CN111518549B - Lead-free halide green luminescent material and preparation method thereof - Google Patents
Lead-free halide green luminescent material and preparation method thereof Download PDFInfo
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Abstract
A lead-free halide green luminescent material and a preparation method thereof relate to the field of luminescent materials. The chemical formula of the lead-free halide green luminescent material is aCsCl & bAgCl, wherein a is more than or equal to 1.75 and less than or equal to 2.25, and b is more than or equal to 0.75 and less than or equal to 1.25. The preparation method comprises the following steps: weighing corresponding salts of each element according to the composition of the general formula aCsCl & bAgCl, and mixing the salts with the organic solvent A; heating to a certain temperature in air atmosphere, preserving heat, cooling to room temperature, and centrifuging to obtain supernatant; under the condition of normal temperature, putting the supernatant into an open beaker, and putting the beaker into a closed reagent bottle containing an organic solvent B; and taking out the colorless needle crystal after the colorless needle crystal grows out of the beaker, and drying to obtain the lead-free halide green luminescent material. The method is simple and feasible, and the prepared target product has bright green broadband luminescence. The material can be used in the fields of illumination and display, and can also be used in the fields of optical detectors, lasers, solar cells and the like.
Description
Technical Field
The invention relates to the field of luminescent materials, in particular to a lead-free halide green luminescent material and a preparation method thereof.
Background
CsPbX was first reported by Kovalenko et al (Nano Letter,2015,15,6,3692-3Since the (X ═ Cl, Br, I) halide perovskite nanocrystals have luminescence properties, the materials are considered to have important application prospects in the fields of illumination, display, solar cells, photoelectric detection, photocatalysis and the like due to the advantages of high luminescent color purity, high quantum efficiency, adjustable luminescent color, high charge carrier mobility and the like, and rapidly become hot spots in the field of luminescent material research. Although CsPbX has been used in recent years3Study of halide light-emitting materials on light-emitting propertiesA series of breakthrough advances are made in aspects of stability, toxicity and the like, but the problems of material stability and toxicity of lead are still not solved, and the defects are still major obstacles which seriously hinder the commercial application of perovskite materials. Therefore, the toxicity research of the lead halide perovskite material has important significance.
At present, the main research scheme for reducing lead toxicity is to use element substitution method such as Sn2+Or Ge2+To replace Pb in lead-halogen perovskites2+. However, Sn2+And Ge2+Is easily oxidized into Sn in the air4+And Ge4+This leads to a problem of poor stability of the material. Another perovskite material of low toxicity obtained by substitution of non-equivalent elements, e.g. with Bi3+Or Sb3+Aliovalent substitution of Pb2+The obtained layered material Cs3B2X9(B ═ Bi, Sb) with an Ag+And a Bi3+Replacement of two Pb2+The obtained double perovskite nanocrystalline Cs2AgBiX6However, these materials have a problem of poor performance (they cannot replace CsPbX yet)3Light-emitting materials), for example, the band gap width is too large, the light-emitting efficiency is low, the emission color is often red or orange (short wavelength emission is poor), and the stability is poor.
The invention develops a lead-free halide green luminescent material with cations of Cs and Ag. At present, halide materials composed of Cs and Ag as cations have no report on luminescence property. In 2004, Stephen Hull et al (Journal of Solid State Chemistry 177,2004, 3156-3173) synthesized Cs by high temperature Solid phase method2AgCl3And the crystal structure and other information are studied, and no luminescence property is found.
Disclosure of Invention
The invention aims to provide a lead-free halide green luminescent material which is simple to synthesize and high in luminous intensity and a preparation method thereof aiming at the defects in the prior art.
The chemical formula of the lead-free halide green luminescent material is aCsCl & bAgCl, wherein a is more than or equal to 1.75 and less than or equal to 2.25, and b is more than or equal to 0.75 and less than or equal to 1.25.
The ranges of a and b are preferably 1.90-2.10 of a and 0.90-1.10 of b.
The preparation method of the lead-free halide green luminescent material comprises the following steps:
1) weighing corresponding salts of each element according to the composition of the general formula aCsCl & bAgCl, and mixing the salts with the organic solvent A;
2) heating to a certain temperature in air atmosphere, preserving heat, cooling to room temperature, and centrifuging to obtain supernatant;
3) at normal temperature, putting the supernatant into an open container, and placing the open container into a closed reagent bottle containing an organic solvent B;
4) and (3) growing a colorless needle crystal in the open container, taking out the crystal and drying to obtain the lead-free halide green luminescent material.
In step 1), the corresponding salts can be silver chloride and cesium chloride; the organic solvent A can be at least one of DMF, dimethyl sulfoxide, methanol, acetonitrile and the like.
In the step 2), the temperature of the heat preservation can be 30-140 ℃, the time of the heat preservation can be 3-24 hours, and the preferable time of the heat preservation can be 6-12 hours; the conditions for the centrifugation may be: the rotating speed is 3000-15000 r/min, and the time is 1-30 min.
In the step 3), the organic solvent B may be one of n-butanol, tetrahydrofuran, ethyl acetate, methyl formate, and the like.
In the step 4), the growth time of the crystal can be 12-72 h; the drying temperature can be 50-70 ℃, and the drying time can be 1-24 h.
The lead-free halide green luminescent material prepared by the invention can be applied to illumination, displays, photodetectors, lasers, solar cells and the like.
The method for preparing the lead-free luminescent material consisting of perovskite-like materials is simple, convenient and feasible, and the prepared target product has bright green broadband luminescence. The invention provides a lead-free low-toxicity halide Cs with simple synthesis and high luminous intensity2AgCl3Green luminescent material, which is found to present novel green luminescence by adjusting the components and synthesis method of halide material consisting of cesium and silverThe light performance adds a new material system for the family of broadband green luminescent materials. After the material is irradiated by ultraviolet light, strong green luminescence can be seen by naked eyes. The green luminescent material of the lead-free halide prepared by the invention can be used in the fields of illumination and display, and can also be used in the fields of photodetectors, lasers, solar cells and the like.
Drawings
FIG. 1 shows Cs prepared in example 42AgCl3A room temperature emission spectrum of the green luminescent material.
FIG. 2 shows Cs prepared in example 42AgCl3A room temperature ultraviolet light physical picture of the green luminescent material.
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the scope of the present invention.
Example 1: synthesis of 1.8 CsCl.0.8 AgCl green luminescent material
0.3031g of CsCl and 0.1146g of AgCl were weighed out and mixed well with 10mL of DMF in a reagent bottle with a cover, and then synthesized in two steps: firstly, keeping the temperature at 60 ℃ for 20h under the air condition, cooling to room temperature, centrifuging, taking out supernatant, sealing in tetrahydrofuran diffusion atmosphere, and standing at normal temperature for 24 h. And taking out the crystal, drying to obtain a final sample, and irradiating by ultraviolet light to obtain the sample emitting stronger green luminescence.
Example 2: synthesis of 1.75 CsCl.1.25 AgCl green luminescent material
0.2947g of CsCl and 0.1791g of AgCl are weighed and mixed uniformly with 10mL of dimethyl sulfoxide in a reagent bottle with a cover, and then the mixture is synthesized in two steps: firstly, preserving the heat for 24h at 30 ℃ under the air condition, cooling to room temperature, centrifuging, taking out supernatant, sealing in a methyl formate diffusion atmosphere, and standing at normal temperature for 48 h. And taking out the crystal, drying to obtain a final sample, and irradiating by ultraviolet light to obtain the sample emitting stronger green luminescence.
Example 3: synthesis of 2.0 CsCl.0.9 AgCl green luminescent material
0.3367g of CsCl and 0.1290g of AgCl are weighed and mixed uniformly with 10mL of acetonitrile in a reagent bottle with a cover, and then the mixture is synthesized by two steps: firstly, keeping the temperature of 100 ℃ for 15h under the air condition, cooling to room temperature, centrifuging, taking out supernatant, sealing in a methyl formate diffusion atmosphere, and standing at normal temperature for 60 h. And taking out the crystal, drying to obtain a final sample, and irradiating by ultraviolet light to obtain the sample emitting stronger green luminescence.
Example 4: synthesis of 2.0 CsCl1.0 AgCl green luminescent material
0.3367g of CsCl and 0.1433g of AgCl are weighed and mixed uniformly with 6mL of DMF and 4mL of dimethyl sulfoxide in a reagent bottle with a cover, and then the mixture is synthesized by two steps: firstly, preserving heat for 12h at 140 ℃ under the air condition, cooling to room temperature, centrifuging, taking out supernatant, sealing in tetrahydrofuran diffusion atmosphere, and standing at normal temperature for 48 h. And taking out the crystal, drying to obtain a final sample, and irradiating by ultraviolet light to obtain the sample emitting stronger green luminescence.
Cs prepared in example 42AgCl3The room temperature emission spectrum of the green emitting material is shown in FIG. 1. Cs prepared in example 42AgCl3A physical diagram of the room temperature ultraviolet light of the green luminescent material is shown in FIG. 2.
Example 5: synthesis of 2.1 CsCl.1.1 AgCl green luminescent material
0.3536g of CsCl and 0.1576g of AgCl are weighed and mixed uniformly with 6mL of DMF and 4mL of acetonitrile in a reagent bottle with a cover, and then the synthesis is carried out by two steps: firstly, preserving the heat for 12h at 120 ℃ under the air condition, cooling to room temperature, centrifuging, taking out supernatant, sealing in an ethyl acetate diffusion atmosphere, and standing at normal temperature for 72 h. And taking out the crystal, drying to obtain a final sample, and irradiating by ultraviolet light to obtain the sample emitting stronger green luminescence.
Example 6: synthesis of 2.25CsCl 0.75AgCl green luminescent material
0.3788g of CsCl and 0.1074g of AgCl are weighed, mixed uniformly with 6mL of dimethyl sulfoxide and 4mL of methanol in a reagent bottle with a cover, and synthesized in two steps: firstly, preserving heat for 6h at 140 ℃ under the air condition, cooling to room temperature, centrifuging, taking out supernatant, sealing in an ethyl acetate diffusion atmosphere, and standing at normal temperature for 36 h. And taking out the crystal, drying to obtain a final sample, and irradiating by ultraviolet light to obtain the sample emitting stronger green luminescence.
The invention provides a2BX3A preparation method of a type (A, B is cation, X is anion) green luminescent material comprises the following steps: aCsCl & bAgCl, wherein a is more than or equal to 1.75 and less than or equal to 2.25, and b is more than or equal to 0.75 and less than or equal to 1.25. The luminescent material can be excited by ultraviolet light to generate strong broadband green luminescence with a main peak at 530 nm. The method can be widely applied to the fields of illumination, display, optical detectors, laser, solar cells and the like.
Claims (7)
1. A preparation method of a lead-free halide green luminescent material is characterized in that the chemical formula of the lead-free halide green luminescent material is aCsCl.bAgCl, wherein a is more than or equal to 1.75 and less than or equal to 2.25, and b is more than or equal to 0.75 and less than or equal to 1.25;
the preparation method comprises the following steps:
1) weighing corresponding salts of each element according to the composition of a general formula aCsCl. bAgCl, and mixing the salts with an organic solvent A; the organic solvent A is at least one of DMF, dimethyl sulfoxide, methanol and acetonitrile;
2) heating to a certain temperature in air atmosphere, preserving heat, cooling to room temperature, and centrifuging to obtain supernatant;
3) at normal temperature, putting the supernatant into an open container and placing the container into a closed reagent bottle containing an organic solvent B; the organic solvent B is one of tetrahydrofuran, ethyl acetate and methyl formate;
4) and (3) after colorless needle crystals grow out from the container, taking out the crystals and drying to obtain the lead-free halide green luminescent material.
2. The method of claim 1, wherein a is 1.90. ltoreq. a.ltoreq.2.10, and b is 0.90. ltoreq. b.ltoreq.1.10.
3. The method according to claim 1, wherein in step 1), the corresponding salts are silver chloride and cesium chloride.
4. The method for preparing the lead-free halide green luminescent material as claimed in claim 1, wherein in the step 2), the temperature for heat preservation is 30-140 ℃ and the time for heat preservation is 3-24 h.
5. The method for preparing the lead-free halide green luminescent material as claimed in claim 4, wherein the time for the heat preservation is 6-12 h.
6. The method according to claim 1, wherein in step 2), the centrifugal separation conditions include a rotation speed of 3000 to 15000r/min for 1 to 30 min.
7. The method for preparing a lead-free halide green luminescent material as claimed in claim 1, wherein in the step 4), the growth time of the crystal is 12-72 h; the drying temperature is 50-70 ℃, and the drying time is 1-24 h.
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| WO2016181465A1 (en) * | 2015-05-11 | 2016-11-17 | 株式会社日立製作所 | Analysis device and analysis method |
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