CN113980669A - High-stability perovskite quantum dot and preparation method thereof - Google Patents
High-stability perovskite quantum dot and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 abstract description 6
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- QWANGZFTSGZRPZ-UHFFFAOYSA-N aminomethylideneazanium;bromide Chemical compound Br.NC=N QWANGZFTSGZRPZ-UHFFFAOYSA-N 0.000 description 2
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
- C07C257/12—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to hydrogen atoms
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Abstract
The invention discloses a high-stability perovskite quantum dot and a preparation method thereof. Even in a high-temperature and high-humidity environment, the fluorescence intensity of the perovskite quantum dots can still be maintained relatively stable. After coating and film forming, the fluorescence intensity can still be maintained above 90% at high temperature of 150 ℃ or under humidity of 85%. The perovskite quantum dot with high stability is expected to be applied to the field of display screens and the field of electroluminescent diodes. The method provides an effective and feasible solution for improving the high-temperature stability of the perovskite quantum dot, and expands the application range of the perovskite quantum dot.
Description
Technical Field
The invention belongs to the technical field of perovskite quantum dot preparation, and particularly relates to a high-stability perovskite quantum dot and a preparation method thereof.
Background
The perovskite quantum dots have great application potential in the photoelectric and electro-optical conversion field due to the excellent characteristics of strong light absorption capacity, high carrier mobility, good defect tolerance, relatively balanced charge transmission process, solution-soluble processing and the like, and are widely concerned. In addition, the perovskite quantum dot has the unique advantages of quantum dot, such as quantum confinement effect, high color purity, adjustable band gap, continuously adjustable luminescent color and suitability for flexible film preparation.
However, perovskite has a special ionic crystal structure, so that the humidity, the temperature and the illumination of the perovskite can influence the service life of the perovskite to a certain extent. Poor thermal and humidity stability leads to rapid degradation under high temperature and high humidity environment, thereby causing the photoelectric performance of the device to be degraded, so that the stability needs to be improved urgently. The preparation methods of perovskite quantum dots commonly used at present comprise a hot injection method, a ligand-assisted coprecipitation method and a ball milling method. Oleic acid, oleylamine and other long-chain organic ligands are generally used in synthesis, but the ligands are unstable in combination with perovskite crystals, and the ligands are easy to desorb from the surfaces of quantum dots, particularly in quantum dot thin films, so that the quantum dots generate a large number of surface defects. In device applications, these surface defects will irreversibly trap charge carriers, inducing non-radiative recombination leading to fluorescence quenching, reduced fluorescence quantum efficiency and poor stability. In addition, the optical performance of the perovskite is deteriorated with the increase of temperature, the perovskite quantum dots are decomposed or phase-changed at about 85 ℃, and the photoelectric device generally generates more heat in the operation process, so the application of the photoelectric device is very unfavorable. Obviously, the stability problem of perovskite quantum dots seriously hinders the application of perovskite quantum dots in photoelectric devices.
Coating a layer of polymer on the surface of the perovskite quantum dot is one of the main methods for solving the problems. The coated layer of polymer can form a core-shell structure with the perovskite quantum dots, so that the perovskite quantum dots are protected, and the phase stability of the perovskite quantum dots is maintained. However, the conventional polymer coating method only mixes the polymer with the perovskite quantum dots, does not coordinate with perovskite surface atoms, has the problems of perovskite segregation, poor coating effect and the like, and cannot effectively inhibit the decomposition of the perovskite and inhibit the diffusion of water and oxygen under severe environments such as high temperature and high humidity. Therefore, a suitable polymer coupling coating method is found, and the method has great significance for obtaining the perovskite quantum dot material with high luminous efficiency and high efficiency and stability.
Disclosure of Invention
The invention aims to provide a high-stability perovskite quantum dot and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
providing a monovalent cation precursor comprising one or more of cesium (Cs), Formamidine (FA), Methylammonium (MA);
providing a lead source precursor containing an anhydride polymer;
and adding the precursor containing univalent cations into the lead source precursor for reaction to obtain the high-stability perovskite quantum dot. In the reaction, in the perovskite quantum dot forming process, oxygen atoms in the anhydride and lead atoms in the perovskite form coordination, so that the perovskite quantum dot is coated with the anhydride in an in-situ coupling mode, the stability of the perovskite quantum dot is improved, and particularly when the perovskite quantum dot is prepared by adopting a hot injection method reaction, the stability of the obtained perovskite quantum dot is excellent when the injection temperature is above 160 ℃.
Further, the stability refers to the combination of shelf stability, high temperature stability, and water and oxygen resistance stability.
Further, the anhydride-containing polymer comprises one or more of poly (isobutylene-alt-maleic anhydride), polymaleic anhydride, polysebacic anhydride, and styrene maleic anhydride copolymer.
Further, the lead source includes lead acetate (Pb (AC)2) Lead chloride (PbCl)2) Lead bromide (PbBr)2) Lead iodide (PbI)2) One or two of them.
Further, the mass ratio of the acid anhydride-containing polymer to the lead source is 0.01-5. Particularly, when the mass ratio of the two is 0.5-5, the prepared perovskite quantum dot has a better stability effect, and if the mass ratio is lower than 0.5, the improvement on the stability of the product is not particularly obvious, but the prepared product can well improve the electrical property of the surface of the perovskite quantum dot and improve the conductivity of the perovskite quantum dot, so that the problem of injection of a current carrier can be improved when the perovskite quantum dot is applied to the field of photoelectric devices, and the electroluminescent efficiency is improved.
The invention has the following beneficial effects:
the invention provides a method for preparing a high-stability perovskite quantum dot, which is characterized in that an anhydride-containing polymer is added in the process of synthesizing the perovskite quantum dot, so that the polymer and a group in a lead source precursor act to generate a ring-opening reaction, and a polymer ligand is coupled and coated on the surface of the perovskite quantum dot, wherein an oxygen atom in an anhydride group and a lead atom in the perovskite can be coordinated and firmly combined, so that the perovskite crystal structure is effectively protected. The perovskite thin film after being coated and formed can keep stable fluorescence intensity in a high-temperature and high-humidity environment. The method provides an effective and feasible solution for improving the stability of the perovskite quantum dots, and expands the application range of the perovskite quantum dots.
Drawings
Fig. 1 shows the uv-vis spectroscopy and the fluorescence spectrum of the stable perovskite quantum dot obtained in example 1 of the present invention.
FIG. 2 is a graph showing the comparison of the fluorescence spectrum of the perovskite quantum dot thin film without the anhydride-containing polymer and the fluorescence spectrum of the stable perovskite quantum dot thin film with the anhydride polymer in example 1 of the present invention at high temperature and room temperature.
FIG. 3 is a graph showing the comparison of the fluorescence spectrum of the perovskite quantum dot thin film without the anhydride-containing polymer and the stable perovskite quantum dot thin film with the anhydride polymer in example 1 of the present invention under the atmosphere with 85% humidity and the fluorescence spectrum under the nitrogen atmosphere in the glove box.
Fig. 4 is an ultraviolet-visible spectrum and a fluorescence spectrum of the stable perovskite quantum dot obtained in example 2 of the present invention.
Detailed Description
The invention provides a method for preparing high-stability perovskite quantum dots, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The method for preparing the high-stability perovskite quantum dot mainly comprises the following steps:
s10, providing a monovalent cation precursor containing one or more of cesium (Cs), Formamidine (FA), Methylammonium (MA);
s20, providing a lead source precursor containing an anhydride polymer;
s30, adding the univalent cation precursor into the lead source precursor for reaction to obtain the high-stability perovskite quantum dot.
In some embodiments, such anhydride-containing polymers may include, but are not limited to, poly (isobutylene-alt-maleic anhydride), polymaleic anhydride, polysebacic anhydride, styrene maleic anhydride copolymers, and the like, as well as mixed polymers thereof in varying proportions, such as polymaleic anhydride and polysebacic anhydride in a 1: 1 are mixed and added.
In some embodiments, the stability of the perovskite quantum dots may include shelf stability, high temperature stability, water and oxygen resistance stability, etc., of the quantum dot solution or quantum dot thin film. The storage stability refers to that the perovskite quantum dot solution is still clear and does not precipitate after the solution is stored at normal temperature for a long time, or the phase structure and the optical performance of the perovskite quantum dot remain unchanged or change little after the perovskite quantum dot film is stored at normal temperature for a long time; the high-temperature stability means that the perovskite quantum dots can still maintain relatively stable fluorescence intensity in a high-temperature environment (generally 80-150 ℃); the water and oxygen resistance stability means that the perovskite quantum dots can still maintain stable fluorescence intensity in a humid atmosphere environment and do not have phase change.
In some embodiments, the method of observing high temperature stability of stable perovskite quantum dots is: taking a proper amount of the perovskite quantum dots prepared in the embodiment of the invention, spin-coating the perovskite quantum dot solution on a substrate by using a spin coater, heating the substrate on a heating table after spin-coating film formation, and monitoring the change of the fluorescence intensity in real time.
In some embodiments, the polymer containing anhydride groups may be dissolved in an amine-based solvent, including but not limited to oleylamine, octylamine, and the like.
In some embodiments, the lead source precursor includes lead acetate (Pb (AC)2) Lead chloride (PbCl)2) Lead bromide (PbBr)2) Lead iodide (PbI)2) And perovskite quantum dots with different luminescent colors can be realized by mixing lead sources in different proportions.
In some embodiments, the monovalent cation precursor in S10 may be cesium oleate cs (oa) and the method of preparation may be: weighing cesium carbonate Cs2CO3Into a three-necked flask, followed by adding Oleic Acid (OA) to the flask for dissolving cesium carbonate (Cs)2CO3) And Octadecene (ODE) as a solvent, vacuumizing the three-neck flask, stirring for a period of time, and filling the three-neck flask with an inert atmosphere.
In some embodiments, the monovalent cation precursor in S10 may be formamidine acetate (FA-acetate) and may be prepared by: 5mmol of FA-acetate was weighed into a three-necked flask, followed by addition of 20mL of Oleic Acid (OA) to the flask, evacuation of the three-necked flask and stirring for a while, then, charging an inert atmosphere into the three-necked flask, and heating and stirring.
In some embodiments, the monovalent cation precursor in S10 may be formamidine bromide (FABr), which is dissolved in N, N-Dimethylformamide (DMF) solvent to make a 0.8mol/L solution of FABr.
In some embodiments, the method of purifying quantum dots may include the following steps, but is not limited to this purification method: transferring the stock solution into a centrifugal tube for high-speed centrifugation, taking the supernatant after centrifugation, and adding a certain amount of anti-solvent to precipitate perovskite quantum dots; after the solution is subjected to high-speed centrifugation treatment, the precipitate is dispersed in octane or toluene and filtered by a 0.22-micron organic filter head, so that a stable perovskite quantum dot solution is obtained. Under certain conditions, the steps can be repeated, and the anti-solvent is continuously added into the perovskite quantum dot solution and the solution is centrifuged at high speed.
In some embodiments, the high-stability perovskite quantum dots can be used in the field of display screens and can also be used in the field of electroluminescent diodes.
The invention is illustrated in further detail by the following examples:
example 1
CsPbBr3Preparing quantum dots: weighing 72.3mg of PbBr2144.6mg of poly (isobutylene-alt-maleic anhydride) was added to a 25mL three-necked flask, to which was added 5mL of Octadecene (ODE), 2mL of Oleic Acid (OA), and 3mL of oleylamine (OAm); the three-necked flask was evacuated to remove excess components such as oxygen from the apparatus, and then heated in an inert atmosphereThe process keeps the magnetic stirring state until 170 ℃; 0.4mL of the prepared cesium oleate precursor is quickly injected into a lead source precursor, and after the cesium oleate precursor reacts for 5s, the cesium oleate precursor is cooled by an ice water bath to obtain stable CsPbBr3And (4) quantum dot stock solution. And obtaining the perovskite quantum dots for testing through subsequent purification treatment. The surface of the perovskite quantum dot of the embodiment is coupled and coated with more perovskite polymers, and the perovskite quantum dot has better high-temperature stability and stability in a high-humidity atmosphere environment. FIG. 1 shows CsPbBr in this example3Ultraviolet-visible spectroscopy and fluorescence spectroscopy of quantum dots. FIG. 2 is a graph showing the comparison of the fluorescence spectrum at high temperature and the fluorescence spectrum at room temperature between the perovskite quantum dot thin film without the anhydride-containing polymer and the stable perovskite quantum dot thin film with the anhydride polymer added in the embodiment of the present invention. FIG. 3 is a graph showing the comparison of the fluorescence spectrum of the perovskite quantum dot thin film without the anhydride-containing polymer and the stable perovskite quantum dot thin film with the anhydride polymer in example 1 of the present invention under the atmosphere with 85% humidity and the fluorescence spectrum under the nitrogen atmosphere in the glove box. After the perovskite quantum dot solution added with the anhydride polymer is placed for a long time at normal temperature, the perovskite quantum dot solution is still clear and does not precipitate, and after the perovskite quantum dot film is placed for a long time at normal temperature, the phase structure and the optical performance of the perovskite quantum dots are also kept unchanged. On the contrary, compared with the perovskite quantum dot solution without the anhydride polymer, the perovskite quantum dot solution has a large amount of precipitates after being placed for a long time at normal temperature due to ligand loss, and the original properties are damaged.
Example 2
CsPbI3Preparing quantum dots: weighing 88mg of PbI21.2mg of poly (isobutylene-alt-maleic anhydride) was added to a 25mL three-necked flask, to which was added 5mL of Octadecene (ODE), 1.5mL of Oleic Acid (OA), and 1.8mL of oleylamine (OAm); vacuumizing the three-neck flask for 20min to remove excessive components such as water and oxygen in the device, heating to 170 ℃ in an inert atmosphere, and keeping the magnetic stirring state in the process; 0.4mL of the prepared cesium oleate precursor is quickly injected into a lead source precursor for mixing, and after the cesium oleate precursor reacts for 5s, the cesium oleate precursor is quickly cooled by an ice water bath to obtain the stable CsPbI3And (4) quantum dot stock solution. Passing through a subsequent purification siteAnd finally, obtaining the perovskite quantum dots for testing. CsPbI as shown in FIG. 43Ultraviolet-visible spectroscopy and fluorescence spectroscopy of quantum dots. The perovskite quantum dot surface of the embodiment is coated with a few polymers in a coupling mode, and compared with the perovskite quantum dot coated with a lot of polymers in a coupling mode, the high-temperature stability and the water-oxygen stability of the perovskite quantum dot are not obviously improved, but the electrical property of the perovskite quantum dot surface can be well improved, the conductivity of the perovskite quantum dot can be improved, the injection problem of carriers can be improved when the perovskite quantum dot is applied to the field of photoelectric devices, and the electroluminescence efficiency can be improved.
Example 3
CsPbBr3Preparing quantum dots: weighing 72.3mg of PbBr2、414mg ZnBr272.3mg polymaleic anhydride, 72.3mg poly (isobutylene-alt-maleic anhydride) was added to a 25mL three-necked flask, to which was added 5mL Octadecene (ODE), 2mL Oleic Acid (OA), and 3mL oleylamine (OAm); vacuumizing the three-neck flask to remove excessive components such as water and oxygen in the device, heating to 160 ℃ in an inert atmosphere, and keeping the magnetic stirring state in the process; 0.4mL of the prepared cesium oleate precursor is quickly injected into a lead source precursor, and after the cesium oleate precursor reacts for 8s, the cesium oleate precursor is cooled by an ice water bath to obtain stable CsPbBr3And (4) quantum dot stock solution. And obtaining the stable perovskite quantum dots through subsequent purification treatment. The embodiment can synthesize CsPbBr in blue light direction3Quantum dots, and can maintain good stability.
Example 4
FAPbBr3Room temperature preparation of quantum dots: firstly, 0.4mol/L PbBr is prepared2N, N-Dimethylformamide (DMF) precursor. Weighing 18.4mg of poly (isobutylene-alt-maleic anhydride) into a 10mL sample bottle, and adding prepared formamidine bromide (FABr) precursor and lead bromide (PbBr)2) The precursor and Oleic Acid (OA) were 250. mu.L each, and oleylamine (OAm) was 35. mu.L each, and they were mixed by vortex stirring to prepare a mixed solution. Taking 8mL of trichloromethane in a beaker, and keeping magnetic stirring; then dropwise adding the mixed solution, and stirring for 35s after the reaction starts to obtain yellow-green FAPBBr3And (4) quantum dot stock solution. Adding a raw solution into the raw solution in a volume ratio of 1: 1 acetonitrile, quantum dots are rapidly separated by centrifugationAnd (4) precipitating. Discarding the supernatant and redispersing the precipitated FAPBR with n-octane3And (4) quantum dots. Filtering to obtain FAPBBr for testing3A quantum dot solution. The perovskite quantum dot synthesized by the embodiment has poor stability improvement effect, the fluorescence intensity is obviously reduced at about 80 ℃, and the synthesized FAPBR3The quantum dot solution is obviously turbid after being placed overnight.
Example 5
FAPbBr3Preparing quantum dots: 69.6mg of lead bromide (PbBr) was weighed2) 72mg of poly (isobutylene-alt-maleic anhydride) was added to a 25mL three-necked flask, to which was added 5mL of Octadecene (ODE), 1mL of Oleic Acid (OA), and 0.7mL of oleylamine (OAm); vacuumizing the three-neck flask to remove excessive components such as water and oxygen in the device, heating to 170 ℃ in an inert atmosphere, and keeping the magnetic stirring state in the process; quickly injecting 2.5mL of prepared formamidine acetate precursor into a lead source precursor, reacting for 5s, and cooling by using an ice water bath to obtain stable FAPBBr3And (4) quantum dot stock solution. Adding 10mL of toluene and 5mL of acetonitrile into the stock solution, centrifuging at a high speed, dissolving the precipitate with octane, and filtering to obtain FAPBR for testing3Perovskite quantum dots. The surface of the perovskite quantum dot of the embodiment is coupled and coated with more perovskite polymer, and compared with the FAPBR synthesized at room temperature in the embodiment 43The perovskite quantum dot has better high-temperature stability and water resistance and oxidation resistance stability in a high-humidity atmospheric environment.
In conclusion, the invention provides a preparation method for improving the stability of perovskite quantum dots, which is characterized in that an anhydride-containing polymer is added in the process of synthesizing the perovskite quantum dots, so that the coupled coating of a polymer ligand is realized on the surface of the perovskite quantum dots, wherein oxygen atoms in anhydride groups and lead atoms in the perovskite can be coordinated and firmly combined, and the perovskite crystal structure is effectively protected. Particularly, perovskite quantum dots with excellent standing stability, temperature stability, water resistance and oxidation resistance stability can be obtained by regulating the proportion of reactants and combining a heat injection method, and after the perovskite quantum dots are coated into a perovskite thin film, the fluorescence intensity can still keep relatively stable (the fluorescence intensity can still keep more than 90% at a high temperature of 150 ℃ or under an environment with 85% of humidity) even in a high-temperature and high-humidity environment, so that the perovskite quantum dots are expected to be applied to the field of display screens and the field of electroluminescent diodes. The method provides an effective and feasible solution for improving the stability of the perovskite quantum dots, and expands the application range of the perovskite quantum dots.
Claims (7)
1. A method for preparing high-stability perovskite quantum dots is characterized by comprising the following steps:
1) providing a monovalent cation precursor comprising one or more of cesium (Cs), Formamidine (FA), Methylammonium (MA);
2) providing a lead source precursor containing an anhydride polymer;
3) and adding the univalent cation precursor into the lead source precursor for reaction to obtain the high-stability perovskite quantum dot.
2. The method for preparing the perovskite quantum dot with high stability according to claim 1, wherein the step 3) is carried out by means of heat injection.
3. The method for preparing high-stability perovskite quantum dots according to claim 1, wherein the stability refers to placement stability, high temperature stability, and water and oxygen resistance stability.
4. The method for preparing the high-stability perovskite quantum dot according to claim 1, wherein the acid anhydride-containing polymer comprises one or more of poly (isobutylene-alt-maleic anhydride), polymaleic anhydride, polysebacic anhydride and styrene maleic anhydride copolymer.
5. The method for preparing high-stability perovskite quantum dots according to claim 1, wherein the lead source comprises lead acetate (Pb (AC)2) Lead chloride (PbCl)2) Lead bromide (PbBr)2) Lead iodide (PbI)2) One or two of them.
6. The method for preparing the perovskite quantum dot with high stability according to claim 1, wherein the mass ratio of the acid anhydride-containing polymer to the lead source is 0.01-5, preferably 0.5-5.
7. A high stability perovskite quantum dot prepared by the method of any one of claims 1 to 6.
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