CN106753356B - Preparation method of perovskite type nanocrystalline - Google Patents

Preparation method of perovskite type nanocrystalline Download PDF

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CN106753356B
CN106753356B CN201611034988.9A CN201611034988A CN106753356B CN 106753356 B CN106753356 B CN 106753356B CN 201611034988 A CN201611034988 A CN 201611034988A CN 106753356 B CN106753356 B CN 106753356B
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drying
oleic acid
centrifugation
cesium salt
molar ratio
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CN106753356A (en
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王恺
孙小卫
刘皓宸
刘培朝
曹万强
郝俊杰
周子明
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Hubei University
Southwest University of Science and Technology
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Abstract

The invention relates to a preparation method of perovskite type nanocrystalline, which is CsPbXaYbWherein X is selected from any one of Cl, Br or I, Y is selected from any one of Cl, Br or I, X is different from Y, a is not less than 0, b is not less than 0, and a + b is 3; the method comprises the steps of mixing cesium salt, long-chain olefin and oleic acid, and heating for reaction under the protection of inert gas to obtain a cesium oleate solution; mixing PbO, ammonium halide and long-chain olefin, injecting oleylamine and oleic acid, heating, injecting cesium oleate solution under the protection of inert gas, reacting, and cooling to obtain CsPbXaYbPerovskite type nanocrystals. The method has the advantages that the type and the proportion of halogen can be regulated and controlled when the perovskite nanocrystalline is synthesized, the performance of the perovskite nanocrystalline is controlled, the method is simple, the synthesized perovskite nanocrystalline is good in photoelectric conversion performance, and meanwhile, the synthetic raw material adopts low-toxicity PbO, so that the method is green and environment-friendly.

Description

Preparation method of perovskite type nanocrystalline
Technical Field
The invention belongs to the field of photoelectric materials, relates to a preparation method of quantum dots, and particularly relates to a preparation method of perovskite type nanocrystals.
Background
In recent years, many studies on inorganic perovskite type quantum dots exist, and the inorganic perovskite type quantum dots have unique performance, simple preparation method, adjustable wavelength of emitted light in a visible light band, narrow half-peak width and high luminous efficiency, and have strong application potential in the application fields of white light LEDs, QLEDs, photodetectors and the like.
CsPbBr3Compared with general quantum dot containing isolating particle, the perovskite quantum dot has stronger ion characteristic, so that it is very sensitive to polar solvent and surfactant, CsPbBr3The inorganic perovskite quantum dot has a dissolution equilibrium principle, CsPbBr3The size of the inorganic perovskite quantum dot is adjusted by washing a polar solvent or adding a surfactant under the room temperature condition and stirring, so that the change of 10 nm-1000 nm is realized.
Furthermore, CsPbBr3The complex ligand of Br and oleylamine on the surface of the perovskite quantum dot has large surface activity and is very unstable, and the complex ligand is easy to lose in the separation and purification processes, thereby causing poor colloidal stability and fluorescence quenching, and being not beneficial to CsPbBr3In the application of perovskite quantum dots, especially in QLED application, the characteristics of the material are the basis of excellent device performance, so that the preparation of high-quality perovskite quantum dots is very necessary.
CsPbBr appeared for the first time in 20153However, the current density, Current Efficiency (CE) and External Quantum Efficiency (EQE) of the QLED are not high, and after that, many research teams prepare CsPbBr by surface engineering of materials and synthesis of perovskite dual-phase component composite materials3The inorganic perovskite luminescent material improves the performance of the QLED.
CN 105647530 a discloses a method for preparing metal halide inorganic perovskite quantum dots, which is described. Firstly, metal halide salt BX2And AX in DMSO, adding surfactant, rapidly injecting the mixture into the reaction solvent, and finally BX2Rapidly react with AX under the action of a surfactant to generate ABX with different morphologies3Type metal halide inorganic perovskite quantum dots.
CN 105733574A discloses a method for preparing perovskite quantum dots by a low-temperature solution method, wherein the method adopts a solution injection method to synthesize metal halide perovskite quantum dots with uniform size and good dispersibility. The method comprises the steps of preserving the temperature of a reaction solvent at a certain temperature, stirring, quickly injecting metal halide precursor salt into the reaction solvent, and finally cooling the reaction solvent to room temperature by water to obtain the metal halide perovskite quantum dot with high luminous efficiency.
However, the halogen atom X is a key factor influencing the performance of the perovskite quantum dot, and high-quality CsPbBr3The enrichment of Br atoms on the surface can achieve the effect of self-passivation, and CsPbBr can be used for simultaneously3The perovskite quantum dot surface may be passivated by a complex of bromine and oleylamine. While the halogen proportion in the synthesis method of the inorganic perovskite type nanocrystalline is fixed and invariable, PbX2The material Pb: X is 1:2, and the perovskite material has poor performance due to the shortage of halogen atoms because of the atomic ratio Pb: X is 1:3 of the perovskite quantum dots.
Therefore, it is very important to research a preparation method of perovskite nanocrystal which can regulate the type and proportion of halogen and control the performance of perovskite nanocrystal during synthesis of perovskite nanocrystal, has simple method and has good photoelectric conversion performance of the synthesized perovskite nanocrystal.
Disclosure of Invention
Aiming at the prior art with PbX2The invention provides a preparation method of perovskite type nanocrystalline, aiming at solving the problem that the proportion of halogen is insufficient in the reaction process and the performance of the synthesized perovskite quantum dot is poor due to the fact that raw materials are insufficient, wherein the method can regulate the type and proportion of the halogen and control the performance of the perovskite nanocrystalline when the perovskite nanocrystalline is synthesized, the method is simple, and the synthesized perovskite nanocrystalline has good photoelectric conversion performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the perovskite type nanocrystal is characterized in that the perovskite type nanocrystal is CsPbXaYbWherein X is selected from any one of Cl, Br or I, Y is selected from any one of Cl, Br or I, X is different from Y, a is not less than 0, b is not less than 0, and a + b is 3;
the method comprises the following steps:
(1) mixing cesium salt, long-chain olefin and oleic acid, and heating for reaction under the protection of inert gas to obtain a cesium oleate solution;
(2) mixing PbO, ammonium halide and long-chain olefin, then injecting oleylamine and oleic acid, heating, injecting the cesium oleate solution obtained in the step (1) under the protection of inert gas, reacting, and cooling to obtain CsPbXaYbPerovskite type nanocrystals.
The perovskite type nanocrystalline synthesized by the method can be used as perovskite type quantum dots. The invention adopts PbO and ammonium halide as raw materials to replace lead halide adopted in the prior art, and overcomes the defects of halogen deficiency and poor perovskite type nanocrystalline performance caused by fixed proportion of halogen and Pb which are brought by taking lead halide as raw materials in the prior art. Meanwhile, the proportion of the halogen can be controlled, so that the halogen in the perovskite type nanocrystalline obtained in the synthesis is doped, and the nature of the perovskite type nanocrystalline is controlled by controlling the type and proportion of the halogen.
The following technical solutions are preferred but not limited to the technical solutions provided by the present invention, and the technical objects and advantages of the present invention can be better achieved and realized by the following technical solutions.
As a preferable technical scheme of the invention, the cesium salt in the step (1) is selected from CsCl, CsBr, CsF and Cs2SO4、CsNO3、CH3COOCs or Cs2CO3Any one or a combination of at least two of the following, typical but non-limiting examples being: combinations of CsCl and CsBr, combinations of CsCl and CsF, combinations of CsBr and CsF, Cs2SO4And CsNO3Combination of (1), CsNO3And CH3Combinations of COOCs, Cs2SO4And Cs2CO3Combinations of CsCl, CsBr and CsF, etc., preferably Cs2CO3。
Preferably, the long-chain olefin of step (1) is selected from any one or a combination of at least two of eicosene, octadecene, hexadecene, tetradecene, or dodecene, typical but non-limiting examples of which are: combinations of eicosene and octadecene, combinations of octadecene and hexadecene, combinations of hexadecene and tetradecene, combinations of tetradecene and dodecene, or combinations of eicosene, octadecene and hexadecene, etc., with octadecene being more preferred.
Preferably, the molar ratio of the long-chain olefin to the cesium salt in step (1) is (35-75: 1), such as 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1 or 75:1, but not limited to the recited values, and other non-recited values included in the range of the values are also applicable, and more preferably 50: 1.
Preferably, the molar ratio of oleic acid to cesium salt in step (1) is (2-5): 1, such as 2, 2.2, 2.5, 2.8, 3, 3.2, 3.5, 4, 4.5, 4.8 or 5, but not limited to the recited values, and other non-recited values included in the range of values are also applicable, and more preferably 3.2: 1.
As a limited means of the present invention, the temperature of the heating reaction in the step (1) is 120 to 180 ℃, for example, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, or 180 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range of values are also applicable, preferably 140 to 160 ℃, and more preferably 150 ℃.
Preferably, the heating reaction time in the step (1) is 0.5-3 h, such as 0.5h, 0.6h, 0.8h, 1h, 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h or 3h, and the like, and further preferably 1 h.
Preferably, the inert gas in step (1) is selected from any one of nitrogen, argon or helium or a combination of at least two thereof, typical but non-limiting examples of which are: a combination of helium and argon, a combination of helium and nitrogen, a combination of nitrogen and argon, or a combination of helium, nitrogen and argon, and the like, and argon is more preferable.
As a preferred technical scheme of the invention, the oleic acid is dried before the oleic acid is added in the step (1).
Preferably, the drying temperature is 100 to 150 ℃, such as 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited within the range of the values are also applicable, and more preferably 110 to 130 ℃, and particularly preferably 120 ℃.
Preferably, the drying time is 10 to 120min, such as 10min, 15min, 30min, 60min, 90min, 105min, 110min, 115min or 120min, but not limited to the recited values, and other non-recited values included in the range of the values are also applicable, and more preferably 30 to 90min, and particularly preferably 60 min.
Preferably, the combined cesium salt, long chain olefin, and oleic acid are dried prior to the heating reaction described in step (1).
Preferably, vacuum degassing is performed before the drying.
Preferably, the drying temperature is 100 to 150 ℃, such as 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃, but is not limited to the recited values, and other non-recited values included in the value range are also applicable, more preferably 110 to 130 ℃, and particularly preferably 120 ℃;
preferably, the drying time is 10 to 120min, such as 10min, 15min, 30min, 60min, 90min, 105min, 110min, 115min or 120min, but not limited to the recited values, and other non-recited values included in the range of the values are also applicable, and more preferably 30 to 90min, and particularly preferably 60 min.
As a preferable technical scheme of the invention, the ammonium halide in the step (2) is selected from NH4Cl、NH4Br or NH4Any one or a combination of at least two of I, typical but non-limiting examples of which are: NH (NH)4Cl and NH4Combination of Br, NH4Br and NH4Combination of I, NH4I and NH4Combination of Cl or NH4Cl、NH4Br and NH4Combinations of I, and the like.
In a preferred embodiment of the present invention, in step (2), the molar ratio of PbO to cesium salt is (4 to 12):1, such as 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, or 12:1, but the molar ratio is not limited to the recited values, and other unrecited values included in the numerical range are also applicable, preferably 8: 1.
Preferably, the molar ratio of the ammonium halide to the cesium salt in step (2) is (20-40: 1), such as 20:1, 22:1, 25:1, 28:1, 30:1, 32:1, 35:1, 38:1, or 40:1, but not limited to the recited values, and other non-recited values included in the range of the values are also applicable, and more preferably 32: 1.
Preferably, the molar ratio of the long-chain olefin to the cesium salt in step (2) is (600 to 1000):1, such as 600:1, 650:1, 700:1, 750:1, 800:1, 850:1, 900:1, 950:1 or 1000:1, but not limited to the recited values, and other non-recited values included in the range of the values are also applicable, and 665:1 is more preferred.
Preferably, the molar ratio of the injected oleic acid to the cesium salt in the step (2) is (50-80): 1, such as 50:1, 53:1, 55:1, 57:1, 60:1, 63:1, 65:1, 67:1, 70:1, 73:1, 75:1, 78:1 or 80:1, but not limited to the enumerated values, and other non-enumerated values included in the numerical range are also applicable, and more preferably 67: 1.
Preferably, the molar ratio of oleylamine to cesium salt injected in step (2) is (50-80): 1, such as 50:1, 54:1, 56:1, 60:1, 64:1, 66:1, 70:1, 74:1, 76:1 or 80:1, but not limited to the recited values, and other unrecited values included in the range of values are also applicable, and more preferably 66: 1.
In a preferred embodiment of the present invention, the heating temperature in the step (2) is 120 to 250 ℃, for example, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range of values are also applicable, preferably 150 to 200 ℃, and more preferably 180 ℃.
Preferably, the reaction time in step (2) is 1 to 15s, such as 1s, 2s, 3s, 4s, 5s, 6s, 7s, 8s, 9s, 10s, 11s, 12s, 13s, 14s, or 15s, but not limited to the recited values, and other non-recited values included in the range of the values are also applicable, more preferably 3 to 10s, and particularly preferably 5 s.
Preferably, the inert gas in step (2) is selected from any one of nitrogen, argon or helium or a combination of at least two thereof, typical but non-limiting examples of which are: a combination of helium and argon, a combination of helium and nitrogen, a combination of nitrogen and argon, or a combination of helium, nitrogen and argon, and the like, and argon is more preferable.
Preferably, the cooling in step (2) is selected from any one or a combination of at least two of natural cooling, ice-bath cooling or liquid nitrogen cooling, and typical but non-limiting examples of the combination are: a combination of natural cooling and ice-bath cooling, a combination of ice-bath cooling and liquid nitrogen cooling, a combination of natural cooling, ice-bath cooling and liquid nitrogen cooling, or the like, and further preferably ice-bath cooling.
As a preferred technical scheme of the invention, before adding oleylamine and oleic acid in the step (2), the PbO, ammonium halide and long-chain olefin mixture are dried.
Preferably, vacuum degassing is performed before the drying.
Preferably, the drying temperature is 100 to 150 ℃, such as 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited within the range of the values are also applicable, and more preferably 110 to 130 ℃, and particularly preferably 120 ℃.
Preferably, the drying time is 10 to 60min, such as 10min, 15min, 20min, 25min, 30min, 35min, 40min, 50min, 55min or 60min, but not limited to the recited values, and other non-recited values included in the range of the values are also applicable, more preferably 20 to 40min, and particularly preferably 30 min.
Preferably, the oleylamine and oleic acid are dried before being added in step (2).
Preferably, the drying temperature is 100 to 150 ℃, such as 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited within the range of the values are also applicable, and more preferably 110 to 130 ℃, and particularly preferably 120 ℃.
Preferably, the drying time is 10 to 120min, such as 10min, 15min, 30min, 60min, 90min, 105min, 110min, 115min or 120min, but not limited to the recited values, and other non-recited values included in the range of the values are also applicable, and more preferably 30 to 90min, and particularly preferably 60 min.
Preferably, after the addition of oleylamine and oleic acid in step (2), the mixed raw materials are dried.
Preferably, vacuum degassing is performed before the drying.
Preferably, the drying temperature is 100 to 150 ℃, such as 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited within the range of the values are also applicable, and more preferably 110 to 130 ℃, and particularly preferably 120 ℃.
Preferably, the drying time is 10 to 120min, such as 10min, 15min, 30min, 60min, 90min, 105min, 110min, 115min or 120min, but not limited to the recited values, and other non-recited values included in the range of the values are also applicable, and more preferably 30 to 90min, and particularly preferably 60 min.
As a preferable technical scheme of the invention, the CsPbX obtained in the step (2) is subjected toaYbPurifying the perovskite type nanocrystalline.
Preferably, the purification method is that acetone is added into the stock solution obtained by reacting and cooling the cesium oleate solution in the step (2), and first centrifugation is carried out to take out a precipitate; dispersing the precipitate in toluene, adding acetonitrile, performing second centrifugation, and taking the precipitate; dispersing the precipitate in n-hexane, performing third centrifugation, and collecting supernatant.
Preferably, the volume ratio of the added acetone to the stock solution is 1: 1.
Preferably, the rotation speed of the first centrifugation is 8000 to 12000rpm, such as 8000rpm, 8500rpm, 9000rpm, 9500rpm, 10000rpm, 11000rpm or 12000rpm, but is not limited to the enumerated values, and other non-enumerated values included in the numerical range are also applicable, and more preferably 10000 rpm.
Preferably, the time of the first centrifugation is 1 to 5min, such as 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min or 5min, but is not limited to the recited values, and other non-recited values included in the range of the values are also applicable, and more preferably 3 min.
Preferably, the volume ratio of toluene to acetonitrile is 1: 1.
Preferably, the rotation speed of the second centrifugation is 3000-8000 rpm, such as 3000rpm, 4000rpm, 5000, rpm, 6000rpm, 7000rpm, 8000rpm, etc., but not limited to the enumerated values, and other non-enumerated values included in the numerical range are also applicable, and further preferably 5000 rpm.
Preferably, the time of the second centrifugation is 0.5 to 2min, such as 0.5min, 1min, 1.5min, or 2min, but is not limited to the recited values, and other non-recited values included in the range of the values are also applicable, and more preferably 1 min.
Preferably, the rotation speed of the third centrifugation is 6000 to 10000rpm, such as 6000rpm, 7000rpm, 8000rpm, 9000rpm or 10000rpm, but not limited to the enumerated values, and other unrecited values included in the numerical range are also applicable, and further preferably 8000 rpm.
Preferably, the time of the third centrifugation is 2-8 min, such as 2min, 3min, 4min, 5min, 6min, 7min or 8min, but not limited to the recited values, and other non-recited values included in the value range are also applicable, and more preferably 4 min.
As a preferable technical scheme of the invention, the method comprises the following steps:
(1) drying oleic acid at 100-150 ℃ for 10-120 min, mixing cesium salt, long-chain olefin and oleic acid, degassing in vacuum, drying at 100-150 ℃ for 10-120 min, and heating to 120-180 ℃ under the protection of inert gas to react to obtain a cesium oleate solution;
(2) drying oleylamine and oleic acid at 100-150 ℃ for 10-120 min, mixing PbO, ammonium halide and long-chain olefin, vacuum degassing, drying at 100-150 ℃ for 10-60 min, injecting oleylamine and oleic acid, vacuum degassing, drying at 100-150 ℃ for 10-120 min, heating to 120-250 ℃, injecting the cesium oleate solution obtained in the step (1) under the protection of inert gas, rapidly reacting for 1-15 s, and cooling to obtain CsPbXaYbPerovskite type nanocrystals;
(3) for CsPbX obtained in the step (2)aYbPurifying the perovskite type nanocrystalline.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the preparation method of the perovskite type nanocrystalline provided by the invention adopts PbO and ammonium halide as raw materials, can adjust the type and proportion of halogen in the synthesized perovskite type nanocrystalline by adjusting the proportion of PbO and ammonium halide, and can selectively synthesize the perovskite type nanocrystalline according to the requirements of device performance.
(2) According to the preparation method of the perovskite type nanocrystalline, the purity of the prepared perovskite type nanocrystalline reaches 95%, and meanwhile, the fluorescence quantum yield of the prepared perovskite type nanocrystalline reaches 75% due to the fact that the proportion of halogen and Pb is guaranteed.
(3) The preparation method of the perovskite type nanocrystalline provided by the invention is simple, and low-toxicity PbO is used as a raw material, so that the damage to the environment is reduced, and the industrial production is facilitated.
Drawings
FIG. 1a shows CsPbCl synthesized by the preparation method of perovskite type nanocrystalline provided by the invention2.1Br0.9TEM images of perovskite quantum dots.
FIG. 1b is a schematic view of the present inventionCsPbBr synthesized by perovskite type nanocrystalline preparation method3TEM images of perovskite quantum dots.
FIG. 1c shows CsPbBr synthesized by the preparation method of perovskite type nanocrystal0.9I2.1TEM images of perovskite quantum dots.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The specific embodiment of the invention partially provides a preparation method of perovskite type nanocrystalline CsPbXaYbWherein X is selected from any one of Cl, Br or I, Y is selected from any one of Cl, Br or I, X is different from Y, a is not less than 0, b is not less than 0, and a + b is 3;
the method comprises the following steps:
(1) mixing cesium salt, long-chain olefin and oleic acid, and heating for reaction under the protection of inert gas to obtain a cesium oleate solution;
(2) mixing PbO, ammonium halide and long-chain olefin, then injecting oleylamine and oleic acid, heating, injecting the cesium oleate solution obtained in the step (1) under the protection of inert gas, reacting, and cooling to obtain CsPbXaYbPerovskite type nanocrystals.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
the parts presented in the following examples are all molar parts.
Example 1
A method of preparing perovskite nanocrystals, the method comprising the steps of:
(1) drying oleic acid at 100 ℃ for 120min, mixing 1 part of CsCl, 35 parts of eicosene and 2 parts of oleic acid, degassing in vacuum, drying at 100 ℃ for 120min, and heating to 120 ℃ under the protection of argon to react for 0.5h to obtain a cesium oleate solution;
(2) mixing oleylamineAnd oleic acid at 100 deg.C for 120min, 4 parts PbO, 20 parts NH4Mixing Cl and 600 parts of eicosene, vacuum degassing, drying at 100 ℃ for 60min, then injecting 50 parts of oleylamine and 50 parts of oleic acid, vacuum degassing, drying at 100 ℃ for 120min, heating to 120 ℃, injecting the cesium oleate solution obtained in the step (1) under the protection of argon, quickly reacting for 15s, and cooling in an ice bath;
(3) adding acetone with the same volume into the stock solution after the reaction and cooling in the step (2), centrifuging for 5min at 8000rpm, and taking a precipitate; dispersing the precipitate in toluene, adding equal volume of acetonitrile, centrifuging at 3000rpm for 2min, and collecting the precipitate; dispersing the precipitate in n-hexane, centrifuging at 6000rpm for 8min, and collecting supernatant to obtain perovskite CsPbCl3And (4) nanocrystals.
The purity of the prepared perovskite type nanocrystalline is 94.6%, and the fluorescence quantum yield is 74.6%.
Example 2
A method of preparing perovskite nanocrystals, the method comprising the steps of:
(1) drying oleic acid at 150 ℃ for 10min, mixing 1 part of CsBr, 75 parts of octadecene and 5 parts of oleic acid, vacuum degassing, drying at 150 ℃ for 10min, and heating to 180 ℃ under the protection of nitrogen to react for 3h to obtain a cesium oleate solution;
(2) drying oleylamine and oleic acid at 150 deg.C for 10min, adding 12 parts of PbO and 40 parts of NH4Mixing Br and 1000 parts of octadecene, vacuum degassing, drying at 150 ℃ for 10min, then injecting 80 parts of oleylamine and 80 parts of oleic acid, vacuum degassing, drying at 150 ℃ for 10min, heating to 250 ℃, injecting the cesium oleate solution obtained in the step (1) under the protection of nitrogen, quickly reacting for 1s, and cooling in an ice bath;
(3) adding acetone with the same volume into the stock solution after the reaction and cooling in the step (2), centrifuging at 12000rpm for 1min, and taking a precipitate; dispersing the precipitate in toluene, adding equal volume of acetonitrile, centrifuging at 8000rpm for 0.5min, and collecting the precipitate; dispersing the precipitate in n-hexane, centrifuging at 10000rpm for 2min, and collecting supernatant to obtain perovskite CsPbBr3And (4) nanocrystals.
The purity of the prepared perovskite type nanocrystalline is 95.3%, and the fluorescence quantum yield is 75.1%.
Example 3
A method of preparing perovskite nanocrystals, the method comprising the steps of:
(1) oleic acid was dried at 120 ℃ for 60min, 1 part Cs2I. Mixing 50 parts of hexadecene and 3.2 parts of oleic acid, degassing in vacuum, drying at 120 ℃ for 60min, and heating to 150 ℃ for reaction for 1h under the protection of argon to obtain a cesium oleate solution;
(2) oleylamine and oleic acid were dried at 120 ℃ for 60min, 8 parts of PbO, 32 parts of NH4Mixing I and 800 parts of hexadecene, vacuum degassing, drying at 120 ℃ for 0.5min, then injecting 66 parts of oleylamine and 67 parts of oleic acid, vacuum degassing, drying at 120 ℃ for 60min, heating to 180 ℃, injecting the cesium oleate solution obtained in the step (1) under the protection of nitrogen, rapidly reacting for 5s, and cooling in an ice bath;
(3) adding acetone with the same volume into the stock solution after the reaction and cooling in the step (2), centrifuging for 3min at 10000rpm, and taking a precipitate; dispersing the precipitate in toluene, adding equal volume of acetonitrile, centrifuging at 5000rpm for 1min, and collecting the precipitate; dispersing the precipitate in n-hexane, centrifuging at 8000rpm for 4min, collecting supernatant to obtain perovskite CsPbI3And (4) nanocrystal.
The purity of the prepared perovskite type nanocrystalline is 95.6%, and the fluorescence quantum yield is 74.5%.
Example 4
A method of preparing perovskite nanocrystals, the method comprising the steps of:
(1) drying oleic acid at 120 deg.C for 60min, adding 1 part of Cs2CO3Mixing 50 parts of octadecene and 3.2 parts of oleic acid, degassing in vacuum, drying at 120 ℃ for 60min, and heating to 150 ℃ for reaction for 1h under the protection of argon to obtain a cesium oleate solution;
(2) oleylamine and oleic acid were dried at 120 ℃ for 60min, 8 parts of PbO, 32 parts of NH4Br and 665 parts of octadecene, vacuum degassing, drying at 120 ℃ for 0.5min, then 66 parts of oleylamine and 67 parts of oleic acid, vacuum degassing, drying at 120 ℃ for 60min, heating to 180 ℃, injecting the cesium oleate solution obtained in the step (1) under the protection of nitrogen, quickly reacting for 5s, and cooling in an ice bath;
(3) adding acetone with the same volume into the stock solution after the reaction and cooling in the step (2), centrifuging for 3min at 10000rpm, and taking a precipitate; dispersing the precipitate in toluene, adding equal volume of acetonitrile, centrifuging at 5000rpm for 1min, and collecting the precipitate; dispersing the precipitate in n-hexane, centrifuging at 8000rpm for 4min, collecting supernatant to obtain perovskite CsPbBr3And (4) nanocrystals.
The purity of the prepared perovskite type nanocrystalline is 95.1%, and the fluorescence quantum yield is 76.6%.
Example 5
A method of preparing perovskite nanocrystals, the method comprising the steps of:
(1) oleic acid was dried at 120 ℃ for 60min, 1 part Cs2CO3Mixing 40 parts of octadecene and 4 parts of oleic acid, vacuum degassing, drying at 120 ℃ for 60min, heating to 150 ℃ under the protection of argon, and reacting for 1.5h to obtain a cesium oleate solution;
(2) oleylamine and oleic acid were dried at 120 ℃ for 60min, 9 parts of PbO, 30 parts of NH4Mixing I and 665 parts of octadecene, vacuum degassing, drying at 120 ℃ for 0.5min, then injecting 60 parts of oleylamine and 60 parts of oleic acid, vacuum degassing, drying at 120 ℃ for 60min, heating to 180 ℃, injecting the cesium oleate solution obtained in the step (1) under the protection of nitrogen, quickly reacting for 5s, and cooling in an ice bath;
(3) adding acetone with the same volume into the stock solution after the reaction and cooling in the step (2), centrifuging for 3min at 10000rpm, and taking a precipitate; dispersing the precipitate in toluene, adding equal volume of acetonitrile, centrifuging at 5000rpm for 1min, and collecting the precipitate; dispersing the precipitate in n-hexane, centrifuging at 8000rpm for 4min, collecting supernatant to obtain perovskite CsPbI3And (4) nanocrystals.
The purity of the prepared perovskite type nanocrystalline is 94.4%, and the fluorescence quantum yield is 74.7%.
Example 6
A method of preparing perovskite nanocrystals, the method comprising the steps of:
(1) drying oleic acid at 120 deg.C for 60min, adding 1 part of Cs2CO3Mixing 60 parts of octadecene and 4.5 parts of oleic acid, degassing in vacuum, drying at 120 ℃ for 60min, heating to 150 ℃ under the protection of argon, and reacting for 2h to obtain a cesium oleate solution;
(2) oleylamine and oleic acid were dried at 120 ℃ for 60min, 7 parts of PbO, 35 parts of NH4Mixing Cl and 665 parts of octadecene, vacuum degassing, drying at 120 ℃ for 0.5min, injecting 55 parts of oleylamine and 55 parts of oleic acid, vacuum degassing, drying at 120 ℃ for 60min, heating to 180 ℃, injecting the cesium oleate solution obtained in the step (1) under the protection of nitrogen, quickly reacting for 5s, and cooling in an ice bath;
(3) adding acetone with the same volume into the stock solution after the reaction and cooling in the step (2), centrifuging for 3min at 10000rpm, and taking a precipitate; dispersing the precipitate in toluene, adding equal volume of acetonitrile, centrifuging at 5000rpm for 1min, and collecting the precipitate; dispersing the precipitate in n-hexane, centrifuging at 8000rpm for 4min, collecting supernatant to obtain perovskite CsPbCl3And (4) nanocrystals.
The purity of the prepared perovskite type nanocrystalline is 94.2%, and the fluorescence quantum yield is 75.0%.
Example 7
A method of preparing perovskite nanocrystals, the method comprising the steps of:
(1) drying oleic acid at 120 deg.C for 60min, adding 1 part of Cs2CO3Mixing 50 parts of octadecene and 3.2 parts of oleic acid, degassing in vacuum, drying at 120 ℃ for 60min, and heating to 150 ℃ for reaction for 1h under the protection of argon to obtain a cesium oleate solution;
(2) oleylamine and oleic acid were dried at 120 ℃ for 60min, 8 parts of PbO, 32 parts of NH4Cl and NH4Mixture of Br (NH)4Cl and NH4Br of 2.1:0.9) and 700 parts of octadecene, vacuum degassing, drying at 120 ℃ for 0.5min, then injecting 66 parts of oleylamine and 67 parts of oleic acid, vacuum degassing, drying at 120 ℃ for 60min, heating to 180 ℃, injecting the cesium oleate solution obtained in step (1) under the protection of nitrogen, and rapidly degassingReacting for 5s, and cooling in ice bath;
(3) adding acetone with the same volume into the stock solution after the reaction and cooling in the step (2), centrifuging for 3min at 10000rpm, and taking a precipitate; dispersing the precipitate in toluene, adding equal volume of acetonitrile, centrifuging at 5000rpm for 1min, and collecting the precipitate; dispersing the precipitate in n-hexane, centrifuging at 8000rpm for 4min, collecting supernatant to obtain perovskite CsPbCl2.1Br0.9And (4) nanocrystals.
The purity of the prepared perovskite type nanocrystalline is 95.5%, and the fluorescence quantum yield is 77.3%.
Example 8
A method of preparing perovskite nanocrystals, the method comprising the steps of:
(1) oleic acid was dried at 120 ℃ for 60min, 1 part Cs2CO3Mixing 50 parts of octadecene and 3.2 parts of oleic acid, degassing in vacuum, drying at 120 ℃ for 60min, and heating to 150 ℃ for reaction for 1h under the protection of argon to obtain a cesium oleate solution;
(2) oleylamine and oleic acid were dried at 120 ℃ for 60min, 8 parts of PbO, 32 parts of NH4I and NH4Mixture of Br (NH)4I and NH4Br of 2.1:0.9) and 650 parts of octadecene, vacuum degassing, drying at 120 ℃ for 0.5min, then injecting 66 parts of oleylamine and 67 parts of oleic acid, vacuum degassing, drying at 120 ℃ for 60min, heating to 180 ℃, injecting the cesium oleate solution obtained in the step (1) under the protection of nitrogen, rapidly reacting for 5s, and cooling in an ice bath;
(3) adding acetone with the same volume into the stock solution after the reaction and cooling in the step (2), centrifuging for 3min at 10000rpm, and taking a precipitate; dispersing the precipitate in toluene, adding equal volume of acetonitrile, centrifuging at 5000rpm for 1min, and collecting the precipitate; dispersing the precipitate in n-hexane, centrifuging at 8000rpm for 4min, collecting supernatant to obtain perovskite CsPbBr0.9I2.1And (4) nanocrystals.
The purity of the prepared perovskite type nanocrystalline is 95.7%, and the fluorescence quantum yield is 76.8%.
Comparative example 1
A calciumThe preparation method of the titanium ore nanocrystal adopts PbBr as the raw material except for the step (2)2Instead of PbO and NH4The procedure was otherwise the same as in example 4 except for Br.
The purity of the prepared perovskite type nanocrystalline is 88.2%, and the fluorescence quantum yield is 52.1%.
Comparative example 2
A preparation method of perovskite nanocrystalline adopts PbI except for the raw material in the step (2)2Instead of PbO and NH4Except for the above step, the procedure was the same as in example 5.
The purity of the prepared perovskite type nanocrystalline is 86.7%, and the fluorescence quantum yield is 47.1%.
Comparative example 3
A preparation method of perovskite nanocrystalline adopts PbCl as raw material except step (2)2Instead of PbO and NH4The procedure was otherwise the same as in example 6 except for Cl.
The purity of the prepared perovskite type nanocrystalline is 87.1%, and the fluorescence quantum yield is 50.7%.
As can be seen from examples 4-6 and comparative examples 1-3, the invention adopts PbO and ammonium halide to replace lead halide as raw materials, and the fluorescence quantum yield of the prepared perovskite type nanocrystalline is obviously improved. The fluorescence quantum yield of the halogen mixed perovskite type nanocrystalline prepared in the embodiments 7 and 8 is also achieved, and is obviously better than that of the quantum dots in the comparative example. According to the preparation method disclosed by the invention, PbO and ammonium halide are adopted to replace lead halide to serve as raw materials, so that the proportion of halogen and Pb is controllable, and the fluorescence quantum yield of the prepared perovskite type nanocrystalline is improved.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (91)

1. The preparation method of the perovskite type nanocrystal is characterized in that the perovskite type nanocrystal is CsPbXaYbWherein X is selected from any one of Cl, Br or I, Y is selected from any one of Cl, Br or I, X is different from Y, a is not less than 0, b is not less than 0, and a + b is 3;
the method comprises the following steps:
(1) mixing cesium salt, long-chain olefin and oleic acid, and heating for reaction under the protection of inert gas to obtain a cesium oleate solution;
(2) mixing PbO, ammonium halide and long-chain olefin, then injecting oleylamine and oleic acid, heating, injecting the cesium oleate solution obtained in the step (1) under the protection of inert gas, reacting, and cooling to obtain CsPbXaYbPerovskite type nanocrystals;
(3) for CsPbX obtained in the step (2)aYbPurifying the perovskite type nanocrystalline.
2. The method according to claim 1, wherein the cesium salt in step (1) is selected from the group consisting of CsCl, CsBr, CsF and Cs2SO4、CsNO3、CH3COOCs or Cs2CO3Any one or a combination of at least two of them.
3. The method according to claim 2, wherein the cesium salt in the step (1) is Cs2CO3。
4. The method according to claim 1, wherein the long-chain olefin in step (1) is selected from any one or a combination of at least two of eicosene, octadecene, hexadecene, tetradecene, and dodecene.
5. The method according to claim 4, wherein the long-chain olefin in the step (1) is octadecene.
6. The preparation method according to claim 1, wherein the molar ratio of the long-chain olefin to the cesium salt in step (1) is (35-75): 1.
7. The method of claim 6, wherein the molar ratio of the long chain olefin to the cesium salt in step (1) is 50: 1.
8. The preparation method of claim 1, wherein the molar ratio of the oleic acid to the cesium salt in the step (1) is (2-5): 1.
9. The method of claim 8, wherein the molar ratio of oleic acid to cesium salt in step (1) is 3.2: 1.
10. The method according to claim 1, wherein the temperature of the heating reaction in step (1) is 120 to 180 ℃.
11. The method according to claim 10, wherein the temperature of the heating reaction in step (1) is 140 to 160 ℃.
12. The method according to claim 11, wherein the temperature of the heating reaction in the step (1) is 150 ℃.
13. The preparation method according to claim 1, wherein the heating reaction time in the step (1) is 0.5-3 h.
14. The method according to claim 13, wherein the heating reaction in step (1) is carried out for 1 hour.
15. The method according to claim 1, wherein the inert gas in step (1) is selected from any one of nitrogen, argon or helium or a combination of at least two of nitrogen, argon or helium.
16. The method according to claim 15, wherein the inert gas in the step (1) is argon gas.
17. The method according to claim 1, wherein the oleic acid is dried before the oleic acid is added in the step (1).
18. The method according to claim 17, wherein the drying temperature is 100 to 150 ℃.
19. The method according to claim 18, wherein the drying temperature is 110 to 130 ℃.
20. The method of claim 19, wherein the drying temperature is 120 ℃.
21. The method of claim 17, wherein the drying time is 10 to 120 min.
22. The method according to claim 21, wherein the drying time is 30 to 90 min.
23. The method of claim 22, wherein the drying time is 60 min.
24. The method of claim 1, wherein the combined cesium salt, long-chain olefin, and oleic acid are dried before the heating reaction in step (1).
25. The method of claim 24, wherein vacuum degassing is performed before the drying.
26. The method according to claim 24, wherein the drying temperature is 100 to 150 ℃.
27. The method according to claim 26, wherein the drying temperature is 110 to 130 ℃.
28. The method of claim 27, wherein the drying temperature is 120 ℃.
29. The method according to claim 24, wherein the drying time is 10 to 120 min.
30. The method according to claim 29, wherein the drying time is 30 to 90 min.
31. The method of claim 30, wherein the drying time is 60 min.
32. The method according to claim 1, wherein the ammonium halide in step (2) is selected from NH4Cl、NH4Br or NH4Any one or a combination of at least two of I.
33. The preparation method according to claim 1, wherein the molar ratio of PbO to cesium salt in step (2) is (4-12): 1.
34. The method of claim 33, wherein the molar ratio of PbO to cesium salt in step (2) is 8: 1.
35. The preparation method according to claim 1, wherein the molar ratio of the ammonium halide to the cesium salt in the step (2) is (20-40): 1.
36. The method of claim 35, wherein the molar ratio of ammonium halide to cesium salt in step (2) is 32: 1.
37. The preparation method according to claim 1, wherein the molar ratio of the long-chain olefin to the cesium salt in step (2) is (600-1000): 1.
38. The method of claim 37, wherein the molar ratio of the long chain olefin to the cesium salt in step (2) is 665: 1.
39. The preparation method according to claim 1, wherein the molar ratio of the injected oleic acid to the cesium salt in the step (2) is (50-80): 1.
40. The method of claim 39, wherein the molar ratio of the injected oleic acid to the cesium salt in step (2) is 67: 1.
41. The preparation method according to claim 1, wherein the molar ratio of the oleylamine to the cesium salt injected in the step (2) is (50-80): 1.
42. The method of claim 41, wherein the molar ratio of oleylamine to cesium salt injected in step (2) is 66: 1.
43. The method according to claim 1, wherein the heating temperature in the step (2) is 120 to 250 ℃.
44. The method according to claim 43, wherein the heating temperature in the step (2) is 150 to 200 ℃.
45. The method of claim 44, wherein the heating temperature in step (2) is 180 ℃.
46. The method according to claim 1, wherein the reaction time in step (2) is 1-15 s.
47. The method according to claim 46, wherein the reaction time in the step (2) is 3 to 10 seconds.
48. The method according to claim 47, wherein the reaction time in the step (2) is 5 seconds.
49. The method according to claim 1, wherein the inert gas in step (2) is selected from any one of nitrogen, argon or helium or a combination of at least two of nitrogen, argon or helium.
50. The method according to claim 49, wherein the inert gas in the step (2) is argon.
51. The method according to claim 1, wherein the cooling in step (2) is selected from any one of natural cooling, ice-bath cooling and liquid nitrogen cooling or a combination of at least two of them.
52. The method according to claim 51, wherein the cooling in step (2) is ice-bath cooling.
53. The method of claim 1, wherein the PbO, ammonium halide and long chain olefin mixture are dried before adding oleylamine and oleic acid in step (2).
54. The method of claim 53, wherein vacuum degassing is performed prior to the drying.
55. The method as claimed in claim 53, wherein the drying temperature is 100 to 150 ℃.
56. The method as claimed in claim 55, wherein the drying temperature is 110-130 ℃.
57. The method as claimed in claim 56, wherein the drying temperature is 120 ℃.
58. The method according to claim 53, wherein the drying time is 10 to 60 min.
59. The method as claimed in claim 58, wherein the drying time is 20-40 min.
60. The method as claimed in claim 59, wherein the drying time is 30 min.
61. The method of claim 1, wherein the oleylamine and the oleic acid are dried before the oleylamine and the oleic acid are added in the step (2).
62. The method as claimed in claim 61, wherein the drying temperature is 100-150 ℃.
63. The method as claimed in claim 62, wherein the drying temperature is 110-130 ℃.
64. The method as claimed in claim 63, wherein the drying temperature is 120 ℃.
65. The method as claimed in claim 61, wherein the drying time is 10-120 min.
66. The method as claimed in claim 65, wherein the drying time is 30 to 90 min.
67. The method as claimed in claim 66, wherein the drying time is 60 min.
68. The method of claim 1, wherein the mixed raw material is dried after adding oleylamine and oleic acid in the step (2).
69. The method of claim 68, wherein vacuum degassing is performed prior to said drying.
70. The method as claimed in claim 68, wherein the drying temperature is 100-150 ℃.
71. The method as claimed in claim 70, wherein the drying temperature is 110 to 130 ℃.
72. The method as claimed in claim 71, wherein the drying temperature is 120 ℃.
73. The method as claimed in claim 68, wherein the drying time is 10-120 min.
74. The method according to claim 73, wherein the drying time is 30 to 90 min.
75. The method of claim 74, wherein the drying time is 60 min.
76. The method according to claim 1, wherein the purification in step (3) is performed by adding acetone to the stock solution obtained by reacting and cooling the cesium oleate solution in step (2), performing a first centrifugation, and collecting a precipitate; dispersing the precipitate in toluene, adding acetonitrile, performing second centrifugation, and taking the precipitate; dispersing the precipitate in n-hexane, performing third centrifugation, and collecting supernatant.
77. The method of claim 76, wherein the volume ratio of the acetone added to the stock solution is 1: 1.
78. The method of claim 76, wherein the first centrifugation is performed at 8000 to 12000 rpm.
79. The method of claim 78, wherein the first centrifugation is performed at 10000 rpm.
80. The method of claim 76, wherein the first centrifugation is performed for 1-5 min.
81. The method of claim 80, wherein the first centrifugation is performed for 3 min.
82. The method of claim 76, wherein the volume ratio of toluene to acetonitrile is 1: 1.
83. The method of claim 76, wherein the second centrifugation is performed at 3000 to 8000 rpm.
84. The method of claim 83, wherein the second centrifugation is performed at 5000 rpm.
85. The method of claim 76, wherein the second centrifugation is performed for 0.5-2 min.
86. The method of claim 85, wherein the second centrifugation is performed for 1 min.
87. The method of claim 76, wherein the third centrifugation is performed at 6000 to 10000 rpm.
88. The method of claim 87, wherein the third centrifugation is performed at 8000 rpm.
89. The method of claim 76, wherein the third centrifugation is performed for 2-8 min.
90. The method of claim 89, wherein the time of the third centrifugation is 4 min.
91. The method for preparing according to claim 1, characterized in that it comprises the following steps:
(1) drying oleic acid at 100-150 ℃ for 10-120 min, mixing cesium salt, long-chain olefin and oleic acid, degassing in vacuum, drying at 100-150 ℃ for 10-120 min, and heating to 120-180 ℃ under the protection of inert gas to react to obtain a cesium oleate solution;
(2) drying oleylamine and oleic acid at 100-150 deg.C for 10-120 min, mixing PbO, ammonium halide and long chain olefin, vacuum degassing, drying at 100-150 deg.C for 10-60 min, injecting oleylamine and oleic acid, vacuum degassing, and drying at 1 ℃Drying at 00-150 ℃ for 10-120 min, heating to 120-250 ℃, injecting the cesium oleate solution obtained in the step (1) under the protection of inert gas, quickly reacting for 1-15 s, and cooling to obtain CsPbXaYbPerovskite type nanocrystals;
(3) for CsPbX obtained in the step (2)aYbPurifying the perovskite type nanocrystalline.
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