CN113481005A - Rare earth doped zirconium fluoride cesium-based up-conversion luminescent nano material and preparation method thereof - Google Patents
Rare earth doped zirconium fluoride cesium-based up-conversion luminescent nano material and preparation method thereof Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 43
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 37
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 34
- PWWTYEKNYQQRRC-UHFFFAOYSA-I [F-].[F-].[F-].[F-].[F-].[Zr+4].[Cs+] Chemical compound [F-].[F-].[F-].[F-].[F-].[Zr+4].[Cs+] PWWTYEKNYQQRRC-UHFFFAOYSA-I 0.000 title claims abstract description 20
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 17
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229910052691 Erbium Inorganic materials 0.000 claims description 14
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 11
- -1 rare earth acetate Chemical class 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 7
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- OSCVBYCJUSOYPN-UHFFFAOYSA-K ytterbium(3+);triacetate Chemical compound [Yb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OSCVBYCJUSOYPN-UHFFFAOYSA-K 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- DBUHPIKTDUMWTR-UHFFFAOYSA-K erbium(3+);triacetate Chemical compound [Er+3].CC([O-])=O.CC([O-])=O.CC([O-])=O DBUHPIKTDUMWTR-UHFFFAOYSA-K 0.000 claims description 3
- BONORRGKLJBGRV-UHFFFAOYSA-N methapyrilene hydrochloride Chemical compound Cl.C=1C=CC=NC=1N(CCN(C)C)CC1=CC=CS1 BONORRGKLJBGRV-UHFFFAOYSA-N 0.000 claims description 3
- SNMVVAHJCCXTQR-UHFFFAOYSA-K thulium(3+);triacetate Chemical compound [Tm+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SNMVVAHJCCXTQR-UHFFFAOYSA-K 0.000 claims description 3
- WQXKGOOORHDGFP-UHFFFAOYSA-N 1,2,4,5-tetrafluoro-3,6-dimethoxybenzene Chemical compound COC1=C(F)C(F)=C(OC)C(F)=C1F WQXKGOOORHDGFP-UHFFFAOYSA-N 0.000 claims description 2
- WYOIGGSUICKDNZ-UHFFFAOYSA-N 2,3,5,6,7,8-hexahydropyrrolizin-1-one Chemical compound C1CCC2C(=O)CCN21 WYOIGGSUICKDNZ-UHFFFAOYSA-N 0.000 claims description 2
- BYDYILQCRDXHLB-UHFFFAOYSA-N 3,5-dimethylpyridine-2-carbaldehyde Chemical compound CC1=CN=C(C=O)C(C)=C1 BYDYILQCRDXHLB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- LYQGMALGKYWNIU-UHFFFAOYSA-K gadolinium(3+);triacetate Chemical compound [Gd+3].CC([O-])=O.CC([O-])=O.CC([O-])=O LYQGMALGKYWNIU-UHFFFAOYSA-K 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- JPDBEEUPLFWHAJ-UHFFFAOYSA-K samarium(3+);triacetate Chemical compound [Sm+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JPDBEEUPLFWHAJ-UHFFFAOYSA-K 0.000 claims description 2
- JQBILSNVGUAPMM-UHFFFAOYSA-K terbium(3+);triacetate Chemical compound [Tb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JQBILSNVGUAPMM-UHFFFAOYSA-K 0.000 claims description 2
- 238000003384 imaging method Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- HIQSCMNRKRMPJT-UHFFFAOYSA-J lithium;yttrium(3+);tetrafluoride Chemical compound [Li+].[F-].[F-].[F-].[F-].[Y+3] HIQSCMNRKRMPJT-UHFFFAOYSA-J 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- OWFHVHWXOGAVRB-UHFFFAOYSA-J sodium;gadolinium(3+);tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Na+].[Gd+3] OWFHVHWXOGAVRB-UHFFFAOYSA-J 0.000 description 1
- HQHVZNOWXQGXIX-UHFFFAOYSA-J sodium;yttrium(3+);tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Na+].[Y+3] HQHVZNOWXQGXIX-UHFFFAOYSA-J 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910021561 transition metal fluoride Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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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- Organic Chemistry (AREA)
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Abstract
The invention discloses a rare earth doped zirconium fluoride cesium based up-conversion luminescent nano material and a preparation method thereof. The rare earth doped zirconium fluoride cesium-based up-conversion luminescent nano material is Cs with hexagonal phase2ZrF6The particle size of the nano material is 5-10 nm; the invention adopts zirconium acetylacetonate as Zr metal salt, and utilizes a high-temperature coprecipitation method to synthesize the rare earth doped zirconium fluoride cesium-based up-conversion luminescent nano material, the synthesis condition is easy to control, the repeatability is good, and the prepared luminescent nano material has good dispersibility, uniformity and luminescent property, can be used as an ideal substrate material for up-conversion luminescence, and has wide application prospect in the fields of luminescent imaging, biological application and the like.
Description
Technical Field
The invention relates to a rare earth doped zirconium fluoride cesium based up-conversion luminescent nano material and a preparation method thereof, belonging to the technical field of luminescent materials.
Background
The rare earth doped up-conversion luminescent nano material has the advantages of weak background interference, long fluorescence life, low excitation energy, deep tissue penetration and the like, thereby showing wide application prospect in the fields of illumination display, drug transportation, biomedical imaging, biological marking and the like, and being a research hotspot at home and abroad in recent years. Rare earth doped nano luminescent materialThe material consists of a matrix material and rare earth doped ions, wherein the matrix material has very important influence on the up-conversion luminescence property of the material. Among the numerous studied host materials, fluoride has stable physicochemical properties and low phonon energy, and is a good luminescent host material. The current research on rare earth doped fluoride luminescent host materials is mainly focused on sodium yttrium fluoride (NaYF)4) Sodium gadolinium fluoride (NaGdF)4) Or yttrium lithium fluoride (LiYF)4) The alkali metal rare earth fluoride systems are less researched, and especially the alkali metal transition metal fluoride system based on the transition metal zirconium is less researched.
Disclosure of Invention
The technical problem solved by the invention is as follows: how to obtain the rare earth doped zirconium fluoride cesium based up-conversion luminescent nano material.
In order to solve the technical problem, the invention provides a rare earth doped zirconium fluoride cesium-based up-conversion luminescent nano material, which has a chemical formula as follows: cs2ZrF6:x％Ln 3+Wherein, 0<x is less than or equal to 50, and the rare earth element Ln is selected from one or more of Yb, Er, Tm, Ho, Gd, Dy, Sm, Nd and Pr.
Preferably, the rare earth elements Ln in the material include Yb and Er; the chemical formula of the material is as follows: cs2ZrF6:x1％Yb 3+/x2％Er3+Wherein, 0<x1+x2≤50。
Preferably, the material has a hexagonal phase structure; the particle size of the material is 5-10 nm.
The invention also provides a preparation method of the rare earth doped zirconium fluoride cesium based up-conversion luminescent nano material, which comprises the following steps:
s1, dissolving rare earth acetate and zirconium acetylacetonate in a solvent;
s2, mixing the solution obtained in the step S1 with an alcohol solution dissolved with cesium carbonate and ammonium fluoride, and then heating to remove alcohol;
s3, heating the solution obtained after the alcohol is removed in the step S2 for reaction, and preparing the rare earth doped zirconium fluoride cesium-based up-conversion luminescent nano material.
Preferably, the dissolving conditions in S1 are: heating to 100-200 ℃ under the protection of inert gas, and preserving heat for 20-90 minutes.
Preferably, the rare earth acetate in S1 is selected from at least one of ytterbium acetate, erbium acetate, thulium acetate, holmium acetate, gadolinium acetate, terbium acetate, dysprosium acetate, samarium acetate, neodymium acetate and praseodymium acetate; the solvent is selected from a mixed solvent consisting of oleic acid and octadecene; the mol ratio of the oleic acid to the octadecene is 1: 0.5-5.
Preferably, the molar ratio of the rare earth acetate to the zirconium acetylacetonate in the S1 is 0.50-0.10: 0.50-0.90; the molar ratio of the rare earth acetate to the solvent is 0.50-0.10: 50-80.
Preferably, the molar ratio of ammonium fluoride to cesium carbonate in S2 is 6: 1-5; the alcohol in the alcohol solution is selected from at least one of methanol, ethanol, propanol and butanol; the molar volume concentration of ammonium fluoride in the alcoholic solution is 5-10 mmol/mL; the molar ratio of the zirconium acetylacetonate to the ammonium fluoride is 0.50-0.90: 6.
Preferably, the conditions for removing the alcohol by heating in S2 are as follows: and (3) heating to 40-100 ℃ in an inert atmosphere, and preserving the heat for 20-90 minutes.
Preferably, the heating reaction conditions in S3 are as follows: the temperature is 250-300 ℃, and the time is 1-4 h; the method also comprises a post-treatment step after the heating reaction is finished: cooling to room temperature, centrifuging, washing and drying.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts zirconium acetylacetonate as metal salt of Zr, and utilizes high-temperature coprecipitation method to synthesize rare earth doped Cs2ZrF6The up-conversion luminescent nano material has the advantages of easy control of synthesis conditions and good repeatability, and the prepared luminescent nano material has good dispersibility, uniformity and up-conversion luminescent performance, can be used as an ideal substrate material for up-conversion luminescent, and has great development potential in the fields of luminescent imaging, biological application and the like.
Drawings
FIG. 1 is hexagonal phase Cs2ZrF6:20mol％Yb3+，2mol％Er3+And (3) a transmission electron microscope photo of the up-conversion luminescent nano material.
FIG. 2 is hexagonal phase Cs2ZrF6:20mol％Yb3+，2mol％Er3+An X-ray powder diffraction pattern of the upconverting luminescent nanomaterial.
FIG. 3 is hexagonal phase Cs2ZrF6:20mol％Yb3+，2mol％Er3+Upconversion fluorescence spectrum of upconversion luminescent nano material under excitation of 980nm laser.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
In the following examples, the starting reagents used are all commercially available products.
Example 1
Preparation of Cs2ZrF6:20mol％Yb3+,2mol％Er3+The preparation method of the up-conversion luminescent nano material comprises the following steps:
0.3804g of zirconium acetylacetonate, 0.007g of erbium acetate and 0.0845g of ytterbium acetate were weighed at room temperature into a 100mL three-necked flask, and 8mL of oleic acid and 12mL of octadecene were added and mixed well with stirring. Under the protection of nitrogen flow, the mixture is heated to 150 ℃, and the temperature is kept for 60 minutes at the temperature, so that zirconium acetylacetonate and rare earth acetate are completely dissolved, and a transparent clear solution is obtained. After cooling to room temperature, 15mL of a methanol solution containing 0.4887g of cesium carbonate and 0.2223g of ammonium fluoride was added dropwise, and the mixture was stirred to react at room temperature for 30 minutes. The mixed solution was then heated to 50 ℃ and incubated for 30 minutes to remove methanol from the reaction system. After the methanol is removed, heating the reaction system to 280 ℃ under the protection of nitrogen flow, preserving the temperature for 60 minutes, naturally cooling to room temperature, precipitating and washing to obtain the hexagonal phase Cs2ZrF6:20mol％Yb3+,2mol％Er3+An upconversion luminescent nanomaterial.
As shown in FIG. 1, Cs2ZrF6:20mol％Yb3+,2mol％Er3+The up-conversion luminescent nano material has good dispersibility, uniform appearance and nano crystal with the grain diameter of about 5 nm.
As shown in FIG. 2, Cs2ZrF6:20mol％Yb3+,2mol％Er3+The up-conversion luminescent nano material has good crystallinity, and the diffraction peak position and relative intensity and Cs thereof2ZrF6The PDF standard cards (JCPDS No.74-0173) are consistent and belong to the hexagonal system.
As shown in FIG. 3, Cs is excited by 980nm near infrared light2ZrF6:20mol％Yb3+,2mol％Er3+The upconversion luminescent nano material presents upconversion emission in a purple light region (400-3+Is/are as follows2H9/2To4I15/2，2H11/2/4S3/2To4I15/2And are and4F9/2to4I15/2Is detected.
Example 2
Cs (volatile organic Compounds)2ZrF6:20mol％Yb3+,2mol％Tm3+The preparation method of the up-conversion luminescent nano material comprises the following steps:
0.3804g of zirconium acetylacetonate, 0.0072g of thulium acetate and 0.0845g of ytterbium acetate were weighed at room temperature and charged into a 100mL three-necked flask, and 8mL of oleic acid and 12mL of octadecene were added and stirred to mix them uniformly. Under the protection of nitrogen flow, the mixture is heated to 150 ℃, and the temperature is kept for 60 minutes at the temperature, so that zirconium acetylacetonate and rare earth acetate are completely dissolved, and a transparent clear solution is obtained. After cooling to room temperature, 15mL of a methanol solution containing 0.4887g of cesium carbonate and 0.2223g of ammonium fluoride was added dropwise, and the mixture was stirred to react at room temperature for 30 minutes. The mixed solution was then heated to 50 ℃ and incubated for 30 minutes to remove methanol from the reaction system. After the methanol is removed, heating the reaction system to 280 ℃ under the protection of nitrogen flow, preserving the temperature for 60 minutes, naturally cooling to room temperature, precipitating and washing to obtain the hexagonal phase Cs2ZrF6:20mol％Yb3+,2mol％Tm3+An upconversion luminescent nanomaterial.
Example 3
Cs (volatile organic Compounds)2ZrF6:20mol％Yb3+,2mol％Ho3+The preparation method of the up-conversion luminescent nano material comprises the following steps:
0.3804g of zirconium acetylacetonate, 0.0068g of holmium acetate and 0.0845g of ytterbium acetate are weighed at room temperature and added into a 100mL three-neck flask, 8mL of oleic acid and 12mL of octadecene are added, and the mixture is stirred to be uniformly mixed. Under the protection of nitrogen flow, the mixture is heated to 150 ℃, and the temperature is kept for 60 minutes at the temperature, so that zirconium acetylacetonate and rare earth acetate are completely dissolved, and a transparent clear solution is obtained. After cooling to room temperature, 15mL of a methanol solution containing 0.4887g of cesium carbonate and 0.2223g of ammonium fluoride was added dropwise, and the mixture was stirred to react at room temperature for 30 minutes. The mixed solution was then heated to 50 ℃ and incubated for 30 minutes to remove methanol from the reaction system. After the methanol is removed, heating the reaction system to 280 ℃ under the protection of nitrogen flow, preserving the temperature for 60 minutes, naturally cooling to room temperature, precipitating and washing to obtain the hexagonal phase Cs2ZrF6:20mol％Yb3+,2mol％Ho3+An upconversion luminescent nanomaterial.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A rare earth doped zirconium fluoride cesium-based up-conversion luminescent nano material is characterized in that the chemical formula of the material is as follows: cs2ZrF6:x％Ln 3+Wherein, 0<x is less than or equal to 50, and the rare earth element Ln is selected from one or more of Yb, Er, Tm, Ho, Gd, Dy, Sm, Nd and Pr.
2. The rare earth-doped cesium zirconium fluoride upconversion luminescent nanomaterial of claim 1, wherein the rare earth element Ln in the material comprises Yb and Er; the chemical formula of the material is as follows: cs2ZrF6:x1％Yb 3+/x2％Er3+Wherein, 0<x1+x2≤50。
3. The rare earth-doped cesium zirconium fluoride-based up-conversion luminescent nanomaterial of claim 1, wherein the material has a hexagonal phase structure; the particle size of the material is 5-10 nm.
4. The preparation method of the rare earth doped zirconium cesium fluoride based up-conversion luminescent nano material as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
s1, dissolving rare earth acetate and zirconium acetylacetonate in a solvent;
s2, mixing the solution obtained in the step S1 with an alcohol solution dissolved with cesium carbonate and ammonium fluoride, and then heating to remove alcohol;
s3, heating the solution obtained after the alcohol is removed in the step S2 for reaction, and preparing the rare earth doped zirconium fluoride cesium-based up-conversion luminescent nano material.
5. The method for preparing the rare earth-doped cesium zirconium fluoride-based up-conversion luminescent nanomaterial of claim 4, wherein the dissolving conditions in S1 are as follows: heating to 100-200 ℃ under the protection of inert gas, and preserving heat for 20-90 minutes.
6. The method of claim 4, wherein the rare earth acetate in S1 is at least one selected from ytterbium acetate, erbium acetate, thulium acetate, holmium acetate, gadolinium acetate, terbium acetate, dysprosium acetate, samarium acetate, neodymium acetate, and praseodymium acetate; the solvent is selected from a mixed solvent consisting of oleic acid and octadecene; the mol ratio of the oleic acid to the octadecene is 1: 0.5-5.
7. The method for preparing the rare earth-doped zirconium fluoride cesium-based up-conversion luminescent nanomaterial according to claim 4, wherein the molar ratio of the rare earth acetate to the zirconium acetylacetonate in S1 is 0.50-0.10: 0.50-0.90; the molar ratio of the rare earth acetate to the solvent is 0.50-0.10: 50-80.
8. The method for preparing the rare earth-doped cesium zirconium fluoride-based up-conversion luminescent nanomaterial according to claim 4, wherein the molar ratio of ammonium fluoride to cesium carbonate in S2 is 6: 1-5; the alcohol in the alcohol solution is selected from at least one of methanol, ethanol, propanol and butanol; the molar volume concentration of ammonium fluoride in the alcoholic solution is 5-10 mmol/mL; the molar ratio of the zirconium acetylacetonate to the ammonium fluoride is 0.50-0.90: 6.
9. The method for preparing the rare earth-doped cesium zirconium fluoride-based up-conversion luminescent nanomaterial according to claim 4, wherein the conditions for removing the alcohol by raising the temperature in S2 are as follows: and (3) heating to 40-100 ℃ in an inert atmosphere, and preserving the heat for 20-90 minutes.
10. The method for preparing the rare earth-doped cesium zirconium fluoride up-conversion luminescent nanomaterial of claim 4, wherein the heating reaction conditions in S3 are as follows: the temperature is 250-300 ℃, and the time is 1-4 h; the method also comprises a post-treatment step after the heating reaction is finished: cooling to room temperature, centrifuging, washing and drying.
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