CN114410292A - Preparation method of passivated inorganic perovskite nanocrystalline - Google Patents
Preparation method of passivated inorganic perovskite nanocrystalline Download PDFInfo
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
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- 150000002367 halogens Chemical class 0.000 claims description 5
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- 238000010438 heat treatment Methods 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
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- 238000004519 manufacturing process Methods 0.000 claims 2
- 125000001475 halogen functional group Chemical group 0.000 claims 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
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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
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- B82—NANOTECHNOLOGY
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Abstract
The invention provides a preparation method of passivated inorganic perovskite nanocrystalline, belonging to the technical field of nano materials. The luminous efficiency and stability of the inorganic perovskite nanocrystalline passivated by the chelating agent ligand are greatly improved, and the inorganic perovskite nanocrystalline can keep high-efficiency luminescence for more than 1 month in an ethanol solvent; the prepared nanocrystalline material not only has enhanced stability in a polar environment, but also has obviously improved external quantum efficiency and brightness after being prepared into a luminescent device, and has a very bright prospect in the fields of luminescent display, photovoltaics, detectors and the like.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method of passivated inorganic perovskite nano crystals.
Background
Due to the excellent photoelectric characteristics of the inorganic cesium-lead halogen perovskite nano-crystal, the inorganic cesium-lead halogen perovskite nano-crystal is widely applied to the fields of luminous display, photovoltaics, detectors and the like, and a breakthrough research result is obtained. The traditional cesium-lead halide perovskite nanocrystalline material is easy to fall off in a polar environment due to the instability of a ligand of the traditional cesium-lead halide perovskite nanocrystalline material, so that the stability and efficiency of the perovskite nanocrystalline are reduced, and the development of the perovskite nanocrystalline material in the application field is severely restricted. Therefore, how to enhance the stability of inorganic perovskite nanocrystalline materials has become a hot research point. Generally, some amine compounds, sulfonates, phosphonates and the like are usually selected for passivating the inorganic perovskite nanocrystals, most of the ligands are bonded to lead ions at a single site, the bonding capability is weak, and the perovskite nanocrystals cannot be effectively protected.
Disclosure of Invention
The invention aims to provide a preparation method of passivated inorganic perovskite nano-crystals, which aims to solve at least one technical problem in the background technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of passivated inorganic perovskite nanocrystalline, which is characterized in that an inorganic lead halogen perovskite nanocrystalline colloidal solution is synthesized by a high-temperature injection method, then the inorganic lead halogen perovskite nanocrystalline colloidal solution is mixed with chelating agent ligand powder, and after a certain period of stirring, the inorganic lead halogen perovskite nanocrystalline colloidal solution is filtered, centrifuged and re-dispersed to obtain a passivated nanocrystalline solution.
Preferably, the synthesis of the inorganic lead-halogen perovskite nanocrystalline colloidal solution by using a high-temperature injection method comprises the following steps:
taking Cs2CO3Adding octadecene and oleic acid, and fully dissolving to obtain cesium oleate;
and taking lead iodide, adding octadecene, adding cesium oleate, reacting and cooling to obtain the inorganic lead halide perovskite nanocrystalline colloidal solution.
Preferably, the inorganic lead-halogen perovskite nanocrystalline colloidal solution is mixed with an anti-solvent methyl acetate, centrifuged and the supernatant is discarded, and the obtained precipitate is dispersed in n-octane again and repeated twice; and after cleaning, mixing the nano-crystalline colloidal solution with the chelating agent ligand, stirring at room temperature, filtering to separate solid chelating agent particles, and centrifugally cleaning to obtain the nano-crystalline colloidal solution after the chelating agent is passivated.
Preferably, the ligand of the chelating agent comprises an organic compound containing 2 or more than 2 special functional groups, and the special functional groups are one or more of amine groups, carboxyl groups, aldehyde groups, cyano groups, phosphate groups, thiol groups or sulfonate groups.
Preferably, 200mgCs is taken2CO3Adding 10ml of octadecene and 0.6ml of oleic acid into a three-neck flask, stirring and vacuum drying for 1h, introducing argon, and heating to 150 ℃ until the solution becomes clear, namely Cs2CO3Fully dissolved to form cesium oleate.
Preferably, 174mg of lead iodide is added into another three-neck flask, 10ml of octadecene is added, stirring and vacuum drying are carried out for 1h, then argon protection is introduced, vacuum pumping is carried out again, and the steps are repeated three times.
Preferably, the ratio of the anti-solvent methyl acetate to the inorganic lead halogen perovskite nanocrystalline colloidal solution is 2: 1-3: 1.
Preferably, the chelating agent ligand is a mixture of ethylenediamine tetraacetic acid and L-glutathione.
The invention has the beneficial effects that: the luminous efficiency and stability of the inorganic perovskite nanocrystalline passivated by the chelating agent ligand are greatly improved, and the inorganic perovskite nanocrystalline can keep high-efficiency luminescence for more than 1 month in an ethanol solvent; the prepared nanocrystalline material not only has enhanced stability in a polar environment, but also has obviously improved external quantum efficiency and brightness after being prepared into a luminescent device, and has a very bright prospect in the fields of luminescent display, photovoltaics, detectors and the like.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic diagram of changes of inorganic lead-halogen perovskite nanocrystals in an ethanol environment after being treated with a chelating agent ligand according to an embodiment of the present invention. Wherein, fig. 1(a) is a schematic diagram of PL intensity variation of perovskite nanocrystals dispersed in an ethanol solution for 1 month; (after normalization); fig. 1(b) is a PL spectrum change diagram before and after 1 month of dispersion of perovskite nanocrystals in an ethanol solution.
Fig. 2 is a schematic diagram illustrating the increase of the photoluminescence quantum yield of the inorganic lead-halogen perovskite nanocrystals after the passivation of the chelating agent ligand according to the embodiment of the present invention. Wherein (a) is a photoluminescence quantum yield (PLQY) of perovskite nanocrystals after passivation by a chelating agent versus untreated CsPbI3 nanocrystals, (b) is a CsPbI3 nanocrystal treated with EDTA, (c) is a CsPbI3 nanocrystal treated with GSH, and (d) is a CsPbI3 nanocrystal treated with both EDTA and GSH.
Fig. 3 is a schematic diagram of an external quantum efficiency curve of an inorganic lead-halogen perovskite nanocrystal passivated with a chelating agent as a light emitting layer after being prepared into a device according to an embodiment of the invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below by way of the drawings are illustrative only and are not to be construed as limiting the invention.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
As used herein, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
In the description of the present specification, the terms "first", "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
For the purpose of facilitating an understanding of the present invention, the present invention will be further explained by way of specific embodiments with reference to the accompanying drawings, which are not intended to limit the present invention.
It should be understood by those skilled in the art that the drawings are merely schematic representations of embodiments and that the elements shown in the drawings are not necessarily required to practice the invention.
Example 1
In this embodiment 1, a preparation method of a passivated inorganic perovskite nanocrystal includes the following steps:
a. collecting 200mgCs2CO3Adding 10ml of octadecene and 0.6ml of oleic acid into a three-neck flask, stirring and vacuum drying for 1h, introducing argon, and heating to 150 ℃ until the solution becomes clear, namely Cs2CO3Sufficiently dissolve to form Cs-olate;
b. 174mg of PbI2Adding into another three-neck flask, adding 10ml of octadecene, stirring and vacuum drying for 1h, introducing argon for protection, vacuumizing again, and repeating for three times to ensure the lowest possible water oxygen content in the reaction system;
c. will be filled with PbI2The temperature of the three-neck flask is raised to 170 ℃, then the Cs-Oleate solution is injected into the three-neck flask, and the three-neck flask is immediately cooled in an ice-water bath after reacting for 5s to obtain dark red CsPbI3A nanocrystalline colloidal solution;
d. mixing the obtained colloidal solution with an anti-solvent methyl acetate, centrifuging and discarding the supernatant, dispersing the obtained precipitate in n-octane again, and repeating twice;
e. after the cleaning is finished, mixing the nano-crystalline colloidal solution with a chelating agent ligand (selected in this time, Ethylene Diamine Tetraacetic Acid (EDTA) and L-Glutathione (GSH)), slowly stirring at room temperature for 12h, filtering to separate solid chelating agent particles, and centrifugally cleaning according to the method of the step d to obtain the nano-crystalline colloidal solution after the chelating agent is passivated.
The invention has the beneficial effects that: the method has the advantages of low material cost, strong operability and obviously improved stability, and the inorganic lead-halogen perovskite nano-crystal with passivated chelating agent ligand is prepared by regulating and controlling experimental parameters. The material can stably emit light in a polar environment, and the external quantum efficiency and brightness of a luminescent device prepared by the material are obviously improved, so that the application of the material in the field of luminescent display is facilitated.
Example 2
This embodiment 2 provides a method for preparing inorganic lead-halogen perovskite nanocrystals through post-treatment passivation of chelating agents, which includes the following steps:
a. collecting 200mgCs2CO3Adding 10ml of octadecene and 0.6ml of oleic acid into a three-neck flask, stirring and vacuum drying for 1h, introducing argon, and heating to 150 ℃ until the solution becomes clear, namely Cs2CO3Sufficiently dissolve to form Cs-olate;
b. 174mg of PbI2Adding into another three-neck flask, adding 10ml of octadecene, stirring and vacuum drying for 1h, introducing argon for protection, vacuumizing again, and repeating for three times to ensure the lowest possible water oxygen content in the reaction system;
c. will be filled with PbI2The temperature of the three-neck flask is raised to 170 ℃, then the Cs-Oleate solution is injected into the three-neck flask, and the three-neck flask is immediately cooled in an ice-water bath after reacting for 5s to obtain dark red CsPbI3A nanocrystalline colloidal solution;
d. mixing the obtained colloidal solution with an anti-solvent methyl acetate, centrifuging and discarding the supernatant, dispersing the obtained precipitate in n-octane again, and repeating twice;
e. and d, after cleaning, mixing the nanocrystalline colloidal solution with chelating agent powder, slowly stirring at room temperature for 12 hours, filtering to separate solid chelating agent particles, and centrifugally cleaning according to the step d to obtain the chelating agent-passivated nanocrystalline colloidal solution.
Example 3
This embodiment 3 provides a method for preparing a luminescent device with a nano-crystal passivated by a chelating agent, including the following steps:
And 2, firstly, carrying out ultraviolet-ozone plasma treatment on the substrate for 90 seconds to increase the wettability of the substrate.
And 3, carrying out PEDOT: PSS was spin-coated on an ITO substrate at 4000 rpm in an atmospheric environment and annealed at 150 ℃ for 15 minutes.
Step 4, spin-coating 2mg/ml of Poly-TPD on a substrate at 4000 rpm in a nitrogen environment, and annealing at 130 ℃ for 10 min;
and 6, respectively preparing a TPBi electron transmission layer of 40nm, a LiF electrode modification layer of 2.5nm and an Al electrode of 100nm by using evaporation equipment to obtain the light-emitting device.
In summary, in the preparation method of the passivated inorganic perovskite nanocrystal, the multidentate chelating agent is used as the surface ligand to passivate the perovskite nanocrystal, and the multidentate chelating agent has a strong binding effect with surface lead ions, so that the surface ligand can replace the original ligand, the defect state density of the surface is reduced, the surface is passivated, the sensitivity of the surface ligand to the environment is greatly reduced, and the performance of the surface ligand in a light-emitting display device is improved. The provided method for post-treatment by using the chelating agent ligand can effectively solve the problem that the inorganic perovskite nanocrystalline is unstable in a polar environment. The chelating agent ligand has a plurality of functional groups to act on the lead ions together, so that the dangling bonds of the lead ions are reduced, the density of surface defect states is greatly reduced, the stability and the efficiency are greatly improved, and the application of the inorganic perovskite nanocrystal in the field of luminescence display is promoted.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts based on the technical solutions disclosed in the present invention.
Claims (8)
1. A preparation method of passivated inorganic perovskite nanocrystalline is characterized by synthesizing inorganic lead halogen perovskite nanocrystalline colloidal solution by a high-temperature injection method, then mixing the colloidal solution with chelating agent ligand powder, stirring for a certain time, filtering, centrifuging, and re-dispersing to obtain passivated nanocrystalline solution.
2. A method of preparing passivated inorganic perovskite nanocrystals according to claim 1 wherein the synthesis of the inorganic lead-halo perovskite nanocrystal colloidal solution using high temperature injection comprises:
taking Cs2CO3Adding octadecene and oleic acid, and fully dissolving to obtain cesium oleate;
and taking lead iodide, adding octadecene, adding cesium oleate, reacting and cooling to obtain the inorganic lead halide perovskite nanocrystalline colloidal solution.
3. A process for preparing passivated inorganic perovskite nanocrystals according to claim 2 wherein the inorganic lead halide perovskite nanocrystal colloidal solution is mixed with the anti-solvent methyl acetate, centrifuged and the supernatant discarded, the resulting precipitate is re-dispersed in n-octane and repeated twice; and after cleaning, mixing the nano-crystalline colloidal solution with the chelating agent ligand, stirring at room temperature, filtering to separate solid chelating agent particles, and centrifugally cleaning to obtain the nano-crystalline colloidal solution after the chelating agent is passivated.
4. The method according to claim 3, wherein the chelating agent ligand comprises an organic compound containing 2 or more than 2 special functional groups, and the special functional groups are one or more of amine groups, carboxyl groups, aldehyde groups, cyano groups, phosphate groups, thiol groups or sulfonate groups.
5. The method for preparing passivated inorganic perovskite nanocrystals according to claim 2, wherein 200mgCs are taken2CO3Adding 10ml of octadecene and 0.6ml of oleic acid into a three-neck flask, stirring and vacuum drying for 1h, introducing argon, and heating to 150 ℃ until the solution becomes clear, namely Cs2CO3Fully dissolved to form cesium oleate.
6. A process for preparing passivated inorganic perovskite nanocrystals according to claim 5 wherein 174mg of lead iodide is added to another three-necked flask, 10ml of octadecene is added, stirred and vacuum dried for 1h, then argon is introduced to protect it, and vacuum is re-pumped three times.
7. The method for preparing passivated inorganic perovskite nanocrystals according to claim 3, wherein the ratio of the anti-solvent methyl acetate to the inorganic lead halide perovskite nanocrystal colloidal solution is 2:1 to 3: 1.
8. A method of preparing passivated inorganic perovskite nanocrystals according to claim 4 wherein the chelator ligand is a mixture of ethylenediaminetetraacetic acid and L-glutathione.
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