CN116426277B - Pure green up-conversion luminescent nano material and preparation method thereof - Google Patents

Pure green up-conversion luminescent nano material and preparation method thereof Download PDF

Info

Publication number
CN116426277B
CN116426277B CN202310417111.1A CN202310417111A CN116426277B CN 116426277 B CN116426277 B CN 116426277B CN 202310417111 A CN202310417111 A CN 202310417111A CN 116426277 B CN116426277 B CN 116426277B
Authority
CN
China
Prior art keywords
trifluoroacetate
pure green
ltoreq
conversion luminescent
erbium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202310417111.1A
Other languages
Chinese (zh)
Other versions
CN116426277A (en
Inventor
乔旭升
戴晓茹
陈东
董文坤
凌世生
冀皓丽
王思源
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hangzhou Anxiu Biotechnology Co ltd
Zhejiang University ZJU
Original Assignee
Hangzhou Anxiu Biotechnology Co ltd
Zhejiang University ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hangzhou Anxiu Biotechnology Co ltd, Zhejiang University ZJU filed Critical Hangzhou Anxiu Biotechnology Co ltd
Priority to CN202310417111.1A priority Critical patent/CN116426277B/en
Publication of CN116426277A publication Critical patent/CN116426277A/en
Application granted granted Critical
Publication of CN116426277B publication Critical patent/CN116426277B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C01G15/006—Compounds containing, besides gallium, indium, or thallium, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biophysics (AREA)
  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention discloses a pure green up-conversion luminescent nanomaterial and a preparation method thereof, wherein the chemical expression general formula of the pure green up-conversion luminescent nanomaterial is K 3 Sr 4‑x‑y‑z In 5 F 26 : xYb, yEr, zPr, wherein 0.1.ltoreq.x.ltoreq.0.4, 0.01.ltoreq.y.ltoreq. 0.03,0.01.ltoreq.z.ltoreq.0.03, the material having a tetragonal phase lattice structure. The invention can solve the problem that the existing green fluorescent coding material has low luminescence monochromaticity or color purity. The rare earth doped pure green up-conversion nano material has the advantages of low reaction temperature, high purity, good uniformity, high luminous intensity, high color purity and excellent monochromaticity, and has great application prospect in the field of biological detection such as fluorescent coding probes.

Description

Pure green up-conversion luminescent nano material and preparation method thereof
Technical Field
The invention relates to a pure green up-conversion luminescent nano material and a preparation method thereof, in particular to a super-bright single green rare earth up-conversion fluorescent nano crystal material and a preparation method thereof.
Background
The rare earth luminescent nano material has wide application prospect in multiple fields such as biological imaging, anti-counterfeiting coding, fluorescent display, temperature sensing and the like by virtue of the characteristics of rich luminescence, stable property, sharp band, long service life, easiness in surface modification, capability of avoiding biological autofluorescence and the like. Taking biological detection as an example, the existing probe materials are mostly quantum dots and organic dyes, however, the materials have the defects of high toxicity, easy photobleaching, background fluorescence interference and the like. The rare earth doped up-conversion luminescent material can absorb light in the range of a biological window (650-1000 nm) and convert the light into visible light, so that the tissue penetration depth is high, the interference of biological autofluorescence is avoided, and the detection sensitivity is improved. However, the rare earth up-conversion nanocrystals are limited by rare earth energy level structures and transition modes, and the problems of low color purity, low luminous efficiency and the like still exist, so that the practical application of the rare earth up-conversion nanocrystals in the biological field is limited. As reported at present, hexagonal phase NaYF doped with rare earth Yb and Er 4 Nanocrystals can achieve green luminescence under 980nm laser irradiation, but lower color purity and fluorescence intensity limit their resolution as biological probes. Therefore, it is necessary to greatly improve the rare earth pure green luminous efficiency from the viewpoint of designing the matrix material.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problem to be solved by the invention is to provide a pure green up-conversion luminescent nano material and a preparation method thereof, and provide a new idea for designing and developing more other types of single-color rare earth up-conversion fluorescent nano crystals.
The technical problems of the invention are realized by the following technical scheme:
a pure green up-conversion luminescent nano material is characterized in that the chemical expression general formula is K 3 Sr 4-x-y- z In 5 F 26 : xYb, yEr, zPr, wherein 0.1.ltoreq.x.ltoreq.0.4, 0.01.ltoreq.y.ltoreq. 0.03,0.01.ltoreq.z.ltoreq.0.03. The pure green up-conversion luminescent nanomaterial has tetragonal lattice junctionThe space group is P42/n.
Preferably, the chemical expression of the pure green up-conversion luminescent nano material is K 3 Sr 3.76 In 5 F 26 ：0.2Yb，0.02Er，0.02Pr。
On the other hand, the invention also provides the technical scheme that:
the preparation method of the pure green up-conversion luminescent nanomaterial is characterized by comprising the following steps of:
s1, respectively dissolving potassium carbonate, strontium carbonate, indium carbonate, ytterbium oxide, erbium oxide and praseodymium oxide in a trifluoroacetic acid aqueous solution to form a corresponding uniformly clarified trifluoroacetic acid salt solution, uniformly stirring at 85 ℃ and evaporating the solvent to obtain corresponding solid powder;
s2, dispersing the solid trifluoroacetate powder obtained in the S1 into a mixed solvent of oleic acid and oleylamine according to a certain stoichiometric ratio, heating to 130 ℃ in a nitrogen atmosphere, and stirring for 2 hours;
s3, rapidly heating the solution obtained in the step S2 to 350 ℃ for reaction for 10min, cooling to 330 ℃ for heat preservation for 1h, rapidly cooling to room temperature, and adding acetone to precipitate a product;
s4, centrifugally washing the product obtained in the step S3 with acetone and cyclohexane for multiple times, and drying in vacuum to obtain the pure green up-conversion fluorescent nanocrystalline material.
In step S1, potassium carbonate, strontium carbonate, indium carbonate, ytterbium oxide, erbium oxide, and praseodymium oxide are dissolved in aqueous trifluoroacetic acid solutions having volume concentrations of 20%, 50%, and 50%, respectively.
Further, in the step S2, the volume ratio of oleic acid to oleylamine is 1:1; the ratio of oleic acid usage to trifluoroacetate solid powder was 6ml/1mmol.
Further, in step S3, the temperature rising rate is 30 ℃/min, and the temperature rises to 350 ℃.
Further, in the solid powder of trifluoroacetate salt in step S2, potassium trifluoroacetate: strontium trifluoroacetate: indium trifluoroacetate: ytterbium trifluoroacetate: erbium trifluoroacetate: the molar ratio of the praseodymium trifluoroacetate is 3:4:3.78:0.2:0.02:0.02.
Further, in the solid powder of trifluoroacetate salt in step S2, potassium trifluoroacetate: strontium trifluoroacetate: indium trifluoroacetate: ytterbium trifluoroacetate: erbium trifluoroacetate: the molar ratio of the praseodymium trifluoroacetate is 3:4:3.88:0.1:0.01:0.01.
Further, in the solid powder of trifluoroacetate salt in step S2, potassium trifluoroacetate: strontium trifluoroacetate: indium trifluoroacetate: ytterbium trifluoroacetate: erbium trifluoroacetate: the molar ratio of the praseodymium trifluoroacetate is 3:4:3.66:0.3:0.02:0.02.
Further, in the solid powder of trifluoroacetate salt in step S2, potassium trifluoroacetate: strontium trifluoroacetate: indium trifluoroacetate: ytterbium trifluoroacetate: erbium trifluoroacetate: the molar ratio of the praseodymium trifluoroacetate is 3:4:3.54:0.4:0.03:0.03.
The invention has the beneficial effects that:
the tetragonal pure green up-conversion luminescent nanomaterial prepared by the invention has the advantages of uniform size distribution, high fluorescence intensity, high luminescent intensity, high color purity and excellent monochromaticity. Wherein K is 3 Sr 3.76 In 5 F 26 : the main wavelength of 0.2Yb,0.02Er and 0.02Pr is 541nm, the spectral line width is 11.46nm, the integral intensity of the green fluorescence wave band accounts for more than 97 percent (97.4 percent) of the total spectral intensity, and the integral intensity of the green fluorescence wave band is enhanced by an order of magnitude compared with the existing single green up-conversion fluorescence nano material, and the color purity is up to 95.9 percent. And compared with the single green up-conversion fluorescent material obtained by traditional calcination, the preparation process is more environment-friendly and simple, and has low reaction temperature and low cost during preparation. The fluorescence intensity of the pure green up-conversion luminescence nano material obtained by the invention is adjustable by four orders of magnitude, and has great application potential in the field of biological detection fluorescence coding.
Drawings
FIG. 1 is a transmission electron microscope image of a pure green up-conversion luminescence nanomaterial prepared in example 1 of the present invention;
FIG. 2 is an X-ray diffraction (XRD) pattern of the pure green up-conversion luminescent nanomaterial prepared in example 1 of the present invention;
FIG. 3 is a spectrum diagram of a pure green up-conversion luminescent nanomaterial under 980nm excitation prepared by an embodiment of the present invention;
FIG. 4 is a transmission electron micrograph of a comparative example, in which (a) is a transmission electron micrograph of the green nanocrystal material prepared in comparative example 1 and (b) is a transmission electron micrograph of the green nanocrystal material prepared in comparative example 2;
FIG. 5 is a graph showing the spectral contrast of the pure green up-conversion luminescent nanomaterials prepared in examples 1, 2, 4, and 6 of the present invention with the nanocrystals prepared in comparative examples 1 and 2 of the prior art under 980nm excitation;
FIG. 6 is a chromaticity diagram of color coordinates of spectra of the present invention in examples 1, 2, 4, 6 and comparative examples 1, 2.
Detailed Description
For a clearer understanding of the present invention, the present invention will be further described with reference to the detailed description and drawings, but should not be construed to limit the scope of the invention.
Example 1: k (K) 3 Sr 3.76 In 5 F 26 : preparation of 0.2Yb,0.02Er and 0.02Pr nanocrystalline
The preparation method of the pure green up-conversion fluorescent nanocrystals comprises the following steps:
s1, respectively dissolving potassium carbonate, strontium carbonate, indium carbonate, ytterbium oxide, erbium oxide and praseodymium oxide in trifluoroacetic acid aqueous solutions with volume concentrations of 20%, 50% and 50% to form corresponding uniform and clear trifluoroacetic acid salt solutions, uniformly stirring at 85 ℃ and evaporating the solvents to obtain corresponding solid powder.
S2, the solid powder of trifluoroacetate obtained in the step S1 is prepared according to potassium trifluoroacetate: strontium trifluoroacetate: indium trifluoroacetate: ytterbium trifluoroacetate: erbium trifluoroacetate: praseodymium trifluoroacetate is dispersed in a mixed solvent of oleic acid and oleylamine (volume ratio is 1:1) in a molar ratio of 3:4:3.78:0.2:0.02:0.02, and is heated to 130 ℃ under nitrogen atmosphere and stirred for 2 hours; wherein the ratio of oleic acid usage to trifluoroacetate solid powder was 6ml/1mmol.
S3, rapidly heating the solution obtained in the step S2 to 350 ℃, reacting for 10min, cooling to 330 ℃, preserving heat for 1h, rapidly cooling to room temperature, and adding acetone to precipitate a product.
S4, centrifugally washing the product obtained in the step S3 with acetone and cyclohexane for multiple times, and drying in vacuum to obtain K 3 Sr 3.76 In 5 F 26 : pure green up-conversion fluorescent nanocrystalline materials of 0.2Yb,0.02Er and 0.02 Pr.
The K is 3 Sr 3.76 In 5 F 26 : the transmission electron microscope diagrams of the 0.2Yb,0.02Er and 0.02Pr pure green up-conversion fluorescent nanocrystalline materials are shown in figure 1, the X-ray diffraction (XRD) diagram is shown in figure 2, and the spectrum diagram under 980nm excitation is shown in figure 3.
Example 2: k (K) 3 Sr 3.88 In 5 F 26 : preparation of 0.1Yb,0.01Er and 0.01Pr nanocrystals
S1, respectively dissolving potassium carbonate, strontium carbonate, indium carbonate, ytterbium oxide, erbium oxide and praseodymium oxide in trifluoroacetic acid aqueous solutions with volume concentrations of 20%, 50% and 50% to form corresponding uniform and clear trifluoroacetic acid salt solutions, uniformly stirring at 85 ℃ and evaporating the solvents to obtain corresponding solid powder.
S2, the solid powder of trifluoroacetate obtained in the step S1 is prepared according to potassium trifluoroacetate: strontium trifluoroacetate: indium trifluoroacetate: ytterbium trifluoroacetate: erbium trifluoroacetate: praseodymium trifluoroacetate is dispersed in a mixed solvent of oleic acid and oleylamine (volume ratio is 1:1) in a molar ratio of 3:4:3.88:0.1:0.01:0.01, and is heated to 130 ℃ under nitrogen atmosphere and stirred for 2 hours; wherein the ratio of oleic acid usage to trifluoroacetate solid powder was 6ml/1mmol.
S3, rapidly heating the solution obtained in the step S2 to 350 ℃, reacting for 10min, cooling to 330 ℃, preserving heat for 1h, rapidly cooling to room temperature, and adding acetone to precipitate a product.
S4, centrifugally washing the product obtained in the step S3 with acetone and cyclohexane for multiple times, and drying in vacuum to obtain K 3 Sr 3.88 In 5 F 26 : up-conversion fluorescent nanocrystalline material of 0.1Yb,0.01Er and 0.01 Pr.
Example 3: k (K) 3 Sr 3.86 In 5 F 26 : preparation of 0.1Yb,0.02Er and 0.02Pr nanocrystalline
S1, respectively dissolving potassium carbonate, strontium carbonate, indium carbonate, ytterbium oxide, erbium oxide and praseodymium oxide in trifluoroacetic acid aqueous solutions with volume concentrations of 20%, 50% and 50% to form corresponding uniform and clear trifluoroacetic acid salt solutions, uniformly stirring at 85 ℃ and evaporating the solvents to obtain corresponding solid powder.
S2, the solid powder of trifluoroacetate obtained in the step S1 is prepared according to potassium trifluoroacetate: strontium trifluoroacetate: indium trifluoroacetate: ytterbium trifluoroacetate: erbium trifluoroacetate: praseodymium trifluoroacetate is dispersed in a mixed solvent of oleic acid and oleylamine (volume ratio is 1:1) in a molar ratio of 3:4:3.86:0.1:0.02:0.02, and is heated to 130 ℃ under nitrogen atmosphere and stirred for 2 hours; wherein the ratio of oleic acid usage to trifluoroacetate solid powder was 6ml/1mmol.
S3, rapidly heating the solution obtained in the step S2 to 350 ℃, reacting for 10min, cooling to 330 ℃, preserving heat for 1h, rapidly cooling to room temperature, and adding acetone to precipitate a product.
S4, centrifugally washing the product obtained in the step S3 with acetone and cyclohexane for multiple times, and drying in vacuum to obtain K 3 Sr 3.88 In 5 F 26 : up-conversion fluorescent nanocrystalline material of 0.1Yb,0.02Er and 0.02 Pr.
Example 4: k (K) 3 Sr 3.66 In 5 F 26 : preparation of 0.3Yb,0.02Er and 0.02Pr nanocrystalline
S1, respectively dissolving potassium carbonate, strontium carbonate, indium carbonate, ytterbium oxide, erbium oxide and praseodymium oxide in trifluoroacetic acid aqueous solutions with volume concentrations of 20%, 50% and 50% to form corresponding uniform and clear trifluoroacetic acid salt solutions, uniformly stirring at 85 ℃ and evaporating the solvents to obtain corresponding solid powder.
S2, the solid powder of trifluoroacetate obtained in the step S1 is prepared according to potassium trifluoroacetate: strontium trifluoroacetate: indium trifluoroacetate: ytterbium trifluoroacetate: erbium trifluoroacetate: praseodymium trifluoroacetate is dispersed in a mixed solvent of oleic acid and oleylamine (volume ratio is 1:1) in a molar ratio of 3:4:3.66:0.3:0.02:0.02, and is heated to 130 ℃ under nitrogen atmosphere and stirred for 2 hours; wherein the ratio of oleic acid usage to trifluoroacetate solid powder was 6ml/1mmol.
S3, rapidly heating the solution obtained in the step S2 to 350 ℃, reacting for 10min, cooling to 330 ℃, preserving heat for 1h, rapidly cooling to room temperature, and adding acetone to precipitate a product.
S4, centrifugally washing the product obtained in the step S3 with acetone and cyclohexane for multiple times, and drying in vacuum to obtain K 3 Sr 3.68 In 5 F 26 : up-conversion fluorescent nanocrystalline material of 0.3Yb,0.02Er and 0.02 Pr.
Example 5: k (K) 3 Sr 3.56 In 5 F 26 : preparation of 0.4Yb,0.02Er and 0.02Pr nanocrystalline
S1, respectively dissolving potassium carbonate, strontium carbonate, indium carbonate, ytterbium oxide, erbium oxide and praseodymium oxide in trifluoroacetic acid aqueous solutions with volume concentrations of 20%, 50% and 50% to form corresponding uniform and clear trifluoroacetic acid salt solutions, uniformly stirring at 85 ℃ and evaporating the solvents to obtain corresponding solid powder.
S2, the solid powder of trifluoroacetate obtained in the step S1 is prepared according to potassium trifluoroacetate: strontium trifluoroacetate: indium trifluoroacetate: ytterbium trifluoroacetate: erbium trifluoroacetate: praseodymium trifluoroacetate is dispersed in a mixed solvent of oleic acid and oleylamine (volume ratio is 1:1) in a molar ratio of 3:4:3.56:0.4:0.02:0.02, and is heated to 130 ℃ under nitrogen atmosphere and stirred for 2 hours; wherein the ratio of oleic acid usage to trifluoroacetate solid powder was 6ml/1mmol.
S3, rapidly heating the solution obtained in the step S2 to 350 ℃, reacting for 10min, cooling to 330 ℃, preserving heat for 1h, rapidly cooling to room temperature, and adding acetone to precipitate a product.
S4, centrifugally washing the product obtained in the step S3 with acetone and cyclohexane for multiple times, and drying in vacuum to obtain K 3 Sr 3.58 In 5 F 26 : up-conversion fluorescent nanocrystalline material of 0.4Yb,0.02Er and 0.02 Pr.
Example 6: k (K) 3 Sr 3.54 In 5 F 26 : preparation of 0.4Yb,0.03Er and 0.03Pr nanocrystalline
S1, respectively dissolving potassium carbonate, strontium carbonate, indium carbonate, ytterbium oxide, erbium oxide and praseodymium oxide in trifluoroacetic acid aqueous solutions with volume concentrations of 20%, 50% and 50% to form corresponding uniform and clear trifluoroacetic acid salt solutions, uniformly stirring at 85 ℃ and evaporating the solvents to obtain corresponding solid powder.
S2, the solid powder of trifluoroacetate obtained in the step S1 is prepared according to potassium trifluoroacetate: strontium trifluoroacetate: indium trifluoroacetate: ytterbium trifluoroacetate: erbium trifluoroacetate: praseodymium trifluoroacetate is dispersed in a mixed solvent of oleic acid and oleylamine (volume ratio is 1:1) in a molar ratio of 3:4:3.54:0.4:0.03:0.03, and is heated to 130 ℃ under nitrogen atmosphere and stirred for 2 hours; wherein the ratio of oleic acid usage to trifluoroacetate solid powder was 6ml/1mmol.
S3, rapidly heating the solution obtained in the step S2 to 350 ℃, reacting for 10min, cooling to 330 ℃, preserving heat for 1h, rapidly cooling to room temperature, and adding acetone to precipitate a product.
S4, centrifugally washing the product obtained in the step S3 with acetone and cyclohexane for multiple times, and drying in vacuum to obtain K 3 Sr 3.56 In 5 F 26 : up-conversion fluorescent nanocrystalline material of 0.4Yb,0.03Er and 0.03 Pr.
Comparative example 1
Preparation of NaY 0.76 F 4 0.2Yb,0.02Er and 0.02Pr nano-crystal, which comprises the following steps:
s1, dissolving yttrium acetate, ytterbium acetate, erbium acetate and praseodymium acetate in a mixed solution of 10ml of oleic acid and 10ml of octadecene according to a molar ratio of 0.76:0.2:0.02:0.02 in total 1mmol of acetate, heating to 150 ℃, stirring to remove oxygen, and removing water for 1h to form a uniform and clear precursor solution.
S2, after the solution obtained in S1 is cooled to room temperature, 10ml of a methanol solution in which 3mmol of ammonium fluoride and 2mmol of sodium hydroxide are dissolved is added, followed by heat preservation at 80℃for 1 hour to remove methanol.
S3, heating the solution obtained in the step S2 to 290 ℃, preserving heat for 2 hours, cooling to room temperature, and adding absolute ethyl alcohol to precipitate a product.
S4, centrifugally washing the product obtained in the step S3 with absolute ethyl alcohol and cyclohexane for multiple times to obtain NaY 0.76 F 4 0.2Yb,0.02Er,0.02Pr nanocrystals, and stored in cyclohexane.
Comparative example 2
Preparation of NaY 0.78 F 4 :0.2Yb,0.02Er nanocrystalline, which specifically comprises the following steps:
s1, dissolving yttrium acetate, ytterbium acetate and erbium acetate into a mixed solution of 10ml of oleic acid and 10ml of octadecene according to the mol ratio of 0.78:0.2:0.02, heating to 150 ℃, stirring to remove oxygen, and removing water for 1h to form a uniform and clear precursor solution.
S2, after the solution obtained in S1 is cooled to room temperature, 10ml of a methanol solution in which 3mmol of ammonium fluoride and 2mmol of sodium hydroxide are dissolved is added, followed by heat preservation at 80℃for 1 hour to remove methanol.
S3, heating the solution obtained in the step S2 to 290 ℃, preserving heat for 2 hours, cooling to room temperature, and adding absolute ethyl alcohol to precipitate a product.
S4, centrifugally washing the product obtained in the step S3 with absolute ethyl alcohol and cyclohexane for multiple times, and NaY 0.78 F 4 0.2Yb and 0.02Er nanocrystalline and stored in cyclohexane.
Test verification
As observed by a transmission electron microscope, fig. 4 (a) shows the nano-crystal of comparative example 1, which is prepared by experiment, and has a hexagonal phase structure and average particle diameters of 25nm, respectively; in FIG. 4, (b) shows the experimentally prepared nanocrystals of comparative example 2, which have a hexagonal phase structure and average particle diameters of 20nm, respectively; whereas K prepared in example 1 of the present invention 3 Sr 3.76 In 5 F 26 : the pure green up-conversion fluorescent nanocrystalline materials of 0.2Yb,0.02Er and 0.02Pr have a tetragonal phase structure, the space group is P42/n, and the average particle size is 40nm, as shown in figures 1 and 3.
The nanoparticles prepared in comparative examples 1, 2 and examples 1, 2, 4, 6 were subjected to laser excitation at 980nm to emit spectra, and the relevant wavelengths, intensities and color purities are shown in table 1.
TABLE 1
Fig. 5 is a spectrum contrast chart of the present invention in examples 1, 2, 4, 6 and comparative examples 1, 2.
With reference to Table 1 and FIG. 5, example 1 of the present invention was preparedPure green up-conversion fluorescent nanocrystalline material K 3 Sr 3.76 In 5 F 26 :0.2Yb,0.02Er and 0.02Pr have the strongest fluorescence and the highest color purity about 541nm, and the color purity is as high as 95.9%. And, the fluorescence intensity of the green band of the pure green up-conversion fluorescent nanocrystalline material prepared in example 1 is improved by 38.6 and 14.4 times compared with that of the nanocrystalline of comparative example 1 and that of the nanocrystalline of comparative example 2, respectively, and the luminescence intensity of the pure green up-conversion fluorescent nanocrystalline material of the invention is increased in order of magnitude.
FIG. 6 is a chromaticity diagram of the color coordinates of the spectra of the present invention in example 1, example 2, example 4, example 6 and comparative example 1, comparative example 2, and it can be seen from FIG. 6 that the present invention is K 3 Sr 4-x-y-z In 5 F 26 : xYb, yEr, zPr pure green nanocrystals (example 1, example 2, example 4, example 6) are generally high in green fluorescence purity, significantly better than that of comparative example 1, and greater than or close to that of comparative example 2, and therefore, K of the present invention 3 Sr 4-x-y-z In 5 F 26 : xYb, yEr and zPr pure green nanocrystals successfully achieve the goal of single green up-conversion luminescence.

Claims (10)

1. A pure green up-conversion luminescent nano material is characterized in that the chemical expression general formula is K 3 Sr 4-x-y-z In 5 F 26 : xYb, yEr, zPr, wherein 0.1.ltoreq.x.ltoreq.0.4, 0.01.ltoreq.y.ltoreq. 0.03,0.01.ltoreq.z.ltoreq.0.03.
2. The pure green up-conversion luminescent nanomaterial of claim 1, characterized in that: the structural formula is K 3 Sr 3.76 In 5 F 26 ：0.2Yb,0.02Er,0.02Pr。
3. The method for preparing the pure green up-conversion luminescent nanomaterial according to claim 1 or 2, comprising the steps of:
s1, respectively dissolving potassium carbonate, strontium carbonate, indium carbonate, ytterbium oxide, erbium oxide and praseodymium oxide in a trifluoroacetic acid aqueous solution to form a corresponding uniformly clarified trifluoroacetic acid salt solution, uniformly stirring at 85 ℃ and evaporating the solvent to obtain corresponding solid powder;
s2, dispersing the solid trifluoroacetate powder obtained in the S1 into a mixed solvent of oleic acid and oleylamine according to a certain stoichiometric ratio, heating to 130 ℃ in a nitrogen atmosphere, and stirring for 2 hours;
s3, rapidly heating the solution obtained in the step S2 to 350 ℃ for reaction for 10min, cooling to 330 ℃ for heat preservation for 1h, rapidly cooling to room temperature, and adding acetone to precipitate a product;
s4, centrifugally washing the product obtained in the step S3 with acetone and cyclohexane for multiple times, and drying in vacuum to obtain the pure green up-conversion fluorescent nanocrystalline material.
4. The method for preparing pure green up-conversion luminescent nanomaterial according to claim 3, characterized by comprising the steps of
In S1, potassium carbonate, strontium carbonate, indium carbonate, ytterbium oxide, erbium oxide and praseodymium oxide are respectively dissolved in trifluoroacetic acid aqueous solutions with volume concentrations of 20%, 50% and 50%.
5. The method for preparing pure green up-conversion luminescent nanomaterial according to claim 3, characterized by comprising the steps of
In S2, the volume ratio of oleic acid to oleylamine is 1:1; the ratio of oleic acid usage to trifluoroacetate solid powder was 6ml/1mmol.
6. The method for preparing pure green up-conversion luminescent nanomaterial according to claim 3, characterized by comprising the steps of
And S3, heating to 350 ℃ at a heating rate of 30 ℃/min.
7. The method for preparing pure green up-conversion luminescent nanomaterial according to claim 3, wherein in the solid powder of trifluoroacetate salt in step S2, potassium trifluoroacetate: strontium trifluoroacetate: indium trifluoroacetate: ytterbium trifluoroacetate: erbium trifluoroacetate: the molar ratio of the praseodymium trifluoroacetate is 3:4:3.78:0.2:0.02:0.02.
8. The method for preparing pure green up-conversion luminescent nanomaterial according to claim 3, wherein in the solid powder of trifluoroacetate salt in step S2, potassium trifluoroacetate: strontium trifluoroacetate: indium trifluoroacetate: ytterbium trifluoroacetate: erbium trifluoroacetate: the molar ratio of the praseodymium trifluoroacetate is 3:4:3.88:0.1:0.01:0.01.
9. The method for preparing pure green up-conversion luminescent nanomaterial according to claim 3, wherein in the solid powder of trifluoroacetate salt in step S2, potassium trifluoroacetate: strontium trifluoroacetate: indium trifluoroacetate: ytterbium trifluoroacetate: erbium trifluoroacetate: the molar ratio of the praseodymium trifluoroacetate is 3:4:3.66:0.3:0.02:0.02.
10. The method for preparing pure green up-conversion luminescent nanomaterial according to claim 3, wherein in the solid powder of trifluoroacetate salt in step S2, potassium trifluoroacetate: strontium trifluoroacetate: indium trifluoroacetate: ytterbium trifluoroacetate: erbium trifluoroacetate: the molar ratio of the praseodymium trifluoroacetate is 3:4:3.54:0.4:0.03:0.03.
CN202310417111.1A 2023-04-19 2023-04-19 Pure green up-conversion luminescent nano material and preparation method thereof Active CN116426277B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310417111.1A CN116426277B (en) 2023-04-19 2023-04-19 Pure green up-conversion luminescent nano material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310417111.1A CN116426277B (en) 2023-04-19 2023-04-19 Pure green up-conversion luminescent nano material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN116426277A CN116426277A (en) 2023-07-14
CN116426277B true CN116426277B (en) 2024-01-09

Family

ID=87092406

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310417111.1A Active CN116426277B (en) 2023-04-19 2023-04-19 Pure green up-conversion luminescent nano material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116426277B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104884573A (en) * 2012-12-26 2015-09-02 三菱化学株式会社 Phosphor, phosphor-containing composition and light emitting device each using said phosphor, and image display device and lighting device each using said light emitting device
CN112940711A (en) * 2021-02-20 2021-06-11 东北林业大学 Biodegradable up-conversion core-shell nanocrystal, preparation method and application thereof
WO2021134786A1 (en) * 2020-01-03 2021-07-08 中国科学院福建物质结构研究所 In vivo degradable upconversion nanomaterial, and preparation method therefor and use thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104884573A (en) * 2012-12-26 2015-09-02 三菱化学株式会社 Phosphor, phosphor-containing composition and light emitting device each using said phosphor, and image display device and lighting device each using said light emitting device
WO2021134786A1 (en) * 2020-01-03 2021-07-08 中国科学院福建物质结构研究所 In vivo degradable upconversion nanomaterial, and preparation method therefor and use thereof
CN112940711A (en) * 2021-02-20 2021-06-11 东北林业大学 Biodegradable up-conversion core-shell nanocrystal, preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Crystal structure of Na3Sr4Al5F26;HEMON, A et al.;《Journal of Solid State Chemistry》;第81卷(第2期);第299-304页 *
Yb3+/Er3+共掺杂BaY2F8纳米颗粒的水热合成与上转换发光;乔旭升 等;《材料科学与工程学报》;第28卷(第5期);第663-666、696页 *

Also Published As

Publication number Publication date
CN116426277A (en) 2023-07-14

Similar Documents

Publication Publication Date Title
Shang et al. (Zn, Mg) 2 GeO 4: Mn 2+ submicrorods as promising green phosphors for field emission displays: hydrothermal synthesis and luminescence properties
WO2021212942A1 (en) Low-temperature doped and high photoluminescence quantum yield perovskite film and manufacturing method therefor
Li et al. Synthesis and luminescence properties of red long-lasting phosphor Y2O2S: Eu3+, Mg2+, Ti4+ nanoparticles
Jia et al. Uniform YVO4: Ln3+ (Ln= Eu, Dy, and Sm) nanocrystals: solvothermal synthesis and luminescence properties
Zhao et al. Synthesis of Sr4Al14O25: Eu2+, Dy3+ phosphor nanometer powders by combustion processes and its optical properties
Niu et al. Multicolor output and shape controlled synthesis of lanthanide-ion doped fluorides upconversion nanoparticles
CN104403672B (en) A kind of up-conversion luminescent material and its preparation method and application
KR101792800B1 (en) Color tunable upconversion nanophosphor and method of fabricating the same
KR102204359B1 (en) Core/multi-shell upconversion fluoride nanophosphor showing luminescence under various excitation wavelengths and methods of forming the same
CN108559511B (en) Rare earth doped up-conversion nanocrystalline luminescent material and preparation method thereof
KR101616363B1 (en) Multicolor tunable nanophosphor and its synthesis method and transparent polymer composite including the nanophosphor
Keskin et al. Structural, optical, luminescence properties and energy transfer mechanism of Tb3+/Eu3+ co-doped SrLa2 (MoO4) 4 phosphors produced by sol-gel process
CN114350361B (en) Up-conversion rare earth doped nano material with high fluorescence intensity and preparation method thereof
CN108441220B (en) Lattice defect regulation and control orthogonal emission rare earth up-conversion nanoparticles and preparation method thereof
Li et al. Screen printing of upconversion NaYF 4: Yb 3+/Eu 3+ with Li+ doped for anti-counterfeiting application
Shafia et al. Synthesis and characterization of SrAl2O4: Eu2+, Dy3+ nanocrystalline phosphorescent pigments
CN110964527A (en) Method for controllably preparing strong-luminescence rare earth up-conversion material
Hussain et al. Photoluminescence and cathodoluminescence properties of Sr2Gd8Si6O26: RE3+ (RE3+= Tb3+ or Sm3+) phosphors
Wang et al. Synthesis of orthorhombic K2YF5: Yb3+, Er3+/Tm3+ nanocrystals and highly efficient multicolor up-conversion luminescence
CN116426277B (en) Pure green up-conversion luminescent nano material and preparation method thereof
CN114752385B (en) Gd (Gd) type drug delivery device 3+ Doped microcrystalline material and preparation method and application thereof
KR102016557B1 (en) Upconversion nanophosphor showing multicolor luminescence with under 10 ㎚ size and methods of fabricating the same
CN103087716A (en) Synthesis method of rare earth doped hexagonal-phase cerium sodium fluoride nanocrystalline
CN108504357B (en) Titanium aluminate based up-conversion luminescent material, preparation method and application
Phaomei et al. Ce3+ sensitize RE3+ (RE= Dy, Tb, Eu, Sm) doped LaPO4 nanophosphor with white emission tunability

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant