CN114717005A - Rare earth-based halide luminescent material, preparation method and application thereof - Google Patents
Rare earth-based halide luminescent material, preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 157
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 63
- 150000004820 halides Chemical class 0.000 title claims abstract description 55
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 32
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 28
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 26
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 37
- 239000002243 precursor Substances 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 229910052792 caesium Inorganic materials 0.000 claims description 14
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 14
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 13
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 claims description 11
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 10
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims description 6
- 229940075624 ytterbium oxide Drugs 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 239000012459 cleaning agent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 49
- 239000000843 powder Substances 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 230000005284 excitation Effects 0.000 description 38
- 239000007795 chemical reaction product Substances 0.000 description 22
- -1 rare earth halide Chemical class 0.000 description 18
- 238000000295 emission spectrum Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/36—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 halogen being the only anion, e.g. NaYF4
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Abstract
The invention relates to the technical field of luminescent materials, in particular to a rare earth-based halide luminescent material, and a preparation method and application thereof. The rare earth-based halide luminescent material has a chemical formula shown in a formula I; in the formula I, x is more than or equal to 0 and less than or equal to 1. The rare earth erbium-based halide double perovskite prepared by the invention has obvious down-conversion green light emission and bright up-conversion emission excited by 980nm and 808 nm. The perovskite produced red emission by substituting the erbium with the element ytterbium, with an emission peak around 665nm, with a high fluorescence quantum efficiency of 62%. And the substitution of ytterbium greatly enhances the near infrared absorption near 980nm and up-conversion emission with up-conversion emission intensity of 40% of that of commercial up-conversion green powder. The rare earth erbium-based halide double perovskite provided by the invention has certain popularization value in the application of up-conversion and down-conversion luminescent materials excited by multiple modes.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a rare earth-based halide luminescent material, and a preparation method and application thereof.
Background
Lead halide perovskites have attracted extensive attention in the field of luminescent materials due to their characteristics of adjustable emission spectra, high quantum efficiency, and the like. However, the lead toxicity and poor stability of lead-perovskite halides limits their further commercial applications and has prompted researchers to search for stable and environmentally friendly luminescent perovskite materials. Solves the toxicity problem of halogenated lead perovskite, and the simplest and feasible method is to replace the halogenated lead perovskite with nontoxic metal ions. Among them, the lead-free metal halide luminescent material has become a very promising luminescent material due to its characteristics of environmental friendliness, flexible structure, excellent luminescent properties, and the like. However, there are few reports on the research of the multi-mode excitation of the halide luminescent material, and particularly, the research of the rare earth-based halide luminescent material system is less.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a rare earth-based halide luminescent material, a preparation method and an application thereof.
The invention provides a rare earth-based halide luminescent material which has a chemical formula shown in a formula I;
Cs2NaEr1-xYbxCl6formula I;
in the formula I, x is more than or equal to 0 and less than or equal to 1.
Preferably, x is 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.
The invention also provides a preparation method of the rare earth-based halide luminescent material, which comprises the following steps:
mixing a cesium source, a sodium source, an erbium source, an ytterbium source and concentrated hydrochloric acid, and carrying out hydrothermal reaction at 170-190 ℃ to obtain a rare earth-based halide luminescent material;
the rare earth-based halide luminescent material has a chemical formula shown in a formula I;
Cs2NaEr1-xYbxCl6formula I;
in the formula I, x is more than or equal to 0 and less than or equal to 1.
Preferably, the preparation method of the rare earth-based halide luminescent material comprises the following steps:
A) mixing the material a with concentrated hydrochloric acid to obtain a precursor solution;
the material a is a cesium source;
B) mixing the material b with the precursor solution, and carrying out hydrothermal reaction at 170-190 ℃ to obtain a rare earth-based halide luminescent material;
the material b comprises a sodium source and a material b 1; the material b1 comprises an erbium source and/or an ytterbium source;
the rare earth-based halide luminescent material has a chemical formula shown in a formula I;
Cs2NaEr1-xYbxCl6formula I;
in the formula I, x is more than or equal to 0 and less than or equal to 1.
Preferably, the preparation method of the rare earth-based halide luminescent material comprises the following steps:
A) mixing the material a with concentrated hydrochloric acid to obtain a precursor solution;
material a comprises a cesium source and material a 1; the material a1 comprises an erbium source and/or an ytterbium source;
B) mixing the material b with the precursor solution, and carrying out hydrothermal reaction at 170-190 ℃ to obtain a rare earth-based halide luminescent material;
the material b is a sodium source;
the rare earth-based halide luminescent material has a chemical formula shown in a formula I;
Cs2NaEr1-xYbxCl6formula I;
in the formula I, x is more than or equal to 0 and less than or equal to 1.
Preferably, the cesium source comprises at least one of cesium chloride and cesium carbonate;
the sodium source comprises at least one of sodium chloride, sodium hydroxide and sodium carbonate;
the erbium source comprises at least one of erbium chloride and erbium oxide;
the ytterbium source comprises at least one of ytterbium chloride and ytterbium oxide.
Preferably, the time of the hydrothermal reaction is 8-12 h.
Preferably, after the hydrothermal reaction, the method further comprises: filtering, cleaning and drying;
the cleaning agent adopted for cleaning is ethanol;
the drying temperature is 50-80 ℃, and the drying time is 3-12 h.
Preferably, before the filtration, the temperature is reduced to room temperature;
the cooling rate is 3-40 ℃/h.
The invention also provides an application of the rare earth halide luminescent material or the rare earth halide luminescent material prepared by the preparation method as an anti-counterfeiting material.
The invention provides a rare earth-based halide luminescent material which has a chemical formula shown in a formula I;
Cs2NaEr1-xYbxCl6formula I;
in the formula I, x is more than or equal to 0 and less than or equal to 1.
According to the invention, the rare earth erbium-based halide double perovskite is synthesized by a hydrothermal method, and the prepared rare earth-based halide luminescent material can realize high-efficiency up-down conversion emission and has high quantum efficiency. Experimental results show that the rare earth erbium-based halide double perovskite prepared by the invention has obvious down-conversion green light emission and bright up-conversion emission excited by 980nm and 808 nm. The perovskite produced red emission by substituting the erbium with the element ytterbium, with an emission peak around 665nm, with a high fluorescence quantum efficiency of 62%. And the substitution of ytterbium greatly enhances the near infrared absorption near 980nm and up-conversion emission with up-conversion emission intensity of 40% of that of commercial up-conversion green powder. The rare earth erbium-based halide double perovskite provided by the invention has certain popularization value in the application of up-conversion and down-conversion luminescent materials excited by multiple modes.
Drawings
FIG. 1 is an XRD spectrum of a luminescent material according to examples 1 to 11 of the present invention;
fig. 2 is an emission spectrum of the luminescent materials of examples 1 to 11 of the present invention under excitation of 379nm ultraviolet light, and the inset in fig. 2 is an emission spectrum of the luminescent material of example 1(x ═ 0) under excitation of 379nm ultraviolet light;
FIG. 3 is a graph of quantum efficiency data of the luminescent material of example 7 under 379nm ultraviolet light excitation;
FIG. 4 is an upconversion emission spectrum of the luminescent materials of examples 1-11 of the present invention under excitation of 980nm near infrared light;
FIG. 5 is a spectrum of upconversion emission spectra of the luminescent material of example 5 of the present invention and a commercial upconversion green powder under 980nm near infrared excitation;
FIG. 6 shows the up-conversion emission spectra of the luminescent materials of examples 1 to 11 under the excitation of near infrared light of 808 nm.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a rare earth-based halide luminescent material which has a chemical formula shown in a formula I;
Cs2NaEr1-xYbxCl6formula I;
in the formula I, x is more than or equal to 0 and less than or equal to 1.
In certain embodiments of the present invention, x is 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.
The invention provides a rare earth-based halide luminescent material, belonging to a double perovskite material.
The invention also provides a preparation method of the rare earth halide luminescent material, which comprises the following steps:
mixing a cesium source, a sodium source, an erbium source, an ytterbium source and concentrated hydrochloric acid, and carrying out hydrothermal reaction at 170-190 ℃ to obtain a rare earth-based halide luminescent material;
the rare earth-based halide luminescent material has a chemical formula shown in a formula I;
Cs2NaEr1-xYbxCl6formula I;
in the formula I, x is more than or equal to 0 and less than or equal to 1.
In some embodiments of the present invention, the method for preparing the rare earth-based halide light emitting material includes the steps of:
A) mixing the material a with concentrated hydrochloric acid to obtain a precursor solution;
the material a is a cesium source;
B) mixing the material b with the precursor solution, and carrying out hydrothermal reaction at 170-190 ℃ to obtain a rare earth-based halide luminescent material;
the material b comprises a sodium source and a material b 1; the material b1 comprises an erbium source and/or an ytterbium source;
the rare earth-based halide luminescent material has a chemical formula shown in a formula I;
Cs2NaEr1-xYbxCl6formula I;
in the formula I, x is more than or equal to 0 and less than or equal to 1.
In some embodiments of the present invention, the method for preparing the rare earth-based halide light emitting material includes the steps of:
A) mixing the material a with concentrated hydrochloric acid to obtain a precursor solution;
material a comprises a cesium source and material a 1; the material a1 comprises an erbium source and/or an ytterbium source;
B) mixing the material b with the precursor solution, and carrying out hydrothermal reaction at 170-190 ℃ to obtain a rare earth-based halide luminescent material;
the material b is a sodium source;
the rare earth-based halide luminescent material has a chemical formula shown in a formula I;
Cs2NaEr1-xYbxCl6formula I;
in the formula I, x is more than or equal to 0 and less than or equal to 1.
In certain embodiments of the present invention, the cesium source comprises at least one of cesium chloride and cesium carbonate;
the sodium source comprises at least one of sodium chloride, sodium hydroxide and sodium carbonate;
the erbium source comprises at least one of erbium chloride and erbium oxide;
the ytterbium source comprises at least one of ytterbium chloride and ytterbium oxide.
In certain embodiments of the invention, the concentrated hydrochloric acid has a mass concentration of 36% to 38%; in certain embodiments, the concentrated hydrochloric acid has a mass concentration of 37%.
In some embodiments of the present invention, the ratio of the material a to the concentrated hydrochloric acid is 2 to 3 mmol: 4.5-5.5 mL. In certain embodiments, the ratio of the amount of material a to concentrated hydrochloric acid is 2 mmol: 5mL or 2.5 mmol: 5 mL.
In certain embodiments of the present invention, the molar ratio of cesium ions in the cesium source to sodium ions in the sodium source is 2: 1.
in certain embodiments of the invention, the molar ratio of erbium ions in the erbium source to ytterbium ions in the ytterbium source is 1-x: x; wherein x is more than or equal to 0 and less than or equal to 1. In certain embodiments of the present invention, x is 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.
In certain embodiments of the present invention, the molar ratio of the sum of the moles of erbium ions in the erbium source and ytterbium ions in the ytterbium source to the moles of sodium ions in the sodium source is 1: 1.
in certain embodiments of the present invention, the temperature of the hydrothermal reaction is 180 ℃.
In some embodiments of the present invention, the hydrothermal reaction time is 8 to 12 hours. In certain embodiments, the hydrothermal reaction time is 10 hours.
In some embodiments of the present invention, after the hydrothermal reaction, the hydrothermal reaction further comprises: filtering, washing and drying.
In some embodiments of the present invention, before the filtering, the temperature is reduced to room temperature. The cooling rate is 3-40 ℃/h. In certain embodiments, the rate of cooling is 3 ℃/h, 4 ℃/h, 5 ℃/h, or 6 ℃/h.
In some embodiments of the present invention, the cleaning agent used for cleaning is ethanol.
In some embodiments of the invention, the drying temperature is 50-80 ℃ and the drying time is 3-12 h. In certain embodiments, the drying is at a temperature of 60 ℃, 70 ℃, 50 ℃ or 80 ℃ for 5h, 4h, 7h or 3 h.
The source of the above-mentioned raw materials is not particularly limited, and the raw materials may be generally commercially available.
The luminescent material prepared by the invention has obvious rare earth erbium ion multimodal emission under the excitation of 379nm ultraviolet light.
The luminescent material prepared by the invention has obvious rare earth erbium ion green light emission under the excitation of near infrared light of 808nm, and the main emission peak positions are 536nm and 558 nm.
The luminescent material prepared by the invention has obvious rare earth erbium ion multimodal adjustable emission under the excitation of 980nm near infrared light, and the emission peak positions are 536nm, 551nm and 667 nm.
The invention also provides an application of the rare earth halide luminescent material or the rare earth halide luminescent material prepared by the preparation method as an anti-counterfeiting material.
The invention synthesizes rare earth erbium-based halide double perovskite by a hydrothermal method, and realizes high-efficiency up-down conversion emission by substituting rare earth ytterbium. The efficient fluorescence emission up-conversion and down-conversion rare earth halide double perovskite has excellent optical performance, and the method has certain value on the anti-counterfeiting application of the perovskite in multi-mode excitation. The invention thus claims the use of the rare earth-based halide luminescent materials as anti-counterfeiting materials. In an embodiment of the present invention, the luminescent material of example 1 is green emitting and the other luminescent materials (0 < x < 1) are red emitting under 365nm UV excitation. Under 980nm near infrared excitation, the luminescent material of example 1 emits orange light, while the other luminescent materials gradually change to yellow light (x 0.6, 0.7) and then green light (x 0.8, 0.9) emission as the ytterbium content increases. However, all samples (0. ltoreq. x < 1) were green emitting under 808nm excitation.
The preparation method provided by the invention is simple in operation steps, low in cost of used raw materials, strong in repeatability and capable of realizing batch preparation.
The rare earth erbium-based halide double perovskite prepared by the invention has obvious down-conversion green light emission and bright up-conversion emission excited by 980nm and 808 nm. The perovskite produced red emission by substituting erbium by the element ytterbium, with an emission peak around 665nm, with a high fluorescence quantum efficiency of 62%. And ytterbium substitution greatly enhanced near infrared absorption near 980nm, enhanced up-conversion emission with up-conversion luminescence intensity 40% of that of commercial up-conversion green powder. The rare earth erbium-based halide double perovskite provided by the invention has certain popularization value in the application of up-conversion and down-conversion luminescent materials excited by multiple modes.
In order to further illustrate the present invention, the following detailed description of the rare earth-based halide luminescent material, the preparation method and the application thereof are provided in connection with the examples, which should not be construed as limiting the scope of the present invention.
The reagents used in the following examples are all commercially available.
Example 1
1) Mixing and dissolving 2mmol of cesium chloride and 5mL of concentrated hydrochloric acid (the mass concentration is 37%) to obtain a precursor solution;
2) mixing 1mmol of sodium chloride and 1mmol of erbium chloride with the precursor solution, then placing the mixture in a 25mL reaction kettle, heating to 180 ℃ for reaction for 10h, and cooling to room temperature at the rate of 3 ℃/h to obtain a reaction product mixed system;
3) filtering the reaction product mixed system, cleaning with ethanol, and drying at 60 deg.C for 5h to obtain Cs2NaErCl6A luminescent material.
Example 2
1) Mixing and dissolving 2mmol of cesium chloride and 5mL of concentrated hydrochloric acid (mass concentration is 37%) to obtain a precursor solution;
2) mixing 1mmol of sodium chloride, 0.9mmol of erbium chloride and 0.1mmol of ytterbium chloride with the precursor solution, then placing the mixture in a 25mL reaction kettle, heating to 180 ℃ for reaction for 10h, and cooling to room temperature at a rate of 4 ℃/h to obtain a reaction product mixed system;
3) filtering the reaction product mixed system to obtain a filtrate,cleaning with ethanol, and drying at 70 deg.C for 4 hr to obtain Cs2NaEr0.9Yb0.1Cl6A luminescent material.
Example 3
1) Mixing and dissolving 2mmol of cesium chloride and 5mL of concentrated hydrochloric acid (the mass concentration is 37%) to obtain a precursor solution;
2) mixing 1mmol of sodium chloride, 0.6mmol of erbium chloride and 0.4mmol of ytterbium chloride with the precursor solution, then placing the mixture in a 25mL reaction kettle, heating to 180 ℃ for reaction for 10h, and cooling to room temperature at the speed of 5 ℃/h to obtain a reaction product mixed system;
3) filtering the reaction product mixed system, washing with ethanol, and drying at 50 deg.C for 7 hr to obtain Cs2NaEr0.6Yb0.4Cl6A luminescent material.
Example 4
1) Mixing and dissolving 2mmol of cesium chloride and 5mL of concentrated hydrochloric acid (the mass concentration is 37%) to obtain a precursor solution;
2) mixing 1mmol of sodium chloride, 0.3mmol of erbium chloride and 0.7mmol of ytterbium chloride with the precursor solution, then placing the mixture in a 25mL reaction kettle, heating to 180 ℃ for reaction for 10h, and cooling to room temperature at the rate of 6 ℃/h to obtain a reaction product mixed system;
3) filtering the reaction product mixed system, washing with ethanol, and drying at 80 deg.C for 3 hr to obtain Cs2NaEr0.3Yb0.7Cl6A luminescent material.
Example 5
1) Mixing and dissolving 2mmol of cesium chloride and 5mL of concentrated hydrochloric acid (mass concentration is 37%) to obtain a precursor solution;
2) mixing 1mmol of sodium chloride, 0.1mmol of erbium chloride and 0.9mmol of ytterbium chloride with the precursor solution, then placing the mixture in a 25mL reaction kettle, heating to 180 ℃ for reaction for 10h, and cooling to room temperature at the speed of 3 ℃/h to obtain a reaction product mixed system;
3) filtering the reaction product mixed system, cleaning with ethanol, and drying at 60 deg.C for 5h to obtain Cs2NaEr0.1Yb0.9Cl6A luminescent material.
Example 6
1) 2mmol of cesium chloride and 0.5mmol of ytterbium oxide (Yb)2O3) Mixing and dissolving the precursor solution with 5mL of concentrated hydrochloric acid (the mass concentration is 37%) to obtain a precursor solution;
2) mixing 1mmol of sodium chloride with the precursor solution, then placing the mixture in a 25mL reaction kettle, heating to 180 ℃, reacting for 10 hours, and cooling to room temperature at the rate of 3 ℃/h to obtain a reaction product mixed system;
3) filtering the reaction product mixed system, cleaning with ethanol, and drying at 60 deg.C for 5h to obtain Cs2NaYbCl6A luminescent material.
Example 7
1) 2mmol of cesium chloride and 0.2mmol of erbium oxide (Er)2O3) 0.3mmol of ytterbium oxide (Yb)2O3) Mixing and dissolving the precursor solution with 5mL of concentrated hydrochloric acid (the mass concentration is 37%) to obtain a precursor solution;
2) mixing 1mmol of sodium chloride with the precursor solution, then placing the mixture in a 25mL reaction kettle, heating to 180 ℃, reacting for 10 hours, and cooling to room temperature at the rate of 3 ℃/h to obtain a reaction product mixed system;
3) filtering the reaction product mixed system, washing with ethanol, and drying at 60 deg.C for 3 hr to obtain Cs2NaEr0.4Yb0.6Cl6A luminescent material.
Example 8
1) 2mmol of cesium chloride and 0.4mmol of erbium oxide (Er)2O3) 0.1mmol of ytterbium oxide (Yb)2O3) Mixing and dissolving the precursor solution with 5mL of concentrated hydrochloric acid (the mass concentration is 37%) to obtain a precursor solution;
2) mixing 1mmol of sodium chloride with the precursor solution, then placing the mixture in a 25mL reaction kettle, heating to 180 ℃, reacting for 10 hours, and cooling to room temperature at the rate of 3 ℃/h to obtain a reaction product mixed system;
3) filtering the reaction product mixed system, washing with ethanol, and drying at 60 deg.C for 3 hr to obtain Cs2NaEr0.8Yb0.2Cl6A luminescent material.
Example 9
1) Mixing and dissolving 2mmol of cesium chloride and 5mL of concentrated hydrochloric acid (the mass concentration is 37%) to obtain a precursor solution;
2) mixing 1mmol of sodium chloride, 0.7mmol of erbium chloride and 0.3mmol of ytterbium chloride with the precursor solution, then placing the mixture in a 25mL reaction kettle, heating to 180 ℃ for reaction for 10h, and cooling to room temperature at the speed of 3 ℃/h to obtain a reaction product mixed system;
3) filtering the reaction product mixed system, washing with ethanol, and drying at 60 deg.C for 3 hr to obtain Cs2NaEr0.7Yb0.3Cl6A luminescent material.
Example 10
1) Mixing and dissolving 2mmol of cesium chloride and 5mL of concentrated hydrochloric acid (the mass concentration is 37%) to obtain a precursor solution;
2) mixing 1mmol of sodium chloride, 0.5mmol of erbium chloride and 0.5mmol of ytterbium chloride with the precursor solution, then placing the mixture in a 25mL reaction kettle, heating to 180 ℃ for reaction for 10h, and cooling to room temperature at the speed of 3 ℃/h to obtain a reaction product mixed system;
3) filtering the reaction product mixed system, washing with ethanol, and drying at 60 deg.C for 3 hr to obtain Cs2NaEr0.5Yb0.5Cl6A luminescent material.
Example 11
1) Mixing and dissolving 2mmol of cesium chloride and 5mL of concentrated hydrochloric acid (the mass concentration is 37%) to obtain a precursor solution;
2) mixing 1mmol of sodium chloride, 0.2mmol of erbium chloride and 0.8mmol of ytterbium chloride with the precursor solution, then placing the mixture in a 25mL reaction kettle, heating to 180 ℃ for reaction for 10h, and cooling to room temperature at the speed of 3 ℃/h to obtain a reaction product mixed system;
3) filtering the reaction product mixed system, washing with ethanol, and drying at 60 deg.C for 3 hr to obtain Cs2NaEr0.2Yb0.8Cl6A luminescent material.
XRD spectrum analysis was performed on the luminescent materials prepared in examples 1 to 11, and the results are shown in FIG. 1. FIG. 1 is an XRD spectrum of the luminescent materials of examples 1 to 11 of the present invention.
The emission spectra of the luminescent materials prepared in examples 1 to 11 under the excitation of 379nm ultraviolet light were studied, and the results are shown in fig. 2. FIG. 2 is an emission spectrum of the luminescent material of examples 1 to 11 of the present invention under excitation of 379nm ultraviolet light; the inset in fig. 2 is a plot of the emission spectrum of the luminescent material of example 1(x ═ 0) under 379nm uv excitation. As can be seen from FIG. 2, the luminescent material prepared by the invention has obvious rare earth erbium ion multi-peak emission, the main emission peak is 664nm, and the luminescent material is red light. Under 379nm ultraviolet excitation, when x is 0, as can be seen from the inset of fig. 2, the main emission peak of the double perovskite is located at 513nm, which is green emission; under the excitation of 379nm ultraviolet light, when x is more than 0 and less than 1, the main emission peak of the double perovskite is positioned at 667nm, and the double perovskite emits red light. Meanwhile, as can be seen from fig. 2, the emission intensity is the strongest with an ytterbium ion content of 60%.
The quantum efficiency data of the luminescent material prepared in example 7 under the excitation of 379nm ultraviolet light are studied, and the result is shown in fig. 3. Fig. 3 is a graph of quantum efficiency data of the luminescent material of example 7 of the present invention under excitation of 379nm ultraviolet light. As can be seen from fig. 3, the luminescent material of example 7 has a high quantum efficiency of 62%.
Table 1 shows the quantum efficiency of the luminescent materials prepared in examples 1-11 under the excitation of 379nm ultraviolet light.
TABLE 1 Quantum efficiency of luminescent materials prepared in examples 1 to 11 under excitation of 379nm ultraviolet light
| Sample | PLQY(％) |
| Cs2NaErCl6 | 4 |
| Cs2NaEr0.9Yb0.1Cl6 | 12 |
| Cs2NaEr0.8Yb0.2Cl6 | 21 |
| Cs2NaEr0.7Yb0.3Cl6 | 34 |
| Cs2NaEr0.6Yb0.4Cl6 | 45 |
| Cs2NaEr0.5Yb0.5Cl6 | 51 |
| Cs2NaEr0.4Yb0.6Cl6 | 62 |
| Cs2NaEr0.3Yb0.7Cl6 | 53 |
| Cs2NaEr0.2Yb0.8Cl6 | 38 |
| Cs2NaEr0.1Yb0.9Cl6 | 32 |
| Cs2NaYbCl6 | 0 |
The up-conversion emission spectra of the luminescent materials prepared in examples 1 to 11 under the excitation of 980nm near infrared light were investigated, and the results are shown in fig. 4. FIG. 4 shows the up-conversion emission spectra of the phosphors of examples 1 to 11 of the present invention under the excitation of 980nm near-infrared light. As can be seen from FIG. 4, under the excitation of 980nm near-infrared laser, the luminescent material prepared by the invention (x is more than or equal to 0 and less than 1) has three main peaks, and the peak positions are 536nm, 551nm and 667nm respectively; as the content of ytterbium ions increases, the up-conversion emission increases, the optimum content of ytterbium ions being 90% (corresponding to x ═ 0.9); when x is 0.9, the green emission of the luminescent material is optimal.
The upconversion emission spectra of the luminescent material prepared in example 5 and a commercial upconversion green powder under 980nm near infrared excitation were studied, and the results are shown in fig. 5. FIG. 5 is a spectrum of upconversion emission spectra of the luminescent material of example 5 of the present invention and a commercial upconversion green powder under excitation of 980nm near infrared light. As can be seen from fig. 5, under excitation of 980nm near-infrared laser, the commercial upconversion green powder and the prepared luminescent material (x is 0.9, the luminescent material of example 5) both generate strong green emission, and the area of the green emission peak of the commercial upconversion green powder and the prepared luminescent material is integrated, so that it can be found that the integrated area of the green emission peak of the luminescent material of example 5 of the present invention accounts for 40% of the corresponding commercial upconversion green powder.
The results of examining the upconversion emission spectra of the luminescent materials prepared in examples 1 to 11 under the excitation of 808nm near infrared light are shown in FIG. 6. FIG. 6 shows the up-conversion emission spectra of the luminescent materials of examples 1 to 11 under the excitation of near infrared light of 808 nm. As can be seen from fig. 6, all samples showed green emission under the excitation of 808nm near infrared light, the main emission peak positions were 558nm and 536nm, and the upconversion luminescence of the luminescent material with the erbium matrix is strongest at the excitation of 808 nm.
The luminescence spectra of the luminescent materials prepared in examples 1 to 11 under the excitation of 365nm ultraviolet light, 980nm and 808nm near infrared light were studied. Fig. 2, 4 and 6 are emission spectra of the luminescent materials of embodiments 1 to 11 of the present invention under excitation of 379nm ultraviolet light, 980nm and 808nm near-infrared light, respectively. As can be seen from the above figure, the luminescent material of example 1 emits green light under 365nm UV excitation, while the other luminescent materials (0 < x < 1) emit red light. Under 980nm near infrared excitation, the luminescent material of example 1 emits orange light, while the other luminescent materials gradually change to yellow light (x is 0.6, 0.7) and then to green light (x is 0.8, 0.9) with increasing ytterbium content. However, all samples (0. ltoreq. x < 1) were green emitting when excited at 808 nm. Thus, different samples exhibit different color emissions under different light source excitations.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A rare earth-based halide luminescent material has a chemical formula shown in formula I;
Cs2NaEr1-xYbxCl6formula I;
in the formula I, x is more than or equal to 0 and less than or equal to 1.
2. The rare-earth-based halide luminescent material according to claim 1, wherein x is 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.
3. A preparation method of a rare earth-based halide luminescent material comprises the following steps:
mixing a cesium source, a sodium source, an erbium source, an ytterbium source and concentrated hydrochloric acid, and carrying out hydrothermal reaction at 170-190 ℃ to obtain a rare earth-based halide luminescent material;
the rare earth-based halide luminescent material has a chemical formula shown in a formula I;
Cs2NaEr1-xYbxCl6formula I;
in the formula I, x is more than or equal to 0 and less than or equal to 1.
4. A method for preparing a rare-earth-based halide light-emitting material according to claim 3, comprising the steps of:
A) mixing the material a with concentrated hydrochloric acid to obtain a precursor solution;
the material a is a cesium source;
B) mixing the material b with the precursor solution, and carrying out hydrothermal reaction at 170-190 ℃ to obtain a rare earth-based halide luminescent material;
the material b comprises a sodium source and a material b 1; the material b1 comprises an erbium source and/or an ytterbium source;
the rare earth-based halide luminescent material has a chemical formula shown in a formula I;
Cs2NaEr1-xYbxCl6formula I;
in the formula I, x is more than or equal to 0 and less than or equal to 1.
5. A method for preparing a rare-earth-based halide light-emitting material according to claim 3, comprising the steps of:
A) mixing the material a with concentrated hydrochloric acid to obtain a precursor solution;
material a comprises a cesium source and material a 1; the material a1 comprises an erbium source and/or an ytterbium source;
B) mixing the material b with the precursor solution, and carrying out hydrothermal reaction at 170-190 ℃ to obtain a rare earth-based halide luminescent material;
the material b is a sodium source;
the rare earth-based halide luminescent material has a chemical formula shown in a formula I;
Cs2NaEr1-xYbxCl6formula I;
in the formula I, x is more than or equal to 0 and less than or equal to 1.
6. The method of any one of claims 3-5, wherein the cesium source comprises at least one of cesium chloride and cesium carbonate;
the sodium source comprises at least one of sodium chloride, sodium hydroxide and sodium carbonate;
the erbium source comprises at least one of erbium chloride and erbium oxide;
the ytterbium source comprises at least one of ytterbium chloride and ytterbium oxide.
7. The preparation method according to any one of claims 3 to 5, wherein the hydrothermal reaction time is 8 to 12 hours.
8. The method according to any one of claims 3 to 5, further comprising, after the hydrothermal reaction: filtering, cleaning and drying;
the cleaning agent adopted for cleaning is ethanol;
the drying temperature is 50-80 ℃, and the drying time is 3-12 h.
9. The preparation method according to any one of claims 3 to 5, further comprising cooling to room temperature before the filtration;
the cooling rate is 3-40 ℃/h.
10. Use of the rare earth-based halide luminescent material according to any one of claims 1 to 2 or the rare earth-based halide luminescent material prepared by the preparation method according to any one of claims 3 to 9 as an anti-counterfeiting material.
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| CN116656357A (en) * | 2023-05-06 | 2023-08-29 | 安徽中公检测科技有限公司 | Yb (Yb) 3+ /Er 3+ Doping Cs 2 NaBiCl 6 Up-conversion luminescence temperature sensing fluorescent material and preparation method thereof |
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| CN115746853A (en) * | 2022-11-30 | 2023-03-07 | 中国科学院长春应用化学研究所 | Method for preparing double perovskite structure rare earth luminescent crystal |
| CN115746853B (en) * | 2022-11-30 | 2024-05-24 | 中国科学院长春应用化学研究所 | Method for preparing double perovskite structure rare earth luminescent crystal |
| CN116656357A (en) * | 2023-05-06 | 2023-08-29 | 安徽中公检测科技有限公司 | Yb (Yb) 3+ /Er 3+ Doping Cs 2 NaBiCl 6 Up-conversion luminescence temperature sensing fluorescent material and preparation method thereof |
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