CN108531172B - Preparation method and application of hybrid perovskite microcrystalline luminescent material - Google Patents
Preparation method and application of hybrid perovskite microcrystalline luminescent material Download PDFInfo
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Abstract
The application discloses a perovskite microcrystalline material, which comprises a perovskite with a chemical formula shown as a formula I and a perovskite with a chemical formula shown as a formula II; AM (amplitude modulation)2X5Formula I; a. the4MX6Formula II; the perovskite shown in the formula I is embedded into the perovskite shown in the formula II; wherein A is selected from CH3NH3 +、NH＝CHNH3 +、C(NH2)3 +、R2NH3 +、Li+、Na+、Rb+Or Cs+At least one of; r2Selected from hydrogen, C1～C10Alkyl of (C)1～C10An unsaturated hydrocarbon group of (1); m is metal ions, and the metal is at least one of Ge, Sn, Pb, Sb, Bi, Cu, Mn, Sr, In, Tl and Ag; x is at least one selected from halogen anions. The perovskite microcrystal material has high luminous efficiency and good stability.
Description
Technical Field
The application relates to a preparation method and application of a hybrid perovskite microcrystalline luminescent material, belonging to the field of materials and preparation thereof.
Background
The perovskite material reported at present is mainly ABX3Structural perovskite materials, less with respect to A4BX6Structural perovskite materials, however no AB is known2X5Reports relating to structural perovskite materials。
Until now, the quantum dot material is mainly applied to the display field, such as a typical II-VI group CdSe quantum dot system, a III-V group InP quantum dot system, or an I-III-VI group CuInS quantum dot system.
In recent years, metal halide ABX3The appearance of perovskite materials further promotes the related knowledge of preparing semiconductor nanocrystalline or quantum dot materials by a solution method. In recent research reports, a new class of perovskite luminescent materials (with the chemical formula of Cs) appears4PbBr6) Such materials having the formula: ABX3The perovskite quantum dot has excellent optical performance comparable to that of perovskite quantum dot and has great application potential. Particularly, as the preparation method of the material is optimized and improved, the semiconductor material called zero-dimensional perovskite is shown to be similar to ABX3The special photoelectric properties (such as high photoluminescence intensity and large exciton binding energy) of perovskite type. These novel properties lead to Cs4PbBr6Applications in devices such as light emitting diodes, electroluminescent devices, lasers and photodetectors are in an unprecedented position.
However, the existing inorganic A4BX6Most of the perovskite luminescent materials are complicated in preparation method, and organic molecules such as Oleic Acid (OA) and Oleylamine (OLA) are introduced to be not beneficial to cleaning and purifying quantum dots in the later period.
Disclosure of Invention
According to one aspect of the present application, there is provided a hybrid perovskite microcrystalline material, first of all
Then prepare AB2X5Type insert A4MX6The hybridized perovskite microcrystal material has high luminous efficiency and good stability.
The hybrid perovskite microcrystalline material comprises a perovskite with a chemical formula shown as a formula I and a perovskite with a chemical formula shown as a formula II;
AM2X5formula I;
A4MX6formula II;
the perovskite shown in the formula I is embedded into the perovskite shown in the formula II;
wherein A is selected from CH3NH3 +、NH＝CHNH3 +、C(NH2)3 +、R2NH3 +、Li+、Na+、Rb+Or Cs+At least one of;
R2selected from hydrogen, C1～C10Alkyl of (C)1～C10An unsaturated hydrocarbon group of (1);
m is metal ions, and the metal is at least one of Ge, Sn, Pb, Sb, Bi, Cu, Mn, Sr, In, Tl and Ag;
x is at least one selected from halogen anions.
Alternatively, R2Is a saturated straight-chain alkyl group or a saturated branched-chain alkyl group or an unsaturated straight-chain alkyl group or an unsaturated branched-chain alkyl group or an aromatic group with the number of chain carbon atoms between 1 and 8.
Alternatively, wherein R2Selected from hydrogen, C1～C4Alkyl groups of (a);
x is selected from Cl-、Br-、I-At least one of (1).
Optionally, the size of the hybrid perovskite microcrystalline material is 0.001 mm-200 mm.
Optionally, the size of the hybrid perovskite microcrystalline material is 101～104mm3。
Alternatively, wherein R2Selected from methyl, ethyl, propyl, isopropyl, butyl or tert-butyl.
Alternatively, A is selected from CH3NH3 +、NH＝CHNH3 +、C(NH2)3 +、R2NH3 +、Cs+One kind of (1).
Optionally, the luminescent wavelength of the hybrid perovskite microcrystalline material is 300nm to 1000 nm.
Optionally, the luminescence wavelength of the hybrid perovskite microcrystalline material is 490nm to 520 nm.
Optionally, the fluorescence quantum yield of the hybrid perovskite microcrystalline material reaches more than 80%.
Optionally, the fluorescence quantum yield of the hybrid perovskite microcrystalline material reaches over 90%.
Specifically, the invention provides a hybrid perovskite microcrystalline luminescent material, and the general formula of the hybrid perovskite microcrystalline luminescent material is AB2X5Wherein A is CH3NH3 +、NH＝CHNH3 +、C(NH2)3 +、R2NH3 +、Li+、Na+、Rb+Or Cs+B is any one of metal ions of Ge, Sn, Pb, Sb, Bi, Cu or Mn, and X is Cl-、Br-And I-At least one of (1). Wherein R is2Is a saturated straight-chain alkyl group or a saturated branched-chain alkyl group or an unsaturated straight-chain alkyl group or an unsaturated branched-chain alkyl group or an aromatic group with the number of chain carbon atoms between 1 and 8. The invention prepares AB for the first time2X5The inorganic perovskite luminescent material has high luminescent efficiency and good stability.
According to another aspect of the application, the method for preparing the hybrid perovskite microcrystalline material is simple, strong in universality, high in material yield which can reach more than 80%, adjustable in light-emitting wavelength between 300nm and 1000nm, less in impurity, easy to clean and purify, low in cost and high in material purity.
The preparation method of the hybrid perovskite microcrystalline material at least comprises the following steps:
s1) adding an additive into the solution containing the perovskite precursor to obtain a solid-liquid two-phase mixed system I;
s2) reacting the solid-liquid two-phase mixed system I in the step S1) to obtain the perovskite microcrystalline material.
Optionally, the additive in step S1) is selected from R31-COOH、R32-OH、R33-SH、R34-C ═ SThere is one;
wherein R is31、R32、R33、R34Independently selected from C1～C18Alkyl of (C)1～C18An unsaturated hydrocarbon group of (1).
Optionally, the additive in step S1) is at least one selected from ethanol and oleic acid.
Optionally, the perovskite precursor in step S1) comprises AX1With metal salts MX2；
Wherein A is selected from CH3NH3 +、NH＝CHNH3 +、C(NH2)3 +、R2NH3 +、Li+、Na+、Rb+Or Cs+At least one of;
m is metal ions, and the metal is at least one of Ge, Sn, Pb, Sb, Bi, Cu, Mn, Sr, In, Tl and Ag;
said X1、X2Independently selected from at least one of halide anions.
Optionally, said AX1With metal salts MX2The molar ratio of (A) to (B) is 1: 1-10.
Optionally, said AX1With metal salts MX2The molar ratio of (A) to (B) is 1: 3.5-4.5.
Optionally, said AX1Ratio to additive is 1: (1-100) mol/. mu.L.
Optionally, said AX1Ratio to additive is 1: (1-64) mol/. mu.L.
Optionally, the solvent of the solution in step S1) is selected from at least one of DMF, HBr, DMSO.
Optionally, said AX1Ratio to solvent 1: (2-10) mol/L.
Optionally, said AX1The upper limit of the ratio to the additive is selected from 1: 8 mol/. mu.L or 1: 64 mol/mu L; the lower limit is selected from 1:1 mol/. mu.L or 1: 8 mol/. mu.L.
Optionally, the solvent in the step S1) is a mixed solvent of DMF and HBr in a volume ratio of 1 (0.1-10).
Optionally, the reaction conditions in step S2) are selected from at least one of stirring, friction, ultrasound, shaking, and heating.
Optionally, the stirring reaction condition is magnetic stirring, mechanical stirring or high-speed dispersion, the reaction time is 30-120 minutes, and the stirring speed is 80-100 r/min;
the friction reaction condition is a mechanical ball milling method, the reaction time is 30-120 minutes, the rotating speed of the cylinder body is 23.8r/min, and the diameter of the steel ball is 100 mm;
the ultrasonic reaction conditions comprise that the ultrasonic time is 30-120 minutes, the ultrasonic frequency is 40-60 KHz, and the power is 100W;
the oscillation reaction condition is constant-temperature water bath oscillation, the reaction time is 30-120 minutes, the oscillation frequency is 80-100 times/min, the amplitude is 40mm, and the water bath temperature is 50-80 ℃;
the heating reaction condition is that the reaction time is 20-60 minutes, and the temperature is heated to 80-120 ℃.
Optionally, step S2) includes at least: heating and dissolving the mixed system I obtained in the step S1) to obtain a solution II; and keeping the solution II at 80-120 ℃ for 20-40 minutes, then gradually reducing the temperature to 60-10 ℃, growing seed crystals after 2-4 days, and obtaining the hybrid perovskite microcrystal material after 25-35 days.
Optionally, the temperature reduction rate in the step S2) is 5-15 ℃/h.
Optionally, the rate of said decreasing temperature in step S2) is 10 ℃/h.
Optionally, in step S2), the mixed system I obtained in step S1) is heated in a water bath to 80-100 ℃ for dissolution.
Alternatively, the hybrid perovskite crystals obtained in step S2) are washed with butyrolactone and toluene.
As a specific embodiment, the preparation method of the hybrid perovskite microcrystalline material at least comprises the following steps:
and adding the additive into the solution containing the perovskite precursor, dissolving the additive in water bath to completely dissolve the perovskite precursor, gradually cooling, growing seed crystals, cleaning and filtering to obtain the hybrid perovskite microcrystal material.
Optionally, the preparation method of the invention is utilized to prepare the hybrid inorganic perovskite luminescent material CsPb2Br5The method is simple, the universality is strong, the yield of the material is high, the yield can reach more than 90 percent, the impurities are few, the cleaning and the purification are easy, the cost is saved, and the cleaned CsPb is2Br5The purity of the material components is high (the purity is close to 100 percent), the process amplification is easy, and the preparation of hectogram level is easy to realize at present.
Specifically, the organic solvent component adopted by the preparation method is matched with the perovskite component, one selected perovskite component can be completely dissolved and dispersed in the organic solvent component, the other selected perovskite component cannot be well dissolved and dispersed in the organic component and exists in a solid phase form, so that a solid-liquid two-phase coexisting body is formed, the formed solid-liquid two-phase coexisting body starts to react under the control of conditions of stirring, friction, ultrasound, oscillation or heating, one perovskite component dispersed in the organic solvent is in full contact reaction with the other perovskite component in the solid phase, and the special solid-liquid contact reaction system ensures that the perovskite component reacts towards AB2X5And (4) transforming the type structure. Avoids the situation that the perovskite component of the reaction system in the prior art has a large part of ABX3The model structure is changed.
In particular, the invention is mainly A4BX6The basis of the original preparation method of the perovskite microcrystalline material is that a novel perovskite material is obtained by adding some organic additives such as R-COOH, R-OH, R-SH, R-C ═ S and the like, wherein R is a saturated straight-chain alkyl group or a saturated branched-chain alkyl group or an unsaturated straight-chain alkyl group or an unsaturated branched-chain alkyl group or an aromatic group with the chain carbon atom number of 1-18. The invention prepares AB for the first time2X5The prepared inorganic perovskite luminescent material has high luminescent efficiency and good stability. The invention also provides a method for preparing AB2X5The method for preparing perovskite microcrystal luminescent material is simple, strong in universality, high in material yield which can be up to above 90%, adjustable in luminescent wavelength between 490nm and 520nm, less in impurity and less in cleaningEasy purification, low cost and high material purity.
According to a further aspect of the application, a luminescent material is provided, comprising at least one of the hybrid perovskite microcrystalline material, the hybrid perovskite microcrystalline material prepared by the method.
All conditions in this application that relate to a numerical range can be independently selected from any point within the numerical range.
In this application "C1～C18”、“C1～C10"and the like refer to the number of carbon atoms which a group contains.
In the present application, an "alkyl group" is a group formed by losing any one hydrogen atom on the molecule of an alkane compound.
In this application, a "hydrocarbyl group" is a group formed by the loss of one hydrogen atom on a carbon atom in a hydrocarbon molecule. The hydrocarbon is a carbohydrate, for example, the alkane, alkene, alkyne are all hydrocarbons.
In the present application, an "aryl group" is a group formed by losing any one of hydrogen atoms on an aromatic ring in an aromatic compound molecule.
The beneficial effects that this application can produce include:
1) the invention prepares AM for the first time2X5Microcrystalline luminescent material of inorganic perovskite and preparation method thereof, and prepared microcrystalline perovskite luminescent material AM2X5The purity can reach more than 90%, the luminous efficiency is high, the fluorescence quantum yield can reach more than 80%, and the stability is good, as shown in figure 4. The prepared microcrystalline perovskite material is subjected to fluorescence test, the test result is shown in figure 3, and a green glittering crystal is formed by irradiating the microcrystalline perovskite material with a ZF-7A portable ultraviolet detection lamp under the dark condition.
2) The preparation method of the invention is utilized to prepare the inorganic perovskite luminescent material CsPb2Br5The method is simple, the universality is strong, the yield of the material is high, the yield can reach more than 90 percent, the impurities are few, the cleaning and the purification are easy, the cost is saved, and the cleaned CsPb is2Br5The purity of the material components is high (the purity is close to 100 percent), the process amplification is easy, and the prior art is easyHectogram-scale preparations have been achieved.
3) The organic solvent component adopted by the method is matched with the perovskite component, one selected perovskite component can be completely dissolved and dispersed in the organic solvent component, the other selected perovskite component can not be well dissolved and dispersed in the organic component and exists in a solid phase form, so that a solid-liquid two-phase coexisting body is formed, the formed solid-liquid two-phase body starts to react under the control of stirring, friction, ultrasound, oscillation or heating conditions, one perovskite component dispersed in the organic solvent and the other perovskite component in the solid phase are in full contact reaction, and the special solid-liquid contact reaction system ensures that the perovskite component reacts towards AM2X5And (4) transforming the type structure. Avoids the situation that the perovskite component of the reaction system in the prior art has a large part of the perovskite component to AMX in the reaction process3The model structure is changed.
4) The method of the invention introduces the additive during the preparation, and can effectively add the additive to the original A4MX6Obtaining novel AM on the basis of perovskite material preparation2X5Perovskite microcrystalline luminescent material, compared with A4MX6The perovskite material has a larger adjustable range of wavelength (490 nm-520 nm).
Drawings
FIG. 1 shows sample 1#And 2#XRD pattern of (a).
FIG. 2 shows sample 3#And 4#XRD pattern of (a).
FIG. 3 is a graph of a sample prepared according to the present application before (a) and after (b) UV irradiation.
FIG. 4 shows sample 2#The fluorescence spectrum of (a).
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and solvents in the examples of the present application were all purchased commercially.
The analysis method in the examples of the present application is as follows:
XRD measurements were performed using a Bruker/D8 FOCUS X-ray diffractometer with a Cu Kr radiation source at a wavelength of 1.5405 angstroms and a sweep of 3 degrees per minute starting at 5 degrees to 60 degrees.
Fluorescence spectroscopy was performed using an F-380 fluorescence spectrophotometer manufactured by Tianjin Hongkong science and technology development Co., Ltd.
Example 1 preparation of perovskite Material CsPb2Br5Sample 1#
(1)1molPbBr24mol CsBr and 8. mu.L oleic acid additive were dissolved in 1.1mL of a fixed mixture of DMF and HBr (1: 0.8 by volume) at room temperature.
(2) And (3) controlling the temperature of the mixture by using an external water bath to completely dissolve the mixture, controlling the temperature of the water bath to be 100 ℃ to completely dissolve the mixture, keeping the temperature for 30 minutes, gradually reducing the temperature to 10 ℃, and reducing the temperature at a rate of 10 ℃/h.
(3) After 3 days the seed slowly grew in the shape of a cube (1 × 1 × 0.2.2 mm)3). One month later, CsPb2Br5Successful nanocrystal intercalation of Cs4PbBr6Among the crystals, the crystals were planted at the bottom of the flask, irradiated with an ultraviolet lamp, exhibited green sparkling, and then washed with butyrolactone and toluene and filtered.
The obtained sample is 1#。
Example 2 preparation of perovskite Material Cs4PbBr6Sample 2#～4#
The procedure is as in example 1, except that sample 2 is used#～4#64 μ L of oleic acid additive, 8 μ L of ethanol additive and 64 μ L of ethanol additive were added, respectively.
Example 3 preparation of perovskite Material sample 5#～10#
The procedure is as in example 1, the starting materials and reaction conditions are as follows.
TABLE 1
Example 4 perovskite Material sample 1#～10#Structural characterization of
Structural analysis was performed on the perovskite materials obtained in examples 1 to 3, and XRD spectra were measured. Typical sample 1 corresponds to FIG. 1#～2#Sample 3 corresponding to FIG. 2#～4#A perovskite material. As can be seen from the figure, AM was successfully prepared in the examples2X5Embedding A4MX6Obtaining the hybrid perovskite material. The test results of other examples are similar to those of examples 1 and 2, and perovskite materials of corresponding chemical formulas are prepared. And the prepared perovskite material has no impurity phase and high purity.
Example 5 perovskite Material sample 1#～10#Fluorescent property of
The perovskite materials obtained in examples 1 to 3 were subjected to fluorescence tests, and the test results were similar to those of fig. 3, and the perovskite materials were irradiated with a ZF-7A portable ultraviolet detection lamp under dark conditions to give green glittering crystals.
Sample 1#～10#All show the same fluorescence properties.
Example 6 perovskite Material sample 1#～10#Fluorescence analysis of
The perovskite materials obtained in examples 1 to 3 were subjected to fluorescence spectrum testing. The light-emitting wavelength is adjustable between 490nm and 520 nm. A typical fluorescence spectrum is shown in FIG. 4, corresponding to sample 2#. As can be seen from FIG. 4, the luminescent efficiency of the hybrid perovskite microcrystalline luminescent material is high, the fluorescence quantum yield can reach more than 80%, and the stability is good.
Sample 1#～10#All showed similar fluorescence spectra.
Claims (18)
1. A hybrid perovskite microcrystalline material is characterized by comprising a perovskite shown as a formula I and a perovskite shown as a formula II;
AM2X5formula I;
A4MX6formula II;
the perovskite shown in the formula I is embedded into the perovskite shown in the formula II;
wherein A is selected from CH3NH3 +、NH=CHNH3 +、C(NH2)3 +、R2NH3 +、Li+、Na+、Rb+Or Cs+At least one of;
R2selected from hydrogen, C1~C10Alkyl of (C)1~C10An unsaturated hydrocarbon group of (1);
m is metal ions, and the metal is at least one of Ge, Sn, Pb, Sb, Bi, Cu, Mn, Sr, In, Tl and Ag;
x is at least one selected from halogen anions.
2. Hybrid perovskite microcrystalline material as claimed in claim 1, wherein R is2Selected from hydrogen, C1~C4Alkyl groups of (a);
x is selected from Cl-、Br-、I-At least one of (1).
3. The hybrid perovskite microcrystalline material as claimed in claim 1, wherein the size of the hybrid perovskite microcrystalline material is 0.001-200 mm;
the size of the hybrid perovskite microcrystalline material is 101~104mm3。
4. The hybrid perovskite microcrystalline material as claimed in claim 1, wherein the luminescent wavelength of the hybrid perovskite microcrystalline material is 300 nm-1000 nm.
5. The hybrid perovskite microcrystalline material as claimed in claim 1, wherein the fluorescence quantum yield of the hybrid perovskite microcrystalline material is above 80%.
6. The preparation method of hybrid perovskite microcrystalline material as claimed in any one of claims 1 to 5, characterized in that it comprises at least the following steps:
s1) adding an additive into the solution containing the perovskite precursor to obtain a solid-liquid two-phase mixed system I;
s2) reacting the solid-liquid two-phase mixed system I obtained in the step S1) to obtain a perovskite microcrystalline material;
the additive in step S1) is selected from R31-COOH、R32-OH、R33-SH、R34-at least one of C = S;
wherein R is31、R32、R33、R34Independently selected from C1~C18Alkyl of (C)1~C18An unsaturated hydrocarbon group of (1);
the perovskite precursor in step S1) comprises AX1With metal salts MX2；
Wherein A is selected from CH3NH3 +、NH=CHNH3 +、C(NH2)3 +、R2NH3 +、Li+、Na+、Rb+Or Cs+At least one of;
m is metal ions, and the metal is at least one of Ge, Sn, Pb, Sb, Bi, Cu, Mn, Sr, In, Tl and Ag;
said X1、X2Independently selected from at least one of halide anions.
7. The method of claim 6,
the additive in the step S1) is at least one selected from ethanol and oleic acid.
8. The method of claim 6,
said AX1With metal salts MX2Is prepared from (A) and (B)The molar ratio is 1: 1-10.
9. The method of claim 6, wherein said AX1The proportion of the additive is 1: (1-100) mol/. mu.L.
10. The method according to claim 6, wherein the solvent of the solution in step S1) is at least one selected from DMF, HBr and DMSO.
11. The method of claim 10, wherein the AX is1Ratio to solvent 1: (2-10) mol/L.
12. The method according to claim 10, wherein the solvent in step S1) is a mixture of DMF and HBr at a volume ratio of 1 (0.1-10).
13. The method as claimed in claim 6, wherein the reaction conditions in step S2) are at least one selected from stirring, friction, ultrasound, shaking and heating.
14. The method according to claim 13, wherein the stirring reaction condition is magnetic stirring, mechanical stirring or high-speed dispersion, the reaction time is 30-120 minutes, and the stirring speed is 80-100 r/min;
the reaction condition of the friction is a mechanical ball milling method, the reaction time is 30-120 minutes, the rotating speed of the cylinder body is 23.8r/min, and the diameter of the steel ball is 100 mm;
the reaction condition of the ultrasound is that the ultrasound time is 30-120 minutes, the ultrasound frequency is 40-60 KHz, and the power is 100W;
the oscillating reaction condition is constant-temperature water bath oscillation, the reaction time is 30-120 minutes, the oscillation frequency is 80-100 times/min, the amplitude is 40mm, and the water bath temperature is 50-80 ℃;
the heating reaction condition is that the reaction time is 20-60 minutes, and the temperature is heated to 80-100 ℃.
15. The method according to claim 6, characterized in that step S2) comprises at least: heating and dissolving the mixed system I obtained in the step S1) to obtain a solution II; and keeping the solution II at 80-100 ℃ for 20-60 minutes, then gradually reducing the temperature to 60-10 ℃, growing seed crystals after 2-4 days, and obtaining the hybrid perovskite microcrystal material after 25-35 days.
16. The method as claimed in claim 15, wherein in step S2), the mixed system I obtained in step S1) is dissolved by heating in water bath at 80-100 ℃.
17. The method according to claim 15, wherein the hybrid perovskite crystals obtained in step S2) are washed with butyrolactone and toluene.
18. A luminescent material, comprising at least one of the hybrid perovskite microcrystalline material according to any one of claims 1 to 5 and the hybrid perovskite microcrystalline material prepared according to the method of any one of claims 6 to 17.
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| CN106883845A (en) * | 2017-04-10 | 2017-06-23 | 北京理工大学 | A kind of perovskite crystallite luminescent material, preparation method and applications |
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