino acid. Including but not limited to one or more of tryptophan, glutamine, threonine, serine, asparagine, cysteine, and tyrosine; further preferred is tryptophan. In experiments, basic amino acids (such as arginine, lysine and histidine) or acidic amino acids with similar structures are tried, and the fact that the performance of the mixed-halogen perovskite quantum dot cannot be improved is found, and the perovskite quantum dot PLQY is reduced, probably because the basic or acidic properties of the mixed-halogen perovskite quantum dot cannot improve due to the fact that the basic or acidic properties of the mixed-halogen perovskite quantum dot PLQY damage the structure of the quantum dot, the quantum dot is degraded, and the performance of the quantum dot cannot be improved.
In some embodiments, the molar ratio of the multifunctional ligand to the quantum dot is 0.1:1 to 1:1, preferably 0.2:1 to 0.3: 1.
In some embodiments, the multifunctional ligand and the mixed halogen perovskite quantum dot solution are mixed and stirred, and a liquid phase is taken after solid-liquid separation, specifically: mixing the multifunctional ligand and the mixed halogen perovskite quantum dot solution, stirring at the rotating speed of 300-600rpm for 15-30 minutes, centrifuging at the rotating speed of 10000-15000rpm for 5-10 minutes, and taking the supernatant to obtain the mixed halogen perovskite quantum dot modified by the multifunctional ligand passivation.
The invention also provides application of the perovskite quantum dot in preparation of a light-emitting diode, a photoelectric detector or a solar cell. A light emitting diode, a photoelectric detector and a solar cell are also provided, and the material of a light emitting layer of the light emitting diode, the photoelectric detector and the solar cell comprises the mixed halogen perovskite quantum dot.
The following are specific examples:
comparative example 1:
a mixed halogen perovskite quantum dot has a CsPbBrI structure2。
0.1682g cesium carbonate was added with 8mL octadecene, 0.5mL oleic acid in a 100mL flask and heated to 120 ℃ with aeration until the cesium carbonate was completely dissolved. 0.0230g PbBr2With 0.0578g PbI2And 5mL of octadecene, 0.5mL of oleic acid and 0.5mL of oleylamine are added into a 100mL flask, the flask is heated to 120 ℃ and then vacuum-dried for 1 hour, nitrogen is introduced, the temperature is raised to 150 ℃, 0.4mL of prepared cesium carbonate solution is injected, and after the reaction is carried out for 5 seconds, the ice-water bath is immediately used for stopping the reaction. Mixing the obtained stock solution with ethyl acetate at a volume ratio of 1:3, centrifuging at the rotation speed of 14000rpm for 7 minutes, taking the precipitate, and dissolving in n-hexane to obtain the mixed halogen perovskite CsPbBrI2A quantum dot solution.
Preparing the light-emitting diode: indium Tin Oxide (ITO) glass was sonicated for 30 minutes sequentially in ITO cleaner, deionized water, acetone and isopropanol. And drying the cleaned ITO by nitrogen, and treating the cleaned ITO in an ultraviolet ozone instrument for 5 minutes. The PEDOT: PSS was then spin-coated as a film at 2000rpm in air and dry annealed at 120 ℃ for 15 minutes, followed by transfer into a nitrogen glove box. A poly-TPD chlorobenzene solution at a concentration of 8mg/mL was spin-coated on an ITO/PEDOT: PSS substrate at 2000rpm in a glove box, followed by annealing at 140 ℃ for 15 minutes. And spin-coating the obtained quantum dot solution on the surface of poly-TPD at the speed of 1000rpm to form a film, annealing at 50 ℃ for 5 minutes, and transferring the substrates into a high vacuum evaporation apparatus to respectively evaporate 30nm TPBi, 1nm LiF and 100nm Al.
Example 1
A mixed halogen perovskite quantum dot modified by multifunctional ligand has a CsPbBrI structure2And the multifunctional ligand is tryptophan.
0.1682g cesium carbonate was added with 8mL octadecene, 0.5mL oleic acid in a 100mL flask and heated to 120 ℃ with aeration until the cesium carbonate was completely dissolved. 0.0230g PbBr2With 0.0578g PbI2And 5mL octadecene, 0.5mL oleic acid, 0.5mL oleylamine were added to a 100mL flask and heated to 1Vacuum drying for 1 hour after 20 ℃, introducing nitrogen, heating to 150 ℃, injecting 0.4mL of prepared cesium carbonate solution, and stopping the reaction by using an ice water bath immediately after the reaction is carried out for 5 seconds. Mixing the obtained stock solution with ethyl acetate at a volume ratio of 1:3, centrifuging at the rotation speed of 14000rpm for 7 minutes, taking the precipitate, and dissolving in n-hexane to obtain the mixed halogen perovskite CsPbBrI2A quantum dot solution. Then 0.02 g of tryptophan is added into the quantum dot solution, after stirring for 5 minutes, the solution is centrifuged for 5 minutes at the rotating speed of 7000rpm, and the supernatant is taken to obtain the tryptophan modified mixed halogen perovskite quantum dot CsPbBrI2。
Preparing the light-emitting diode: consistent with the preparation method in comparative example 1, except that the tryptophan-modified mixed-halogen perovskite quantum dot CsPbBrI prepared in the embodiment2Replaces the mixed halogen perovskite CsPbBrI prepared in the comparative example 12A quantum dot solution.
Fig. 1 shows transmission electron microscope images of the halogen-mixed perovskite quantum dots obtained in comparative example 1 and example 1. As can be seen from the TEM image, the quantum dot modified by tryptophan in example 1 has a more regular morphology, which may be caused by the easy shedding of the original quantum dot surface ligand such as oleylamine oleate, which leads to the aggregation of the quantum dot, while the tryptophan modified quantum dot can fill the surface vacancy of the quantum dot, passivate the defect, and reconstruct the surface of the quantum dot, thus having a regular morphology.
FIG. 2 is a comparison graph of fluorescence spectrum and PLQY of the mixed-halogen perovskite quantum dots obtained in example 1 and comparative example 1. As can be seen from fig. 2, the quantum dot modified with tryptophan in example 1 has a higher PLQY, which is probably because tryptophan can fill the surface vacancies of the quantum dot, passivate the defects, and suppress the non-radiative transition.
FIG. 3 is a graph comparing the stability of the mixed-halogen perovskite quantum dots obtained in example 1 and comparative example 1. As can be seen from fig. 3, the fluorescence relative intensity of the quantum dot modified by tryptophan in example 1 is higher and more stable than that of the original quantum dot in comparative example 1, and it is probably because the tryptophan and the surface of the perovskite quantum dot have stronger interaction force and are not easy to fall off, thereby improving the stability of the perovskite quantum dot.
Content a and content b of fig. 5 are graphs showing the changes of electroluminescence spectra of the light-emitting diode prepared by the mixed halogen perovskite quantum dots obtained in comparative example 1 and example 1 respectively along with the current. As can be seen from fig. 5, the electroluminescence spectrum of the original mixed-halogen red perovskite quantum dot light-emitting diode gradually red-shifts under the action of the electric field, and the half-peak width gradually widens, which indicates that the original mixed-halogen red perovskite quantum dots are phase-separated under the action of the electric field. The electroluminescent spectrum of the mixed halogen red perovskite quantum dot light-emitting diode modified by tryptophan keeps stable under the action of an electric field and does not generate red shift, which shows that the hydrogen bond directly formed by tryptophan and halogen can well inhibit the phase separation of the mixed halogen perovskite quantum dot.
Example 2
A mixed halogen perovskite quantum dot modified by multifunctional ligand has a CsPbBrI structure2The multifunctional ligand is threonine.
0.1682g cesium carbonate was added with 8mL octadecene, 0.5mL oleic acid in a 100mL flask and heated to 120 ℃ with aeration until the cesium carbonate was completely dissolved. 0.0230g PbBr2With 0.0578g PbI2And 5mL of octadecene, 0.5mL of oleic acid and 0.5mL of oleylamine are added into a 100mL flask, the flask is heated to 120 ℃ and then vacuum-dried for 1 hour, nitrogen is introduced, the temperature is raised to 150 ℃, 0.4mL of prepared cesium carbonate solution is injected, and after the reaction is carried out for 5 seconds, the ice-water bath is immediately used for stopping the reaction. Mixing the obtained stock solution with ethyl acetate at a volume ratio of 1:3, centrifuging at the rotation speed of 14000rpm for 7 minutes, taking the precipitate, and dissolving in n-hexane to obtain the mixed halogen perovskite CsPbBrI2A quantum dot solution. Then adding 0.02 g threonine into the quantum dot solution, stirring for 5 minutes, centrifuging for 5 minutes at the rotating speed of 7000rpm, and taking the supernatant to obtain the threonine modified mixed halogen perovskite quantum dot CsPbBrI2。
Preparing the light-emitting diode: consistent with the preparation method in comparative example 1, except that the threonine-modified mixed-halogen perovskite quantum dot CsPbBrI prepared in the embodiment2Replaces the mixed halogen perovskite CsPbBrI prepared in the comparative example 12QuantumAnd (4) spotting the solution.
Example 3
A mixed halogen perovskite quantum dot modified by multifunctional ligand has a CsPbBrI structure2The multifunctional ligand is serine.
0.1682g cesium carbonate was added with 8mL octadecene, 0.5mL oleic acid in a 100mL flask and heated to 120 ℃ with aeration until the cesium carbonate was completely dissolved. 0.0230g PbBr2With 0.0578g PbI2And 5mL of octadecene, 0.5mL of oleic acid and 0.5mL of oleylamine are added into a 100mL flask, the flask is heated to 120 ℃ and then vacuum-dried for 1 hour, nitrogen is introduced, the temperature is raised to 150 ℃, 0.4mL of prepared cesium carbonate solution is injected, and after the reaction is carried out for 5 seconds, the ice-water bath is immediately used for stopping the reaction. Mixing the obtained stock solution with ethyl acetate at a volume ratio of 1:3, centrifuging at the rotation speed of 14000rpm for 7 minutes, taking the precipitate, and dissolving in n-hexane to obtain the mixed halogen perovskite CsPbBrI2A quantum dot solution. Then 0.02 serine acid is added into the quantum dot solution, after stirring for 5 minutes, the solution is centrifuged for 5 minutes at the rotating speed of 7000rpm, and the supernatant is taken to obtain the serine modified mixed halogen perovskite quantum dot CsPbBrI2。
Preparing the light-emitting diode: consistent with the preparation method in comparative example 1, except that the serine-modified mixed-halogen perovskite quantum dot CsPbBrI prepared in the embodiment2Replaces the mixed halogen perovskite CsPbBrI prepared in the comparative example 12A quantum dot solution.
Example 4
A mixed halogen perovskite quantum dot modified by multifunctional ligand has a CsPbBrI structure2The multifunctional ligand is tyrosine.
0.1682g cesium carbonate was added with 8mL octadecene, 0.5mL oleic acid in a 100mL flask and heated to 120 ℃ with aeration until the cesium carbonate was completely dissolved. 0.0230g PbBr2With 0.0578g PbI2And 5mL of octadecene, 0.5mL of oleic acid and 0.5mL of oleylamine are added into a 100mL flask, the flask is heated to 120 ℃ and then vacuum-dried for 1 hour, nitrogen is introduced, the temperature is raised to 150 ℃, 0.4mL of prepared cesium carbonate solution is injected, and after the reaction is carried out for 5 seconds, the ice-water bath is immediately used for stopping the reaction. The volume ratio of the obtained stock solution to ethyl acetate is 1:3Mixing, centrifuging at 14000rpm for 7 minutes, taking the precipitate and dissolving in n-hexane to obtain the mixed halogen perovskite CsPbBrI2A quantum dot solution. Then 0.02 of the complex amino acid is added into the quantum dot solution, after stirring for 5 minutes, the solution is centrifuged for 5 minutes at the rotating speed of 7000rpm, and the supernatant is taken to obtain the complex amino acid modified mixed halogen perovskite quantum dot CsPbBrI2。
Preparing the light-emitting diode: consistent with the preparation method in comparative example 1, except that the complex amino acid modified mixed-halogen perovskite quantum dot CsPbBrI prepared in the embodiment2Replaces the mixed halogen perovskite CsPbBrI prepared in the comparative example 12A quantum dot solution.
FIG. 4 is a graph comparing the efficiency of light emitting diodes prepared with different multifunctional ligand treated perovskite quantum dots under otherwise identical conditions. As can be seen from FIG. 4, tryptophan has a good passivation effect on the mixed halogen red perovskite quantum dots, and the external quantum efficiency of the light emitting diode is improved from 4.8% to 18.3%. The quantum dot efficiency obtained by modifying the mixed halogen perovskite quantum dot by different amino acid types has certain difference. Wherein the light emitting diode efficiency of the complex amino acid treated perovskite quantum dots is 8.1%, the light emitting diode efficiency of the threonine treated perovskite quantum dots is 12.9%, the light emitting diode efficiency of the serine treated perovskite quantum dots is 16.1%, and the light emitting diode efficiency of the tryptophan treated perovskite quantum dots is 18.3%. The efficiency of the light-emitting diode obtained by treating the quantum dots with different amino acids is different, which is probably because the interaction force between different amino acids and perovskite quantum dots is different, so that the passivation effect on the surface defects of the quantum dots is different, and the efficiency of the obtained device is different.
Example 5
A mixed halogen perovskite quantum dot modified by multifunctional ligand has a CsPbClBr structure2And the multifunctional ligand is tryptophan.
0.1682g cesium carbonate was added with 8mL octadecene, 0.5mL oleic acid in a 100mL flask and heated to 120 ℃ with aeration until the cesium carbonate was completely dissolved. 0.0460g PbBr2With 0.0174g PbCl2And 5mL of tenOctaene, 0.5mL of oleic acid and 0.5mL of oleylamine were added to a 100mL flask, heated to 120 ℃ and vacuum dried for 1 hour, nitrogen was introduced, the temperature was raised to 150 ℃, 0.4mL of a previously prepared cesium carbonate solution was injected, and the reaction was terminated immediately after 5 seconds by an ice-water bath. Mixing the obtained stock solution with ethyl acetate at a volume ratio of 1:3, centrifuging at the rotation speed of 14000rpm for 7 minutes, taking the precipitate, and dissolving in n-hexane to obtain the mixed halogen perovskite CsPbBrI2A quantum dot solution. Then 0.02 g of tryptophan is added into the quantum dot solution, after stirring for 5 minutes, the solution is centrifuged for 5 minutes at the rotating speed of 7000rpm, and the supernatant is taken to obtain the tryptophan modified mixed halogen perovskite quantum dot CsPbBrI2。
Preparing the light-emitting diode: consistent with the preparation method in comparative example 1, except that the tryptophan-modified mixed-halogen perovskite quantum dot CsPbBrI prepared in the embodiment2Replaces the mixed halogen perovskite CsPbBrI prepared in the comparative example 12A quantum dot solution.
Example 6
A multifunctional ligand modified mixed halogen perovskite quantum dot has a FAPBBrI structure2And the multifunctional ligand is tryptophan.
0.05g formamidine acetate was added to a 100mL flask with 8mL octadecene, 0.5mL oleic acid and heated to 120 ℃ with aeration until the formamidine acetate was completely dissolved. 0.0230g PbBr2With 0.0578g PbI2And 5mL of octadecene, 0.5mL of oleic acid and 0.5mL of oleylamine are added into a 100mL flask, the flask is heated to 120 ℃ and then vacuum-dried for 1 hour, nitrogen is introduced, the temperature is raised to 150 ℃, 0.4mL of prepared formamidine acetate solution is injected, and the reaction is stopped by using an ice water bath immediately after 5 seconds of reaction. Mixing the obtained stock solution with ethyl acetate at a volume ratio of 1:3, centrifuging at the rotation speed of 14000rpm for 7 minutes, taking the precipitate, and dissolving in n-hexane to obtain the mixed halogen perovskite FAPBBrI2A quantum dot solution. Then 0.02 g of tryptophan is added into the quantum dot solution, after stirring for 5 minutes, the solution is centrifuged for 5 minutes at the rotating speed of 7000rpm, and the supernatant is taken to obtain the tryptophan modified mixed halogen perovskite quantum dot FAPBBrI2。
Preparing the light-emitting diode: preparation method I in comparative example 1Different from the above, the tryptophan modified mixed halogen perovskite quantum dot solution FAPBBrI prepared in the embodiment is used for preparing the tryptophan modified mixed halogen perovskite quantum dot solution FAPBBrI2Replaces the mixed halogen perovskite CsPbBrI prepared in the comparative example 12A quantum dot solution.
Example 7
A mixed halogen perovskite quantum dot modified by multifunctional ligand has a MAPbBrI structure2And the multifunctional ligand is tryptophan.
0.05g methylamine acetate was charged with 8mL octadecene, 0.5mL oleic acid into a 100mL flask and heated to 120 ℃ with aeration until methylamine acetate was completely dissolved. 0.0230g PbBr2With 0.0578g PbI2And 5mL of octadecene, 0.5mL of oleic acid and 0.5mL of oleylamine are added into a 100mL flask, the flask is heated to 120 ℃ and then vacuum-dried for 1 hour, nitrogen is introduced, the temperature is raised to 150 ℃, 0.4mL of prepared methylamine acetate solution is injected, and after the reaction is carried out for 5 seconds, the ice water bath is immediately used for stopping the reaction. Mixing the obtained stock solution with ethyl acetate at a volume ratio of 1:3, centrifuging at the rotation speed of 14000rpm for 7 minutes, taking the precipitate, and dissolving the precipitate in n-hexane to obtain the mixed halogen perovskite MAPBBrI2A quantum dot solution. Then 0.02 g of tryptophan is added into the quantum dot solution, after stirring for 5 minutes, the mixture is centrifuged for 5 minutes at the rotating speed of 7000rpm, and the supernatant is taken to obtain the tryptophan modified mixed halogen perovskite quantum dot MAPbBrI2。
Preparing the light-emitting diode: consistent with the preparation method in comparative example 1, except that the tryptophan-modified mixed-halogen perovskite quantum dot solution MAPbBrI prepared in the embodiment2Replaces the mixed halogen perovskite CsPbBrI prepared in the comparative example 12A quantum dot solution.
According to the invention, the mixed halogen perovskite quantum dots prepared in the embodiment are used as the luminescent layer material of the light-emitting diode, and the tested external quantum efficiency performance is excellent, and the electroluminescent spectrum stability is good. The performances of the perovskite quantum dot solar cell and the photoelectric detector are related to the mass of quantum dots, and it can be speculated that the high-quality mixed halogen perovskite quantum dots prepared by the embodiment of the invention are used as light absorption layer materials of the photoelectric detector and the solar cell, and high-efficiency and stable devices can be obtained.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The mixed-halogen perovskite quantum dot is characterized in that the mixed-halogen perovskite quantum dot is modified by a multifunctional ligand, the multifunctional ligand has a structure containing amino groups and carboxyl groups capable of passivating surface defects of the mixed-halogen perovskite quantum dot, and further contains functional groups capable of forming hydrogen bonds with halogen in the mixed-halogen perovskite quantum dot.
2. The perovskite quantum dot of claim 1, wherein the preparation method of the perovskite quantum dot comprises the following steps: and mixing and stirring the multifunctional ligand and the mixed halogen perovskite quantum dot solution, and performing solid-liquid separation to obtain a liquid phase, namely the multifunctional ligand modified mixed halogen perovskite quantum dot.
3. The perovskite quantum dot of claim 1, wherein the functional group contained in the structure of the multifunctional ligand capable of forming a hydrogen bond with the halogen in the mixed-halogen perovskite quantum dot is one or more of an amino group, an imino group, a hydroxyl group, and a thiol group.
4. The perovskite quantum dot of claim 1, wherein the multifunctional ligand is a neutral amino acid, preferably one or more of tryptophan, glutamine, threonine, serine, asparagine, cysteine, and tyrosine.
5. The perovskite quantum dot of claim 1, wherein the molar ratio of multifunctional ligand to quantum dot is 0.1:1 to 1: 1.
6. The perovskite quantum dot as claimed in claim 1, wherein the multifunctional ligand is mixed with the mixed halogen perovskite quantum dot solution and stirred, and the filtrate is taken after solid-liquid separation, and the method specifically comprises the following steps: mixing the multifunctional ligand and the mixed halogen perovskite quantum dot solution, stirring at 300-600rpm for 15-30 minutes, centrifuging at 10000-15000rpm for 5-10 minutes, and taking the supernatant to obtain the mixed halogen perovskite quantum dot modified by the multifunctional ligand passivation.
7. Use of a perovskite quantum dot as defined in any one of claims 1 to 6 for the preparation of a light emitting diode, a photodetector or a solar cell.
8. A light emitting diode characterized in that the material of the light emitting layer comprises the perovskite quantum dot as claimed in any one of claims 1 to 6.
9. A photodetector characterised in that its light absorbing layer material comprises perovskite quantum dots according to any of claims 1 to 6.
10. A solar cell, characterized in that its light absorbing layer material comprises perovskite quantum dots according to any of claims 1 to 6.
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| CN114377724A (en) * | 2022-01-27 | 2022-04-22 | 山东大学 | Halide perovskite-based platinum monatomic photocatalytic material and preparation method and application thereof |
| CN115172520A (en) * | 2022-07-08 | 2022-10-11 | 陕西师范大学 | Method for improving efficiency and stability of all-inorganic perovskite solar cell |
| CN116218524A (en) * | 2023-03-07 | 2023-06-06 | 中国科学院宁波材料技术与工程研究所 | CsPbI 3 Quantum dot, synthesis method thereof and quantum dot light-emitting device |
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|---|---|---|---|---|
| CN112618794A (en) * | 2020-12-23 | 2021-04-09 | 蚌埠泰鑫材料技术有限公司 | Bone defect repair material based on modified perovskite quantum dots and preparation method thereof |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Non-Patent Citations (1)
| Title |
|---|
| DONGLIN JIA ET AL.: ""Dual Passivation of CsPbI3 Perovskite Nanocrystals with Amino Acid Ligands for Efficient Quantum Dot Solar Cells"", SMALL, vol. 16, pages 1 - 12 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114377724A (en) * | 2022-01-27 | 2022-04-22 | 山东大学 | Halide perovskite-based platinum monatomic photocatalytic material and preparation method and application thereof |
| CN115172520A (en) * | 2022-07-08 | 2022-10-11 | 陕西师范大学 | Method for improving efficiency and stability of all-inorganic perovskite solar cell |
| CN115172520B (en) * | 2022-07-08 | 2023-09-22 | 陕西师范大学 | Method for improving efficiency and stability of all-inorganic perovskite solar cell |
| CN116218524A (en) * | 2023-03-07 | 2023-06-06 | 中国科学院宁波材料技术与工程研究所 | CsPbI 3 Quantum dot, synthesis method thereof and quantum dot light-emitting device |
| CN116218524B (en) * | 2023-03-07 | 2024-04-19 | 中国科学院宁波材料技术与工程研究所 | CsPbI3Quantum dot, synthesis method thereof and quantum dot light-emitting device |
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