CN109456763B - Synthesis method of lead-iodine perovskite quantum dots - Google Patents
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Abstract
A method for synthesizing lead-iodine perovskite quantum dots relates to quantum dot synthesis. Mixing Cs2CO3Mixing at least one of methylamine and formamidine acetate, oleic acid and octadecene according to a stoichiometric ratio, introducing nitrogen, heating, and cooling to room temperature for later use; mixing PbO with oleic acid and octadecene according to stoichiometric ratio, introducing nitrogen, heating until PbO powder is dissolved, and cooling to room temperature for later use; preheating the obtained solution, mixing the preheated solution with oleylamine and octadecene solution respectively, heating the mixed solution to 50-300 ℃, adding iodotrimethylsilane, reacting, and cooling the reaction device by using an ice water bath to obtain the solution, namely the lead-iodine perovskite quantum dot. The obtained lead-iodine perovskite quantum dot has high fluorescence quantum efficiency and stability. Such high performance and stable lead-iodine perovskite quantum dots contribute to future display and lighting applications. The operation is simple, the raw materials are easy to obtain, and the method is easy to popularize and apply on a large scale.
Description
Technical Field
The invention relates to quantum dot synthesis, in particular to a method for synthesizing lead-iodine-perovskite quantum dots.
Background
In recent years, lead-halo perovskite quantum dots have received much attention due to their high fluorescence quantum efficiency, high color purity, and luminescent color that can be adjusted over the entire visible range. Compared with the traditional cadmium-based chalcogenide quantum dots, the lead-halogen perovskite quantum dots also have low preparation temperature and high defect tolerance. These excellent properties enable the lead-halogen perovskite quantum dots to be applied in many fields, such as light emitting diodes, lasers, photodetectors, and photocatalysis. However, their practical application is greatly limited by poor chemical and structural stability (ACS Energy lett.,2017,2(9), 2071-. In particular, the red fluorescent lead-iodine perovskite quantum dots are sensitive to light, oxygen, water and high temperature, and the optically active perovskite phase can only exist at room temperature for a plurality of weeks. Recent studies show that the iodine-rich synthetic environment contributes to the improvement of the stability of the lead-iodine perovskite quantum dots (chem. mater, 2017,29(12), 5168-5173), and the iodine-rich surface structure generated in the environment can induce lattice stress and increase the difficulty of phase transformation. The existing synthesis method highly depends on lead iodide as a raw material, and the ratio of iodide ions/lead ions in a reaction system is only 2 and is far lower than the standard stoichiometric ratio of 3. Therefore, in order to further increase the ratio of iodide ions/lead ions in the reaction system to obtain more stable lead-iodine perovskite quantum dots, it is necessary to develop a new synthesis method.
Disclosure of Invention
The present invention is directed to solve the above problems of the background art, and an object of the present invention is to provide a method for synthesizing a stable lead-iodine perovskite quantum dot.
The invention uses trimethyl iodosilane as raw material, and comprises the following steps:
1) mixing Cs2CO3Mixing at least one of methylamine and formamidine acetate, oleic acid and octadecene according to a stoichiometric ratio, introducing nitrogen, heating, and cooling to room temperature for later use;
in the step 1), the temperature of the temperature rise can be 80-120 ℃, and the time of the temperature rise can be 1 hour.
2) Mixing PbO with oleic acid and octadecene according to stoichiometric ratio, introducing nitrogen, heating until PbO powder is dissolved, and cooling to room temperature for later use;
in step 2), the temperature of the temperature rise may be 120 ℃.
3) Preheating the solution obtained in the steps 1) and 2), respectively mixing the solution with oleylamine and octadecene solution, heating the mixed solution to 50-300 ℃, adding iodotrimethylsilane, reacting, and cooling the reaction device by using an ice water bath to obtain the solution, namely the lead-iodine-perovskite quantum dots.
In step 3), the temperature of the preheating may be 80 ℃.
The Cs2CO3Methylamine, formamidine acetate, PbO, oleic acid, oleylamine and trimethyl iodosilane in a molar ratio of (0-1): 1-10): 2-10).
The lead-iodine perovskite quantum dot prepared by the method has high fluorescence quantum efficiency (more than 90%) and stability. Such high performance and stable lead-iodine perovskite quantum dots contribute to future display and lighting applications. In addition, the method is simple to operate, easily available in raw materials and easy to popularize and apply on a large scale.
The invention is to inject the iodotrimethylsilane into the sample containing Cs2CO3At least one of methylamine and formamidine acetate, PbO, oleic acid and octadecene of oleylamine, the synthesized quantum dot has a fluorescence quantum yield close to 100% while exhibiting high room-temperature standing stability. The invention can further improve the performance of the lead-iodine-perovskite quantum dots and is beneficial to future display and illumination application.
Drawings
FIG. 1 is a graph showing fluorescence, UV and visible absorption spectra of a sample obtained in example 1 of the present invention.
FIG. 2 is an XRD pattern of samples obtained in example 1 of the present invention on different days of standing.
FIG. 3 is a TEM image of a sample obtained in example 1 of the present invention.
Detailed Description
The following examples will further illustrate the present invention with reference to the accompanying drawings.
Comparative example 1
0.2035g of cesium carbonate were weighed, added to a 100mL flask along with 0.625mL of oleic acid and 10mL of octadecene, purged with nitrogen, heated to 120 ℃ until cesium carbonate was completely dissolved, and then cooled to room temperature for further use. 0.087g of lead iodide, 0.5mL of oleic acid, 0.5mL of oleylamine and 5mL of octadecene were weighed out and added into a 100mL flask, nitrogen was introduced, the flask was heated to 120 ℃ until lead iodide was completely dissolved, then the flask was heated to 150 ℃ and 0.4mL of a preheated cesium oleate solution was rapidly injected, and the flask was cooled in an ice-water bath after 5 seconds. The fluorescence of this sample disappeared completely after 5 days.
Example 1
Mixing Cs2CO3(analytically pure) and oleic acid (analytically pure) were mixed in a stoichiometric ratio of 1: 3, followed by addition of 5mL octadecene (analytically pure), nitrogen was bubbled through, the mixture was heated to 120 ℃ until the powder was completely dissolved, and then cooled to room temperature. The Cs ion concentration of the resulting solution was 5.0mol/42.5 mL. Mixing PbO (analytically pure) and oleic acid at a stoichiometric ratio of 1: 3, adding 5mL octadecene, and introducing nitrogenThe mixture was heated to 120 ℃ until the powder was completely dissolved and then cooled to room temperature. The concentration of Pb ions in the resulting solution was 1.0 mol/L. Preheating the two solutions at 80 ℃, mixing 0.4mL and 0.5mL with 0.4mL oleylamine and 5mL octadecene respectively, heating the mixture to 150 ℃, then quickly injecting 0.2mL of iodotrimethylsilane, reacting for 5s, and cooling with an ice-water bath device to obtain the solution CsPbI3Crude product of perovskite quantum dots.
The material obtained in example 1 was characterized by fluorescence spectroscopy and uv-vis absorption spectroscopy, and the results are shown in fig. 1. The XRD pattern of example 1 is shown in fig. 2, from which it can be seen that the XRD pattern of the obtained sample coincides with the card numbered 161481 in the Inorganic Crystal Structure Database (ICSD), demonstrating that it is a cubic phase crystal structure and can be maintained for 43 days. The TEM image of example 1 is shown in FIG. 3, from which it can be seen that the resulting sample has a single particle size of 11 nm.
Example 2
Mixing Cs2CO3(analytically pure) and oleic acid (analytically pure) were mixed in a stoichiometric ratio of 1: 3, followed by addition of 5mL octadecene (analytically pure), nitrogen was bubbled through, the mixture was heated to 120 ℃ until the powder was completely dissolved, and then cooled to room temperature. The Cs ion concentration of the resulting solution was 5.0mol/42.5 mL. Mixing PbO (analytically pure) and oleic acid according to a stoichiometric ratio of 1: 3, adding 5mL of octadecene, introducing nitrogen, heating the mixture to 120 ℃, completely dissolving the powder, and cooling to room temperature. The concentration of Pb ions in the resulting solution was 1.0 mol/L. Preheating the two solutions at 80 ℃, mixing 0.4mL and 0.5mL with 0.5mL oleylamine and 5mL octadecene respectively, heating the mixture to 150 ℃, then quickly injecting 0.2mL of iodotrimethylsilane, reacting for 5s, and cooling with an ice-water bath device to obtain the solution CsPbI3Crude product of perovskite quantum dots.
Example 3
Mixing Cs2CO3(analytically pure) and oleic acid (analytically pure) were mixed in a stoichiometric ratio of 1: 2, followed by addition of 5mL octadecene (analytically pure), nitrogen was bubbled through, the mixture was heated to 120 ℃ until the powder was completely dissolved, and then cooled to room temperature. Cs ion in the obtained solutionThe concentration was 5.0mol/42.5 mL. Mixing PbO (analytically pure) and oleic acid according to a stoichiometric ratio of 1: 2, adding 5mL of octadecene, introducing nitrogen, heating the mixture to 120 ℃, completely dissolving the powder, and cooling to room temperature. The concentration of Pb ions in the resulting solution was 1.0 mol/L. Preheating the two solutions at 80 ℃, mixing 0.4mL and 0.5mL with 0.4mL oleylamine and 5mL octadecene respectively, heating the mixture to 150 ℃, then quickly injecting 0.2mL of iodotrimethylsilane, reacting for 5s, and cooling with an ice-water bath device to obtain the solution CsPbI3Crude product of perovskite quantum dots.
Example 4
Formamidine acetate (analytically pure) and oleic acid (analytically pure) were mixed in a stoichiometric ratio of 1: 3, followed by addition of 5mL octadecene (analytically pure), nitrogen was bubbled through, the mixture was heated to 80 ℃ until the powder was completely dissolved, and then cooled to room temperature. The resulting solution had a formamidine ion concentration of 5.0mol/42.5 mL. Mixing PbO (analytically pure) and oleic acid according to a stoichiometric ratio of 1: 3, adding 5mL of octadecene, introducing nitrogen, heating the mixture to 120 ℃, completely dissolving the powder, and cooling to room temperature. The concentration of Pb ions in the resulting solution was 1.0 mol/L. Preheating the two solutions at 80 ℃, mixing 0.4mL and 0.5mL with 0.4mL oleylamine and 5mL octadecene respectively, heating the mixture to 80 ℃, then quickly injecting 0.2mL of iodotrimethylsilane, reacting for 5s, and cooling the mixture by using an ice-water bath cooling device to obtain the solution, namely the crude product of the formamidine lead-perovskite quantum dots.
Example 5
Mixing methylamine and oleic acid (analytically pure) at the concentration of 30-33 wt.% according to the stoichiometric ratio of 1: 3 (methylamine: oleic acid), then adding 5mL octadecene (analytically pure), introducing nitrogen, heating the mixture to 80 ℃, reacting for 1h, and cooling to room temperature. The concentration of methylamine cation in the resulting solution was 5.0mol/42.5 mL. Mixing PbO (analytically pure) and oleic acid according to a stoichiometric ratio of 1: 3, adding 5mL of octadecene, introducing nitrogen, heating the mixture to 80 ℃, completely dissolving the powder, and cooling to room temperature. The concentration of Pb ions in the resulting solution was 1.0 mol/L. Preheating the two solutions at 80 ℃, mixing 0.4mL and 0.5mL of oleylamine with 0.4mL of octadecene with 5mL of octadecene respectively, heating the mixture to 80 ℃, then quickly injecting 0.2mL of iodotrimethylsilane, reacting for 5s, and cooling the mixture by using an ice water bath cooling device to obtain a solution, namely the crude product of the methylamine lead perovskite quantum dot.
Claims (1)
1. A synthesis method of lead-iodine perovskite quantum dots is characterized by comprising the following steps:
1) mixing Cs2CO3Mixing at least one of methylamine and formamidine acetate, oleic acid and octadecene according to a stoichiometric ratio, introducing nitrogen, heating, and cooling to room temperature for later use; the temperature rise is 80-120 ℃, and the time for temperature rise is 1 h;
2) mixing PbO with oleic acid and octadecene according to stoichiometric ratio, introducing nitrogen, heating until PbO powder is dissolved, and cooling to room temperature for later use; the temperature for raising the temperature is 120 ℃;
3) preheating the solution obtained in the steps 1) and 2), respectively mixing the solution with oleylamine and octadecene solution, heating the mixed solution, adding iodotrimethylsilane, reacting, and cooling the reaction device by using ice water bath to obtain the solution, namely the lead-iodine perovskite quantum dots;
the Cs2CO3Methylamine, formamidine acetate, PbO, oleic acid, oleylamine and trimethyl iodosilane in a molar ratio of (0-1): 1-10): 2-10);
the preheating temperature is 80 ℃; the temperature rise is 50-300 ℃.
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| CN106379932A (en) * | 2016-08-19 | 2017-02-08 | 湖北大学 | A method of synthesizing a perovskite CsPbX3 quantum dot at room temperature |
| CN106753356A (en) * | 2016-11-09 | 2017-05-31 | 南方科技大学 | Preparation method of perovskite type nanocrystalline |
| CN108192606A (en) * | 2018-03-08 | 2018-06-22 | 河北工业大学 | Full-inorganic perovskite quantum dot preparation method |
| CN108531987A (en) * | 2018-03-30 | 2018-09-14 | 南京理工大学 | A kind of preparation method that halogen perovskite is nanocrystalline |
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| CN106379932A (en) * | 2016-08-19 | 2017-02-08 | 湖北大学 | A method of synthesizing a perovskite CsPbX3 quantum dot at room temperature |
| CN106753356A (en) * | 2016-11-09 | 2017-05-31 | 南方科技大学 | Preparation method of perovskite type nanocrystalline |
| CN108192606A (en) * | 2018-03-08 | 2018-06-22 | 河北工业大学 | Full-inorganic perovskite quantum dot preparation method |
| CN108531987A (en) * | 2018-03-30 | 2018-09-14 | 南京理工大学 | A kind of preparation method that halogen perovskite is nanocrystalline |
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