CN116606646B - Transition metal ion sensitized rare earth ion luminescent nano probe and synthesis method thereof - Google Patents

Transition metal ion sensitized rare earth ion luminescent nano probe and synthesis method thereof Download PDF

Info

Publication number
CN116606646B
CN116606646B CN202310523502.1A CN202310523502A CN116606646B CN 116606646 B CN116606646 B CN 116606646B CN 202310523502 A CN202310523502 A CN 202310523502A CN 116606646 B CN116606646 B CN 116606646B
Authority
CN
China
Prior art keywords
transition metal
rare earth
near infrared
sensitized
trifluoroacetate
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
CN202310523502.1A
Other languages
Chinese (zh)
Other versions
CN116606646A (en
Inventor
张凡
明江
郭芷秀
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.)
Fudan University
Original Assignee
Fudan University
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 Fudan University filed Critical Fudan University
Priority to CN202310523502.1A priority Critical patent/CN116606646B/en
Publication of CN116606646A publication Critical patent/CN116606646A/en
Application granted granted Critical
Publication of CN116606646B publication Critical patent/CN116606646B/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
    • C09K11/7756—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing neodynium
    • C09K11/7757—Halogenides
    • 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
    • C09K11/7704—Halogenides
    • C09K11/7705—Halogenides with alkali or alkaline earth metals
    • 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
    • C09K11/7708—Vanadates; Chromates; Molybdates; Tungstates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention belongs to the technical field of nano materials, and particularly relates to a rare earth ion luminescent nano probe sensitized by transition metal ions and a synthesis method thereof. The nano probe consists of transition metal ions and rare earth luminescent ions; the transition metal ion is selected from chromium, manganese and nickel, and the rare earth luminescent ion is selected from ytterbium, neodymium, thulium and erbium; adjusting the probe absorption and near infrared emission wavelength by changing the transition metal ion and the rare earth ion doped type; the near infrared fluorescence signal intensity of the probe is regulated by changing the types and the proportion of the reaction solvent, the reaction temperature rising speed, the reaction concentration, the reaction time, the reaction temperature and the like; in addition, the nano probe is used as a core layer, and a transition metal ion sensitized shell layer is coated outside to form a luminescent nano probe with a core-shell structure, so that quenching of the external environment on near infrared light is reduced; the optical nano probe has wide application prospect in imaging equipment, information coding and storage, multichannel biological detection, living body imaging and the like.

Description

Transition metal ion sensitized rare earth ion luminescent nano probe and synthesis method thereof
Technical Field
The invention belongs to the technical field of nano biological materials, and particularly relates to a transition metal ion sensitized rare earth ion luminescent nano probe and a synthesis method thereof.
Background
The use of lanthanide doped nanoparticles in agricultural, military and medical applications has driven a further need for near infrared emissive materials. Conventionally, rare earth ions such as ytterbium or neodymium are used as sensitizers and doped together with thulium ions and erbium ion plasma as activators in NaLnF 4 (ln= Y, gd and Lu) nanocrystals with low phonon energy to achieve efficient near infrared emission. However, the low extinction coefficient and high doping level of the excited state concentration quenching of these lanthanide rare earth ion sensitizers limit their wide range of applications.
To address this challenge, we turned to transition metals such as chromium, manganese, and nickel as alternative sensitizers. The molar extinction coefficient of chromium ions (17.1 liter moles -1 cm -1) is significantly higher than ytterbium ions (1.2 liter moles -1 cm -1) and neodymium ions (7.4 liter moles -1 cm -1) making them potential candidates for more efficient light collection. Although chromium ion sensitized lanthanide luminescent materials, such as silicate glass and yttrium aluminum garnet crystals, have been developed for near infrared luminescence, these materials suffer from low luminescence brightness due to concentration quenching at high chromium ion doping levels. In addition, their fabrication requires complex crystal growth processes at extremely high temperatures (> 1000 degrees celsius), lacks modulation of nanostructures and tunability of surface properties, and is detrimental to the application of transition metal ion sensitized rare earth ion luminescent nanoprobes. Therefore, the design and the high-efficiency regulation of the transition metal sensitized rare earth ion luminescent nano probe on the nano scale have important significance in the aspects of imaging equipment, laser material design, information coding and storage, multichannel biological detection, living body imaging and analysis, operation navigation and the like.
Disclosure of Invention
The invention aims to provide a transition metal ion sensitized rare earth ion luminescent nano probe which has a simple preparation process and can be used for information storage, optical illumination and living body imaging and analysis and a synthesis method thereof.
The transition metal ion sensitized rare earth ion luminescence nano probe provided by the invention consists of transition metal ions and rare earth luminescence ions which are used as matrixes, wherein the transition metal ions are selected from chromium ions, manganese ions and nickel ions, and the rare earth luminescence ions are selected from ytterbium ions, neodymium ions, thulium ions and erbium ions; the doping concentration of the rare earth ions in the matrix is 0.1 to 10 percent; the probe absorption and near infrared emission wavelength are regulated by changing the types of transition metal ions and rare earth ion doping; the near infrared fluorescence signal intensity of the probe is regulated by changing the types and proportion of the reaction solvent, the reaction temperature rising speed, the reaction concentration, the reaction time, the reaction temperature, the doping concentration of rare earth ions and the like.
Further, the nano probe is used as a nuclear layer, and the transition metal ion sensitized shell layer is coated outside to form the transition metal ion sensitized rare earth ion luminescent nano probe with a nuclear shell structure. Wherein, the material of the transition metal ion sensitization layer serving as a shell layer is transition metal ions; the transition metal ion is selected from chromium ion, manganese ion and nickel ion; the inner core layer is used for absorbing energy transferred by the shell layer and emitting near infrared light, the outer shell layer is used for absorbing excitation light energy and transferring the excitation light energy to transition metal ions and rare earth ions of the core layer, and meanwhile, the inner core layer plays a role in protecting and reduces quenching of the near infrared light by the external environment. The near infrared fluorescence signal intensity of the probe is regulated by changing the type of the solvent and the shell thickness of the core-shell structure in the reaction process, and the solvent quenches the probe.
In the invention, the size of the nano probe (i.e. the nuclear layer) is 50-200 nanometers; the thickness of the transition metal ion sensitized shell layer is 1-100 nanometers; the reaction solvent is one or more of oleic acid, stearic acid, capric acid, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, hexadecylamine, octadecylamine, undecylenamine, dodecenamine, tridecenylamine, tetradecylenamine, pentadecenylamine, hexadecylenamine, heptadecenylamine and octadecylamine, and olive oil;
The invention also provides a synthesis method of the transition metal ion sensitized rare earth ion near infrared luminescence nano probe, which comprises the following specific steps:
(1) Preparation of rare earth and transition metal precursors
(1.1) Preparation of rare earth trifluoroacetate precursor solution:
Dissolving rare earth salt and rare earth oxide in trifluoroacetic acid reagent under the condition of magnetic stirring to form a rare earth trifluoroacetate solution; wherein the rare earth salt is selected from corresponding rare earth chloride, rare earth nitrate, rare earth acetate and rare earth acetylacetonate, and the rare earth oxide is a compound formed by chemically positive trivalent rare earth ions and oxygen anions; wherein the rare earth elements contained in the rare earth salt and the rare earth oxide are neodymium, erbium, thulium and ytterbium; the dissolution temperature is 20-150 ℃ and kept for 1-48 hours, and finally solid powder is obtained; and dissolving the solid powder in a certain amount of methanol to obtain a clear and transparent rare earth trifluoroacetate solution, wherein the concentration of the finally obtained solution is 0.1 to 10 mmol/ml.
(1.2) Preparation of trifluoroacetic acid transition metal salt precursor solution:
Preparation of chromium trifluoroacetate: adding chromium chloride into distilled water to dissolve until the chromium chloride is clear and transparent, then adding sodium hydroxide solution dropwise under stirring, centrifuging and washing to obtain chromium hydroxide precipitate. Adding trifluoroacetic acid, heating to 50-150 ℃ under magnetic stirring and maintaining for 0.5-24 hours to finally obtain solid powder, and dissolving the solid powder in a certain amount of methanol to obtain clear and transparent chromium trifluoroacetate solution, wherein the concentration of the finally obtained solution is 0.1-10 mmol/ml.
Preparation of manganese trifluoroacetate: dissolving manganese carbonate in trifluoroacetic acid, heating to 50-150 ℃ under magnetic stirring and maintaining for 0.5-24 hours to finally obtain solid powder, and dissolving the solid powder in a certain amount of methanol to obtain clear and transparent manganese trifluoroacetate solution, wherein the concentration of the finally obtained solution is 0.1-10 mmol/ml.
Preparation of nickel trifluoroacetate: and (3) dissolving nickel carbonate in trifluoroacetic acid, heating to 50-150 ℃ under magnetic stirring and maintaining for 0.5-24 hours to finally obtain solid powder, and dissolving the solid powder in a certain amount of methanol to obtain a clear and transparent nickel trifluoroacetate solution, wherein the concentration of the finally obtained solution is 0.1-10 mmol/ml.
(2) Preparing a transition metal ion sensitized rare earth ion luminescence nano probe:
Under the vacuum condition, the precursor raw material required for synthesizing the nanocrystals is dissolved in a high boiling point solvent, stirred and heated to 80-150 ℃ and kept for 5-30 minutes. Wherein the high boiling point solvent is selected from one or more of oleic acid, stearic acid, capric acid, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, hexadecylamine, octadecylamine, undecylenamine, dodecenamine, tridecenylamine, tetradecylenamine, pentadecenylamine, hexadecenamine, heptadecenylamine, octadecylamine and olive oil; the raw materials comprise sodium trifluoroacetate, trifluoroacetic acid transition metal salt and trifluoroacetic acid rare earth salt as matrixes; wherein the matrix trifluoroacetic acid transition metal salt is one or more of chromium, manganese and nickel, and the luminescent rare earth contains one or more of ytterbium, neodymium, thulium and erbium. The doping concentration of the rare earth ions in the matrix is 0.1 to 10 percent; the concentration of the total amount of the metal ion and the rare earth ion in the solvent in the reaction system is 0.1 mmol/ml to 10 mmol/ml. Heating the reaction system to 250-330 ℃ at a speed of 1-20 ℃ per minute; and (3) reacting for 0.1-12 hours under the protection of argon atmosphere to obtain the rare earth ion luminescent nano probe sensitized by the transition metal ions.
(3) Further, preparing a transition metal ion sensitized rare earth ion luminescence nano probe with a core-shell structure:
The nano probe prepared in the previous step is taken as a crystal nucleus, fully mixed in a high boiling point solvent, and simultaneously, a trifluoroacetate solution of a shell material is added into the solvent; wherein the high boiling point solvent is one or more of oleic acid, stearic acid, capric acid, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, hexadecylamine, octadecylamine, undecylenamine, dodecenamine, tridecenylamine, tetradecylenamine, pentadecenylamine, hexadecylenamine, heptadecenylamine and octadecylamine, and olive oil; the shell raw material comprises sodium trifluoroacetate and trifluoroacetic acid transition metal salt serving as a protective shell; the concentration of the metal ion in the solvent in the reaction system is 0.1 mmol/ml to 10 mmol/ml. Heating the reaction system to 250-330 ℃ at a speed of 1-20 ℃ per minute; reacting for 0.1-12 hours under the protection of argon atmosphere to obtain the rare earth ion luminescent nano probe sensitized by the transition metal ions with the core-shell structure.
In the invention, the probe absorption and near infrared emission wavelength are regulated by changing the types of transition metal ions and rare earth ion doped ions; for example, when thulium ions are luminescent ions and chromium ions are sensitizing ions, the excitation wavelength is preferably 420 nm, the strongest emission is at 1438 nm; when ytterbium ions are luminescent ions and manganese ions are sensitized ions, the excitation wavelength is preferably 396 nanometers, and the strongest emission is 980 nanometers; when erbium ions are luminescent ions and nickel ions are sensitized ions, the excitation wavelength is preferably 1150 nm, and the strongest emission is at 1525 nm. The near infrared fluorescence signal intensity of the probe is regulated by changing the types and the proportion of the reaction solvent, the reaction temperature rising speed, the reaction concentration, the reaction time, the reaction temperature, the doping concentration of rare earth ions and the like; specifically:
when the temperature rising speed is 5 ℃ per minute to 10 ℃ per minute, the near infrared fluorescence emission intensity is enhanced along with the increase of the temperature rising speed.
When the temperature rising speed is 5 ℃ per minute to 10 ℃ per minute, the near infrared fluorescence emission intensity is reduced along with the increase of the temperature rising speed.
At a reaction concentration of 0.0375 mmol/ml to 0.1 mmol/ml, the near infrared fluorescence emission intensity was increased as the reaction concentration was increased.
When the reaction concentration is 0.1 mmol/ml to 0.2 mmol/ml, the near infrared fluorescence emission intensity decreases as the reaction concentration increases.
At a reaction time of 0.25 to 10 hours, the near infrared fluorescence emission intensity increases with increasing reaction time.
When the reaction temperature is 230-310 ℃, the near infrared fluorescence emission intensity is enhanced along with the increase of the reaction temperature.
When the doping concentration of ytterbium ions is 0.7 mol% to 3.5 mol%, the near infrared fluorescence emission intensity is enhanced as the doping concentration increases.
When the doping concentration of ytterbium ions is 3.5 mol% to 4.7 mol%, the near infrared fluorescence emission intensity decreases as the doping concentration increases.
When the doping concentration of neodymium ions is 0.2 mol% to 5.6 mol%, the near infrared fluorescence emission intensity is enhanced with increasing doping concentration.
When the doping concentration of neodymium ions is 5.6 mol% to 7.4 mol%, the near infrared fluorescence emission intensity decreases as the doping concentration increases.
When the doping concentration of erbium ions is 0.7 mol% to 4.2 mol%, the near infrared fluorescence emission intensity is enhanced as the doping concentration increases.
When the doping concentration of erbium ions is 4.2 mol% to 5.8 mol%, the near infrared fluorescence emission intensity decreases as the doping concentration increases.
When the doping concentration of thulium ions is 0.5 mol% to 4.1 mol%, the near infrared fluorescence emission intensity is enhanced with increasing doping concentration.
When the doping concentration of thulium ions is 4.1 mol% to 5.2 mol%, the near infrared fluorescence emission intensity decreases as the doping concentration increases.
In the invention, the rare earth ion luminescent nano probe sensitized by the transition metal ions of the core-shell structure is arranged inside and is used as a rare earth luminescent core layer, and the transition metal ion sensitized shell layer is arranged outside; the core layer is used for absorbing energy transferred by the shell layer and emitting near infrared light, the outer shell layer is used for absorbing excitation light energy and transferring the excitation light energy to transition metal ions or rare earth ions of the core layer, and meanwhile, the core layer plays a role in protection and reduces quenching of the near infrared light by the outer environment. The near infrared fluorescence signal intensity of the probe and the quenching of the probe by the solvent can be influenced by changing the type of the solvent, the shell reaction temperature of the core-shell structure and the shell thickness in the reaction process. Specifically:
when the shell reaction temperature of the core-shell structure is 270-330 ℃, the near infrared fluorescence emission intensity is enhanced along with the increase of the reaction temperature.
When the shell thickness of the core-shell structure is 1-20 nanometers, the near infrared fluorescence emission intensity is enhanced along with the increase of the shell thickness.
The transition metal sensitized rare earth luminescence strategy adopted by the invention effectively improves the near infrared fluorescence signal intensity of the probe; the transition metal ion sensitized rare earth ion near infrared luminous nano probe has wide application prospect in the aspects of information coding and storage, multichannel biological detection, living body imaging and analysis, operation navigation and the like.
Drawings
FIG. 1 is a schematic diagram of the basic structure of a prepared transition metal ion sensitized rare earth ion near infrared luminescence nano probe.
FIG. 2 is a transmission electron micrograph of the prepared Na 3CrF6:Er,Na3CrF6:Tm,Na3CrF6:Yb and Na 3CrF6:Nd near-infrared luminescent nanoprobe.
FIG. 3 is a near infrared fluorescence emission spectrum of the prepared Na 3CrF6:Er,Na3CrF6:Tm,Na3CrF6:Yb and Na 3CrF6:Nd near infrared luminescence nanoprobe at 655 nm excitation wavelength.
FIG. 4 is a transmission electron micrograph of the prepared NaMnF 3:Yb,NaMnF3:Nd,NaMnF3:Er and KNIF 3:Er near infrared luminescent nanoprobe.
FIG. 5 is a near infrared fluorescence emission spectrum of the prepared NaMnF 3:Yb,NaMnF3:Nd,NaMnF3:Er and KNIF 3:Er near infrared luminescence nanoprobe at 396 nm or 1150 nm excitation wavelength.
Fig. 6 is a transmission electron micrograph of the prepared Na 3CrF6:Er@Na3CrF6 near infrared light emitting nanoprobe.
FIG. 7 is a near infrared fluorescence emission spectrum of the prepared Na 3CrF6:Er@Na3CrF6 near infrared light-emitting nanoprobe at 655 nm excitation wavelength.
Detailed Description
Example 1:
and preparing the transition metal ion sensitized rare earth ion near infrared luminescent nanocrystals. The method comprises the following specific steps:
(1) Preparation of rare earth and transition metal precursors
A. Preparing a rare earth trifluoroacetate precursor solution:
Preparation of ytterbium trifluoroacetate: taking a 100 ml three-neck round bottom flask as a reaction container, sequentially adding 0.5 mmol of ytterbium oxide and 50ml of trifluoroacetic acid and 20 ml of distilled water, heating to 70 ℃ under the magnetic stirring condition, and keeping for 12 hours to obtain solid powder, and dissolving the solid powder in a certain amount of methanol to obtain a clear and transparent ytterbium trifluoroacetate solution.
Preparation of neodymium trifluoroacetate: taking a 100 ml three-neck round bottom flask as a reaction container, sequentially adding 0.5 mmol of neodymium oxide and 50ml of trifluoroacetic acid and 20 ml of distilled water, heating to 70 ℃ under the magnetic stirring condition, and keeping for 12 hours to obtain solid powder, and dissolving the solid powder in a certain amount of methanol to obtain a clear and transparent neodymium trifluoroacetate solution.
Preparation of thulium trifluoroacetate: taking a 100 ml three-neck round bottom flask as a reaction container, sequentially adding 0.5 mmol of thulium oxide and 50ml of trifluoroacetic acid and 20 ml of distilled water, heating to 70 ℃ under the magnetic stirring condition and keeping for 12 hours, finally obtaining solid powder, and dissolving in a certain amount of methanol to obtain a clear and transparent thulium trifluoroacetate solution.
Preparation of erbium trifluoroacetate: taking a 100 ml three-neck round bottom flask as a reaction container, sequentially adding 0.5 mmol of erbium oxide and 50ml of trifluoroacetic acid and 20 ml of distilled water, heating to 70 ℃ under the magnetic stirring condition, and keeping for 12 hours to obtain solid powder, and dissolving the solid powder in a certain amount of methanol to obtain a clear and transparent erbium trifluoroacetate solution.
B. Preparation of trifluoroacetic acid transition metal salt (chromium/manganese/nickel) precursor solution:
preparation of chromium trifluoroacetate: adding chromium chloride into distilled water to dissolve until the chromium chloride is clear and transparent, then adding sodium hydroxide solution dropwise under stirring, centrifuging and washing to obtain chromium hydroxide precipitate. Adding trifluoroacetic acid, heating to 50-150 ℃ under magnetic stirring and maintaining for 0.5-24 hours to finally obtain solid powder, and dissolving the solid powder in a certain amount of methanol to obtain clear and transparent chromium trifluoroacetate solution, wherein the concentration of the finally obtained solution is 0.1-10 mmol/ml.
Preparation of manganese trifluoroacetate: dissolving manganese carbonate in trifluoroacetic acid, heating to 50-150 ℃ under magnetic stirring and maintaining for 0.5-24 hours to finally obtain solid powder, and dissolving the solid powder in a certain amount of methanol to obtain clear and transparent manganese trifluoroacetate solution, wherein the concentration of the finally obtained solution is 0.1-10 mmol/ml.
Preparation of nickel trifluoroacetate: and (3) dissolving nickel carbonate in trifluoroacetic acid, heating to 50-150 ℃ under magnetic stirring and maintaining for 0.5-24 hours to finally obtain solid powder, and dissolving the solid powder in a certain amount of methanol to obtain a clear and transparent nickel trifluoroacetate solution, wherein the concentration of the finally obtained solution is 0.1-10 mmol/ml.
(2) And (3) synthesizing the transition metal ion sensitized rare earth ion near infrared luminescent nanocrystals containing the transition metal Cr (the molar content is 95.8%) and the rare earth element Er (the molar content is 4.2%). A100 ml three-necked round bottom flask was taken as a reaction vessel, and 0.958 mmol of chromium trifluoroacetate, 0.042 mmol of erbium trifluoroacetate, 5mmol of sodium trifluoroacetate and then 10ml of oleylamine were sequentially added. The reaction was heated to 130 degrees celsius with stirring under vacuum dehydration deoxygenation conditions and maintained for 15 minutes, and the reaction was warmed to 310 degrees celsius at a rate of 10 degrees celsius per minute under the protection of high purity argon and then incubated for 150 minutes. Cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 10ml of cyclohexane to obtain transition metal ion sensitized rare earth near infrared luminescent nanocrystals with good dispersibility and uniformity, wherein the nanocrystals are oil-soluble and have a particle size of 100-200 nanometers.
The prepared transition metal ion sensitized Er ion near infrared luminous nanocrystals are oil-soluble, and emit near infrared fluorescence with a wave band of 1400-1600 nm under the excitation light with a visible light (390-780 nm) wavelength, and the wavelength corresponding to the maximum peak value is 1540 nm.
And (3) synthesizing the transition metal ion sensitized rare earth ion near infrared luminescent nanocrystals containing the transition metal Cr (the molar content is 95.8%) and the rare earth element Tm (the molar content is 4.1%). A100 ml three-neck round bottom flask was taken as a reaction vessel, and 0.959 mmol of chromium trifluoroacetate, 0.041 mmol of thulium trifluoroacetate, 5 mmol of sodium trifluoroacetate and then 10 ml of oleylamine were added sequentially. The reaction was heated to 130 degrees celsius with stirring under vacuum dehydration deoxygenation conditions and maintained for 15 minutes, and the reaction was warmed to 310 degrees celsius at a rate of 10 degrees celsius per minute under the protection of high purity argon and then incubated for 150 minutes. Cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 10 ml of cyclohexane to obtain transition metal ion sensitized rare earth near infrared luminescent nanocrystals with good dispersibility and uniformity, wherein the nanocrystals are oil-soluble and have a particle size of 100-200 nanometers.
The prepared transition metal ion sensitized Tm ion near infrared luminous nanocrystals are oil-soluble, and emit near infrared fluorescence with the wave band of 1400-1600 nanometers under the excitation light with the wavelength of visible light (390-780 nanometers), and the wavelength corresponding to the maximum peak value is 1438 nanometers.
And (3) synthesizing the transition metal ion sensitized rare earth ion near infrared luminescence nano crystal containing the transition metal Cr (the molar content is 95.8%) and the rare earth element Nd (the molar content is 5.6%). A100 ml three-necked round bottom flask was taken as a reaction vessel, and 0.944 mmol of chromium trifluoroacetate, 0.056 mmol of neodymium trifluoroacetate, 5 mmol of sodium trifluoroacetate and then 10ml of oleylamine were sequentially added. The reaction was heated to 130 degrees celsius with stirring under vacuum dehydration deoxygenation conditions and maintained for 15 minutes, and the reaction was warmed to 310 degrees celsius at a rate of 10 degrees celsius per minute under the protection of high purity argon and then incubated for 150 minutes. Cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 10ml of cyclohexane to obtain transition metal ion sensitized rare earth near infrared luminescent nanocrystals with good dispersibility and uniformity, wherein the nanocrystals are oil-soluble and have a particle size of 100-200 nanometers.
The prepared transition metal ion sensitized Nd ion near infrared luminous nanocrystals are oil-soluble, emit near infrared fluorescence with the wave band of 1000-1400 nanometers under the excitation light of visible light (390-780 nanometers), and the wavelength corresponding to the maximum peak value is 1056 nanometers.
The synthesis of near infrared luminescent nanometer crystal of transition metal ion sensitized rare earth ion containing transition metal Cr (mol content 95.8%) and rare earth element Yb (mol content 3.5%). A100 ml three-neck round bottom flask was taken as a reaction vessel, and 0.965 mmol of chromium trifluoroacetate, 0.035 mmol of ytterbium trifluoroacetate, 5mmol of sodium trifluoroacetate and then 10ml of oleylamine were added sequentially. The reaction was heated to 130 degrees celsius with stirring under vacuum dehydration deoxygenation conditions and maintained for 15 minutes, and the reaction was warmed to 310 degrees celsius at a rate of 10 degrees celsius per minute under the protection of high purity argon and then incubated for 150 minutes. Cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 10ml of cyclohexane to obtain transition metal ion sensitized rare earth near infrared luminescent nanocrystals with good dispersibility and uniformity, wherein the nanocrystals are oil-soluble and have a particle size of 100-200 nanometers.
The prepared transition metal ion sensitized Yb ion near infrared luminous nanocrystals are oil-soluble, and emit near infrared fluorescence with a wave band of 900-1100 nanometers under the excitation light with a wavelength of visible light (390-780 nanometers), and the wavelength corresponding to the maximum peak value is 996 nanometers.
(3) Synthesis of near-infrared luminescent nanocrystals containing transition metal Mn (95% by mole) and rare earth element Er (5% by mole). A50 ml three-neck round bottom flask was taken as a reaction vessel, and 0.95 mmol of manganese trifluoroacetate, 0.05 mmol of erbium trifluoroacetate, 1mmol of sodium trifluoroacetate, followed by 4 ml of oleic acid, 1 ml of oleylamine and 5ml of 1-octadecene were sequentially added. The reaction was heated to 140 degrees celsius with stirring under vacuum dehydration deoxygenation conditions until the solution was clear and transparent. The reactants are heated to 260 ℃ at a speed of 10 ℃ per minute under the protection of high-purity argon, and then the temperature is kept for reaction for 30 minutes. Cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 10ml of cyclohexane to obtain transition metal ion sensitized rare earth near infrared luminescent nanocrystals with good dispersibility and uniformity, wherein the nanocrystals are oil-soluble and have a particle size of 50-100 nanometers.
The prepared transition metal Mn ion sensitized Er ion near infrared luminescent nanocrystals emit near infrared fluorescence with the wave band of 1400-1600 nanometers under the excitation light of ultraviolet light and blue light (350-480 nanometers), and the wavelength corresponding to the maximum peak value is 1532 nanometers.
Synthesis of near-infrared luminescent nanocrystals containing transition metal Mn (93% by mole) and rare earth Yb (7% by mole). A50 ml three-neck round bottom flask was taken as a reaction vessel, and 0.93 mmole of manganese trifluoroacetate, 0.07 mmole of ytterbium trifluoroacetate, 1 mmole of sodium trifluoroacetate, followed by 4 ml of oleic acid, 1 ml of oleylamine and 5ml of 1-octadecene were sequentially added. The reaction was heated to 140 degrees celsius with stirring under vacuum dehydration deoxygenation conditions until the solution was clear and transparent. The reactants are heated to 260 ℃ at a speed of 10 ℃ per minute under the protection of high-purity argon, and then the temperature is kept for reaction for 30 minutes. Cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 10 ml of cyclohexane to obtain transition metal ion sensitized rare earth near infrared luminescent nanocrystals with good dispersibility and uniformity, wherein the nanocrystals are oil-soluble and have a particle size of 50-100 nanometers.
The prepared transition metal Mn ion sensitized Yb ion near infrared luminescent nanocrystals emit near infrared fluorescence with a wave band of 900-1200 nanometers under the excitation light of ultraviolet light and blue light (350-480 nanometers), and the wavelength corresponding to the maximum peak value is 980 nanometers.
Synthesis of near-infrared luminescent nanocrystals containing transition metal Mn (95% by mole) and rare earth element Nd (5% by mole). A50 ml three-neck round bottom flask was taken as a reaction vessel, and 0.95 mmol of manganese trifluoroacetate, 0.05 mmol of neodymium trifluoroacetate, 1mmol of sodium trifluoroacetate, followed by 4 ml of oleic acid, 1 ml of oleylamine and 5 ml of 1-octadecene were sequentially added. The reaction was heated to 140 degrees celsius with stirring under vacuum dehydration deoxygenation conditions until the solution was clear and transparent. The reactants are heated to 260 ℃ at a speed of 10 ℃ per minute under the protection of high-purity argon, and then the temperature is kept for reaction for 30 minutes. Cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 10ml of cyclohexane to obtain transition metal ion sensitized rare earth near infrared luminescent nanocrystals with good dispersibility and uniformity, wherein the nanocrystals are oil-soluble and have a particle size of 50-100 nanometers.
The prepared transition metal Mn ion sensitized Nd ion near infrared luminous nanocrystals emit near infrared fluorescence with the wave band of 1000-1400 nanometers under the excitation light of ultraviolet light and blue light (350-480 nanometers), and the wavelength corresponding to the maximum peak value is 1060 nanometers.
The prepared transition metal ion sensitized rare earth ion luminescent nano material has wide application prospect in the aspects of illumination imaging equipment, laser material design, information coding and storage, multichannel biological detection, living body imaging and analysis, operation navigation and the like.
(4) Synthesis of near-infrared luminescent nanocrystals containing transition metal Ni (98% molar content) and rare earth element Er (2% molar content). A50 ml three-neck round bottom flask was taken as a reaction vessel, and 1mmol of nickel trifluoroacetate, 0.02 mmol of erbium trifluoroacetate, 1mmol of potassium trifluoroacetate, followed by 5ml of oleic acid, 5ml of oleylamine and 10 ml of 1-octadecene were sequentially added. The reaction was heated to 140 degrees celsius with stirring under vacuum dehydration deoxygenation conditions until the solution was clear and transparent. The reactants are heated to 280 ℃ at a speed of 10 ℃ per minute under the protection of high-purity argon, and then the temperature is kept for reaction for 15 minutes. Cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 10 ml of cyclohexane to obtain transition metal ion sensitized rare earth near infrared luminescent nanocrystals with good dispersibility and uniformity, wherein the nanocrystals are oil-soluble and have a particle size of 100-200 nanometers.
The prepared transition metal Ni ion sensitized Er ion near infrared luminescent nanocrystals emit near infrared fluorescence with a wave band of 1450-1600 nanometers under the excitation light with a wavelength of a near infrared region (1100-1200 nanometers), and the wavelength corresponding to the maximum peak value is 1525 nanometers.
The prepared transition metal ion sensitized rare earth ion luminescent nano material has wide application prospect in the aspects of illumination imaging equipment, laser material design, information coding and storage, multichannel biological detection, living body imaging and analysis, operation navigation and the like.
Example 2
And (3) synthesizing the transition metal ion sensitized rare earth ion near infrared luminescent nanocrystals of the core-shell transition metal Cr (the molar content is 96%) and the rare earth element Er (the molar content is 4%) with the water quenching prevention characteristic. The specific steps are as follows.
(1) And (3) synthesizing the transition metal ion sensitized rare earth ion near infrared luminescent nanocrystals containing the transition metal Cr (the molar content is 95.8%) and the rare earth element Er (the molar content is 4.2%). A100 ml three-necked round bottom flask was taken as a reaction vessel, and 0.958 mmol of chromium trifluoroacetate, 0.042 mmol of erbium trifluoroacetate, 5 mmol of sodium trifluoroacetate and then 10 ml of oleylamine were sequentially added. The reaction was heated to 130 degrees celsius with stirring under vacuum dehydration deoxygenation conditions and maintained for 15 minutes, and the reaction was warmed to 310 degrees celsius at a rate of 10 degrees celsius per minute under the protection of high purity argon and then incubated for 150 minutes. Cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 10 ml of cyclohexane to obtain transition metal ion sensitized rare earth near infrared luminescent nanocrystals with good dispersibility and uniformity, wherein the nanocrystals are oil-soluble and have a particle size of 100-200 nanometers.
The prepared transition metal ion sensitized Er ion near infrared luminous nanocrystals are oil-soluble, and emit near infrared fluorescence with a wave band of 1400-1600 nm under the excitation light with a visible light (390-780 nm) wavelength, and the wavelength corresponding to the maximum peak value is 1540 nm.
(2) And (3) synthesizing the transition metal ion sensitized rare earth ion near infrared luminescent nanocrystals containing the transition metal Cr protective shell. A100 ml three-necked round bottom flask was taken as a reaction vessel, and 1mmol of chromium trifluoroacetate, 5mmol of sodium trifluoroacetate and 0.2 mmol of the particles of (1) were sequentially added, followed by 10 ml of oleylamine. The reaction was heated to 130 degrees celsius with stirring under vacuum dehydration deoxygenation conditions and maintained for 15 minutes, and the reaction was warmed to 310 degrees celsius at a rate of 10 degrees celsius per minute under the protection of high purity argon and then incubated for 150 minutes. Cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 2 ml of cyclohexane to obtain transition metal ion sensitized rare earth near infrared luminescent nanocrystals with good dispersibility and uniformity, wherein the nanocrystals are oil-soluble and have a particle size of 200-300 nanometers.
The prepared transition metal ion sensitized Er ion near infrared luminous nanocrystals are oil-soluble, and emit near infrared fluorescence with a wave band of 1400-1600 nm under the excitation light with a visible light (390-780 nm) wavelength, and the wavelength corresponding to the maximum peak value is 1540 nm.
The prepared transition metal ion sensitized rare earth ion luminescent nano material has wide application prospect in the aspects of illumination imaging equipment, laser material design, information coding and storage, multichannel biological detection, living body imaging and analysis, operation navigation and the like.

Claims (6)

1. A transition metal ion sensitized near infrared luminescent nanocrystal, wherein the composition of the nanocrystal is one of Na3CrF6:Er、Na3CrF6:Tm、Na3CrF6:Yb、Na3CrF6:Nd、Na3CrF6:Er@Na3CrF6.
2. The method for preparing the near-infrared luminescent nanocrystals sensitized by transition metal ions according to claim 1, wherein the synthesis steps of the near-infrared luminescent nanocrystals sensitized by transition metal ions containing transition metal Cr and rare earth element Er are as follows:
Taking a 100 ml three-neck round bottom flask as a reaction container, sequentially adding 0.958 mmol of chromium trifluoroacetate, 0.042 mmol of erbium trifluoroacetate, 5mmol of sodium trifluoroacetate and then adding 10 ml of oleylamine; stirring and heating the reactant to 130 ℃ under the vacuum dehydration and deoxidation condition, keeping the temperature for 15 minutes, heating the reactant to 310 ℃ at the speed of 10 ℃ per minute under the protection of high-purity argon, and then keeping the temperature for reaction for 150 minutes; cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 10 ml of cyclohexane to obtain the transition metal ion sensitized near infrared luminescent nanocrystals containing transition metal Cr and rare earth element Er.
3. The method for preparing the transition metal ion sensitized near infrared light emitting nanocrystal according to claim 1, wherein,
The synthesis method of the transition metal ion sensitized near infrared luminescent nanocrystals containing transition metal Cr and rare earth element Tm comprises the following steps:
Taking a 100 ml three-neck round bottom flask as a reaction container, sequentially adding 0.959 mmol of chromium trifluoroacetate, 0.041 mmol of thulium trifluoroacetate and 5mmol of sodium trifluoroacetate, and then adding 10 ml of oleylamine; stirring and heating the reactant to 130 ℃ under the vacuum dehydration and deoxidation condition, keeping the temperature for 15 minutes, heating the reactant to 310 ℃ at the speed of 10 ℃ per minute under the protection of high-purity argon, and then keeping the temperature for reaction for 150 minutes; cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 10 ml of cyclohexane to obtain the transition metal ion sensitized near infrared luminescent nanocrystals containing transition metal Cr and rare earth elements Tm.
4. The method for preparing the transition metal ion sensitized near infrared light emitting nanocrystals according to claim 1, wherein the synthesis steps of the transition metal ion sensitized near infrared light emitting nanocrystals containing transition metal Cr and rare earth element Nd are as follows:
Taking a 100 ml three-neck round bottom flask as a reaction container, sequentially adding 0.944 mmol of chromium trifluoroacetate, 0.056 mmol of neodymium trifluoroacetate, 5mmol of sodium trifluoroacetate and then adding 10 ml of oleylamine; stirring and heating the reactant to 130 ℃ under the vacuum dehydration and deoxidation condition, keeping the temperature for 15 minutes, heating the reactant to 310 ℃ at the speed of 10 ℃ per minute under the protection of high-purity argon, and then keeping the temperature for reaction for 150 minutes; cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 10 ml of cyclohexane to obtain the transition metal ion sensitized near infrared luminescent nanocrystals containing transition metal Cr and rare earth element Nd.
5. The method for preparing the transition metal ion sensitized near infrared light emitting nanocrystals according to claim 1, wherein the synthesis steps of the transition metal ion sensitized near infrared light emitting nanocrystals containing transition metal Cr and rare earth element Yb are as follows:
Taking a 100 ml three-neck round bottom flask as a reaction container, sequentially adding 0.965 mmol of chromium trifluoroacetate, 0.035 mmol of ytterbium trifluoroacetate and 5mmol of sodium trifluoroacetate, and then adding 10 ml of oleylamine; stirring and heating the reactant to 130 ℃ under the vacuum dehydration and deoxidation condition, keeping the temperature for 15 minutes, heating the reactant to 310 ℃ at the speed of 10 ℃ per minute under the protection of high-purity argon, and then keeping the temperature for reaction for 150 minutes; cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 10 ml of cyclohexane to obtain the transition metal ion sensitized near infrared luminescent nanocrystals containing transition metal Cr and rare earth element Yb.
6. The method for preparing the near-infrared luminescent nanocrystals sensitized by transition metal ions according to claim 1, wherein the synthesis steps of the near-infrared luminescent nanocrystals sensitized by transition metal ions of transition metal Cr and rare earth element Er with core-shell structure are as follows:
(1) Synthesizing transition metal ion sensitized rare earth ion near infrared luminescence nano crystal containing transition metal Cr and rare earth element Er: taking a 100ml three-neck round bottom flask as a reaction container, sequentially adding 0.958 mmol of chromium trifluoroacetate, 0.042 mmol of erbium trifluoroacetate, 5mmol of sodium trifluoroacetate and then adding 10ml of oleylamine; stirring and heating the reactant to 130 ℃ under the vacuum dehydration and deoxidation condition, keeping the temperature for 15 minutes, heating the reactant to 310 ℃ at the speed of 10 ℃ per minute under the protection of high-purity argon, and then keeping the temperature for reaction for 150 minutes; cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 10ml of cyclohexane to obtain transition metal ion sensitized rare earth near infrared luminescent nanocrystals containing transition metal Cr and rare earth Er;
(2) Synthesis of near infrared luminescent nanocrystals sensitized with transition metal ions of core-shell transition metal Cr and rare earth element Er: taking a 100ml three-neck round bottom flask as a reaction container, sequentially adding 1 mmol of chromium trifluoroacetate, 5 mmol of sodium trifluoroacetate and 0.2 mmol of the nano-crystal synthesized in the step (1), and then adding 10 ml of oleylamine; stirring and heating the reactant to 130 ℃ under the vacuum dehydration and deoxidation condition, keeping the temperature for 15 minutes, heating the reactant to 310 ℃ at the speed of 10 ℃ per minute under the protection of high-purity argon, and then keeping the temperature for reaction for 150 minutes; cooling the reactant to room temperature, adding ethanol to precipitate a product from the solution, centrifuging to remove supernatant, repeatedly washing 3 times by using absolute ethanol, and dissolving in 2 ml of cyclohexane to obtain the near infrared luminescent nanocrystal sensitized by transition metal ions of transition metal Cr and rare earth element Er with a core-shell structure.
CN202310523502.1A 2023-05-10 2023-05-10 Transition metal ion sensitized rare earth ion luminescent nano probe and synthesis method thereof Active CN116606646B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310523502.1A CN116606646B (en) 2023-05-10 2023-05-10 Transition metal ion sensitized rare earth ion luminescent nano probe and synthesis method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310523502.1A CN116606646B (en) 2023-05-10 2023-05-10 Transition metal ion sensitized rare earth ion luminescent nano probe and synthesis method thereof

Publications (2)

Publication Number Publication Date
CN116606646A CN116606646A (en) 2023-08-18
CN116606646B true CN116606646B (en) 2024-05-17

Family

ID=87679204

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310523502.1A Active CN116606646B (en) 2023-05-10 2023-05-10 Transition metal ion sensitized rare earth ion luminescent nano probe and synthesis method thereof

Country Status (1)

Country Link
CN (1) CN116606646B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106905959A (en) * 2017-01-22 2017-06-30 苏州大学 A kind of preparation method containing manganese fluoride nano crystal
KR20180041540A (en) * 2016-10-14 2018-04-24 창원대학교 산학협력단 Upconversion nanophosphor having improved quantum yield
CN114806564A (en) * 2022-03-18 2022-07-29 佛山科学技术学院 Trivalent chromium ion doped fluorine antimonate near-infrared fluorescent material, preparation method and LED light source thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180041540A (en) * 2016-10-14 2018-04-24 창원대학교 산학협력단 Upconversion nanophosphor having improved quantum yield
CN106905959A (en) * 2017-01-22 2017-06-30 苏州大学 A kind of preparation method containing manganese fluoride nano crystal
CN114806564A (en) * 2022-03-18 2022-07-29 佛山科学技术学院 Trivalent chromium ion doped fluorine antimonate near-infrared fluorescent material, preparation method and LED light source thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A Chemical Precipitation Method to Synthesize Na3CrF6 Crystal with Unique Shapes;Zhen Zhou et al.;J Inorg Organomet Polym;20130830;第23卷;第1529-1533页 *
Single-Crystalline and Near-Monodispersed NaMF3 (M=Mn, Co, Ni, Mg) and LiMAlF6 (M=Ca, Sr) Nanocrystals from Cothermolysis of Multiple Trifluoroacetates in Solution;Ya-Ping Du et al.;Chem. Asian J.;20070530;第2卷;第965-974页 *
Synthesis of Er3+/Yb3+ codoped NaMnF3 nanocubes with single-band red upconversion luminescence;Zhenhua Bai et al.;RSC Advances;20141111;第4卷;第61891-61897页 *

Also Published As

Publication number Publication date
CN116606646A (en) 2023-08-18

Similar Documents

Publication Publication Date Title
Gupta et al. Optical nanomaterials with focus on rare earth doped oxide: A Review
Sharma et al. Effects of annealing on luminescence of CaWO4: Eu3+ nanoparticles and its thermoluminescence study
WO2021004078A1 (en) Praseodymium-doped gadolinium scandate visible waveband laser crystal and preparation method therefor
Tamrakar et al. Upconversion and colour tunability of Gd2O3: Er3+ phosphor prepared by combustion synthesis method
Krishnan et al. Recent advances in microwave synthesis for photoluminescence and photocatalysis
CN112080278B (en) Up/down conversion dual-mode luminescent nanocrystal and preparation method and application thereof
CN108559511B (en) Rare earth doped up-conversion nanocrystalline luminescent material and preparation method thereof
CN112940726B (en) Blue-violet and near-infrared two-region dual-mode luminescent nanocrystal and preparation method thereof
CN102994089A (en) Preparation method of alkaline earth fluoride nanocrystal with ultra small core-shell structure
Kaczorowska et al. Synthesis and tunable emission studies of new up-converting Ba2GdV3O11 nanopowders doped with Yb3+/Ln3+ (Ln3+= Er3+, Ho3+, Tm3+)
KR102204359B1 (en) Core/multi-shell upconversion fluoride nanophosphor showing luminescence under various excitation wavelengths and methods of forming the same
Vishwakarma et al. Intense red and green emissions from Ho3+/Yb3+ co-doped Sodium Gadolinium Molybdate Nano-phosphor: Effect of calcination temperature and Intrinsic optical bistability
CN111253942A (en) Up-conversion nano luminescent material with perovskite structure and preparation method and application thereof
Wei et al. Recent progress in synthesis of lanthanide-based persistent luminescence nanoparticles
Costa et al. ZnAl 2 O 4 co-doped with Yb 3+/Er 3+ prepared by combustion reaction: evaluation of photophysical properties
Hassan et al. Investigation of sintering temperature and Ce3+ concentration in YAG: Ce phosphor powder prepared by microwave combustion for white-light-emitting diode luminance applications
US7976727B1 (en) Chromium-doped zinc-nitro-antimony-gallium-tellurium infrared phosphors
Wang et al. Polyol-mediated synthesis and photoluminescent properties of Ce3+ and/or Tb3+-doped LaPO4 nanoparticles
Peng et al. Intense single-band red upconversion emission in BiOCl: Er3+ layered semiconductor via co-doping Ho3+
Fan et al. Hydrothermal synthesis and luminescence behavior of lanthanide-doped GdF/sub 3/nanoparticles
CN116606646B (en) Transition metal ion sensitized rare earth ion luminescent nano probe and synthesis method thereof
Pan et al. Unravelling phase and morphology evolution of NaYbF 4 upconversion nanoparticles via modulating reaction parameters
CN111826154B (en) Preparation method of rare earth doped alkaline earth metal sulfide nano material
CN110041928B (en) Mg2+/Ge4+Substituted Ga3+Doped with Cr3+Zinc gallate based near-infrared long afterglow material and preparation method thereof
CN112457849A (en) Near-infrared fluoride core-shell nanocrystalline scintillator

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