CN112625687A - Rare earth doped elpasolite nanometer luminescent material and preparation method thereof - Google Patents

Rare earth doped elpasolite nanometer luminescent material and preparation method thereof Download PDF

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CN112625687A
CN112625687A CN202110120857.7A CN202110120857A CN112625687A CN 112625687 A CN112625687 A CN 112625687A CN 202110120857 A CN202110120857 A CN 202110120857A CN 112625687 A CN112625687 A CN 112625687A
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宋晓荣
周畅
高航
陈学元
涂大涛
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Fuzhou University
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Abstract

The invention provides rare earth doped Cs2NaYF6A nano luminescent material and a preparation method thereof, belonging to the technical field of fluorescent nano materials. The method adopts sodium salt, rare earth salt and cesium fluoride as raw materials, and obtains the rare earth doped Cs by using a high-temperature coprecipitation method2NaYF6The synthesis conditions of the nano luminescent material are easy to control, and the prepared nano luminescent material is hexagonal, and has good dispersibility, uniformity and synthesis repeatability. By changing the solvent ratio, Cs can also be regulated2NaYF6The particle size of the nano material; and the obtained Cs can be obtained through co-doping of different rare earths2NaYF6The nano material realizes different up-conversion and down-conversion nano luminescence. Therefore, the rare earth doped Cs prepared by the invention2NaYF6The nano material is a novel nano luminescent material and has potential application value.

Description

Rare earth doped elpasolite nanometer luminescent material and preparation method thereof
Technical Field
The invention belongs to the technical field of fluorescent nano materials, and particularly relates to rare earth doped Cs2NaYF6A method for preparing nano material.
Background
The rare earth doped inorganic nano luminescent material has the advantages of narrow emission line, high color purity, long fluorescence lifetime, good luminescent stability and the like, and is a commonly seen luminescent material at present. Lead-based halogen perovskites have excellent optical properties, but due to the poor toxicity and stability of lead, the practical application of lead is seriously hindered, so that the search for novel non-lead and stable perovskites is focused on by researchers. The structural formula of the elpasolite structural material is A2BⅠBⅢX6(X = F, Cl, Br, I), is stable and nontoxic compared with lead-based perovskite, is a luminescent material with great development potential, and is applied to the aspects of X-ray images, laser, solar cells, the illumination field, detectors, photocatalysis and the like. The crystal structure of the elpasolite has univalent and trivalent cations, trivalent rare earth ions are easy to be doped into the crystal structure, and by utilizing the structural characteristics of the elpasolite and the unique luminescence property of the rare earth ions, the next generation of the all-inorganic perovskite luminescent material with excellent performance is expected to be developed.
Cs2NaYF6Has lower phonon energy and stable chemical and physical properties, and is a good luminescent material which can be used as a matrix. Cs2NaYF6Is a rather traditional matrix material, which researchers have studied for more than half a century, but is now about Cs2NaYF6The reports of the materials are concentrated on the bulk materials, and no related nano materials are reported. This is because the material itself has unique elpasolite structural characteristics, i.e., the crystals are first conformed to the octahedral factor andthe thermodynamic stability of the material can be guaranteed only by the constraint of tolerance factors, and the material cannot be spontaneously decomposed at normal temperature and normal pressure; and Cs2NaYF6The material itself is a three cation to one anion structure, and if more traditional reactant precursors are used, such as hydroxides and ammonium fluoride, binary, ternary or even quaternary mixed phases are particularly easy to form, mainly because the complex balance between different reactivity of the multiple cations and anion precursors during nucleation and growth may lead to the formation of intermediate by-products such as two-phase nanomaterials or heterostructures. These by-products can severely affect the fluorescence quantum yield of the materials, which limits their practical applications. Thus, Cs2NaYF6The nanometer material is always difficult to synthesize, so that no synthesis report of the related type fluoride elpasolite structure nanometer material exists so far.
Disclosure of Invention
The invention aims to provide rare earth doped Cs2NaYF6Preparation method of nano luminescent material and rare earth doped Cs prepared by method2NaYF6A nano luminescent material. The preparation method of the invention has the advantages of easy control of synthesis conditions, good dispersibility, uniformity and repeatability of the prepared nano material, and solving the problem of the existing Cs2NaYF6The problems of impurity phase, difficult synthesis of small particles and the like easily occur in the preparation of the nano material.
In order to achieve the purpose, the invention adopts the following technical scheme:
rare earth doped Cs2NaYF6The preparation method of the nano luminescent material adopts cesium fluoride as a cesium source and utilizes a high-temperature coprecipitation method to prepare the rare earth doped Cs2NaYF6The preparation method of the nano luminescent material comprises the following steps:
s1, dissolving sodium salt and rare earth salt in a solvent;
s2, mixing the solution obtained in the step S1 with cesium fluoride;
s3, carrying out heating reaction on the mixed solution obtained in the step S2, then carrying out centrifugal separation, and collecting precipitates;
s4, ultrasonically dispersing the precipitate obtained in the step S3 by using a dispersing agent, settling, centrifuging and washing the precipitating agent to obtain the rare earth doped Cs2NaYF6A nano luminescent material.
In the step S1, the molar ratio of the sodium salt to the rare earth salt is (0.5-2) to 1; the sodium salt is sodium chloride, sodium oleate, sodium hydroxide, sodium sulfate or sodium acetate, preferably sodium acetate; the rare earth salt is hydrochloride, sulfate or acetate of one or more of conventional rare earth elements La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc, preferably acetate, such as La (CH)3COO)3、Ce(CH3COO)3、Pr(CH3COO)3、Nd(CH3COO)3、Pm(CH3COO)3、Sm(CH3COO)3、Eu(CH3COO)3、Gd(CH3COO)3、Tb(CH3COO)3、Dy(CH3COO)3、Ho(CH3COO)3、Er(CH3COO)3、Tm(CH3COO)3、Yb(CH3COO)3、Lu(CH3COO)3、Y(CH3COO)3、Sc(CH3COO)3One or more of; the solvent is one or more of oleic acid, oleylamine and octadecene, and when the solvent is a mixture, the solvent can be prepared from oleic acid, oleylamine and octadecene according to the volume ratio of (1-2) to (1-2), and preferably 1:1: 2.
In step S1, in order to dissolve the raw materials in the solvent well, the raw materials may be mixed and heated, for example, heated to 100 to 200 ℃, and then kept warm for 10 to 60 minutes; the heating is preferably carried out under an inert gas blanket.
In step S2, the ratio of the molar amount of cesium fluoride to the molar amount of sodium salt + rare earth salt used is (3 to 6):1, preferably 4: 1.
In step S2, to promote the mixing of cesium fluoride, cesium fluoride may be dissolved in a solvent, which may be an alcohol solvent such as methanol, and then mixed with the solution obtained in step S1.
In step S3, the heating reaction is performed under the protection of an inert gas, such as nitrogen, and the reaction temperature is 280 to 360 ℃, preferably 300 to 340 ℃, and the reaction time is 20 to 180 minutes.
In step S4, the dispersant is one or more of cyclohexane, n-hexane, and toluene, and the precipitant is one or more of ethanol, methyl acetate, and ethyl acetate.
In step S4, the ultrasound may be performed under normal temperature or heating condition, and the time t of ultrasound is 0< t ≦ 15 min, preferably 10 min.
Obtained rare earth doped Cs2NaYF6The nano luminescent material is hexagonal, uniform in size, oil-soluble and colloidal in dispersion liquid; under the excitation of 980 nm light, the nano luminescent material can realize the up-conversion luminescence of rare earth, thereby emitting blue, green and yellow light or the mixed light of any more than two of the blue, green and yellow light, such as red and the like; under the excitation of xenon lamp, the material can also realize the down-transfer luminescence of rare earth, such as the Ce ion sensitized Tb ion5D4→7FJTransmit (J =3, 4, 5, 6).
The invention has the beneficial effects that:
1) the invention utilizes cesium fluoride as a raw material to replace the combination of the traditional cesium hydroxide and ammonium fluoride, synthesizes a series of monodisperse morphology-controllable different rare earth doped fluoride potassium cryolite structure nano materials by a high-temperature coprecipitation method, has easily controlled synthesis conditions and good repeatability, greatly improves the atom utilization rate, and prepares the rare earth doped Cs2NaYF6The particle size of the nano material can be regulated and controlled within the range of 15-25 nm in different solvents, and the obtained particles have good dispersibility, uniformity and repeatability. The traditional hydrothermal method and high-temperature solid phase method can not synthesize Cs with the particle size less than 1 mu m2NaYF6And (3) nanoparticles.
2) The invention provides the rare earth doped Cs for the first time2NaYF6The synthesis method of the nano material has potential value for being popularized to the synthesis of other nano materials of the type.
3) The present invention utilizes Cs2NaYF6The nano material is easy to dopeBy adding the characteristics of various rare earth ions, the luminous performance of the nano material can be effectively regulated and controlled by regulating the concentration of metal salt in the reactant, and the multicolor luminescence of up-conversion and down-conversion of one or more rare earth ions at different doping concentrations is realized.
Drawings
FIG. 1 shows the synthesis of rare earth doped Cs by high temperature coprecipitation method2NaYF6A process schematic of a nanomaterial;
FIG. 2 shows Cs obtained in example 12NaYF6An upconversion luminescence physical diagram of Tm ions of the Yb/Tm nano material under the excitation of 980 nm light;
FIG. 3 shows Cs obtained in example 12NaYF6An up-conversion luminescence spectrum of Tm ions of the Yb/Tm nano material under the excitation of 980 nm light;
FIG. 4 shows cubic phase Cs synthesized in example 1 at different solvent ratios2NaYF6X-ray powder diffraction pattern of 19% Yb/1% Tm nanocrystals;
FIG. 5 shows cubic phase Cs synthesized in example 1 with different solvent ratios2NaYF6Transmission electron micrographs (a-c) and particle size distribution plots (d-f) of 19% Yb/1% Tm nanocrystals;
FIG. 6 shows Cs obtained in example 22NaYF6An up-conversion luminescence spectrum of Er ions of the Yb/Er nano material under the excitation of 980 nm light;
FIG. 7 shows Cs obtained in example 32NaYF6An excitation spectrum (225-400 nm) collected by the Ce/Tb nano material when the emission wavelength is 543 nm;
FIG. 8 shows Cs obtained in example 32NaYF6The lower transfer luminescence emission spectrum (300-650 nm) of the Ce/Tb nano material under the excitation wavelength of 290 nm.
Detailed Description
The technical solution of the present invention is explained in detail by the exemplary embodiments below. These examples should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise stated, the starting materials and reagents described in the examples are all commercially available products.
The apparatus used in the present invention is as follows: the X-ray powder diffraction of the nanocrystals (instrument model is MiniFlex2, manufacturer is Rigaku, copper target radiation wavelength is λ = 0.154187 nm), transmission electron microscopy (instrument model is JEM-2010, manufacturer is JEOL), near-infrared emission spectrum of the nanocrystals (instrument model is FLS980, manufacturer is Edinburgh, excitation light source is 980 nm laser).
Example 1
Preparing oil-soluble Cs by using rare earth acetate and sodium oleate as raw materials through high-temperature coprecipitation method2NaYF619% Yb/1% Tm nanocrystalline:
(1) preparing a metal ion precursor solution: 0.40 mmol of yttrium acetate (Y (CH) was weighed3COO)3·6H2O), 0.095 mmol of ytterbium acetate (Yb (CH)3COO)3·6H2O), 0.005 mmol of thulium acetate (Tm (CH)3COO)3·6H2O), 0.50 mmol of sodium oleate, 4 mL of oleic acid, 8 mL of oleylamine and 8 mL of octadecene were placed in a two-necked flask, and a thermo-well tube and a straight suction adapter were attached to the flask. Opening a gas bottle, exhausting air in the flask by using nitrogen, stirring at room temperature by using a magnetic stirrer, simultaneously heating the mixed solution to 120 ℃ by using a heating sleeve, keeping the temperature for 30 min, exhausting water molecules generated after the metal acetate hydrate is dissolved in the flask until the oily solution becomes clear and transparent, and then cooling to room temperature, wherein the solution is used as a metal ion precursor solution for later use.
(2) Adding a methanol solution containing cesium fluoride: weighing 3 mmol of cesium fluoride, ultrasonically dissolving the cesium fluoride into 5 mL of methanol until the solution is clear and transparent and no obvious particulate matter exists, slowly dropwise adding the cesium fluoride into the metal ion precursor solution prepared in the step (1), and stirring at room temperature for 30 min to fully and uniformly stir the solution.
(3) The high-temperature coprecipitation preparation of the rare earth fluoride elpasolite structure nano material comprises the following steps: the mixed solution obtained in the step (2) is carried out at 7 ℃ for min under the protection of nitrogen-1The temperature is raised to 320 ℃, the methanol and the water in the flask are drained, and the temperature is keptReacting for 0.5-2 h, growing and crystallizing the nano material in the oily solution through high temperature, and then finishing the reaction at 5 ℃ for min-1Slowly cooled to room temperature.
(4) Purifying and separating the rare earth fluoride elpasolite structure nano material: adding 10 mL of ethanol into the oily solution obtained by the reaction in the step (3), stirring for 30 min to uniformly mix the mixture, transferring the mixture into a centrifuge tube, performing centrifugal separation to collect precipitate, performing ultrasonic dispersion on the precipitate by using cyclohexane, performing sedimentation and centrifugation by using ethanol, washing the obtained precipitate for multiple times by using ethanol, and re-dispersing the precipitate in the cyclohexane to obtain the rare earth doped Cs2NaYF6Colloidal solutions of nanomaterials.
FIG. 2 shows the obtained Cs2NaYF6The up-conversion luminescence physical diagram of Tm ions of the Yb/Tm nano material under the excitation of 980 nm light. FIG. 3 shows the obtained Cs2NaYF6An up-conversion luminescence spectrum of Tm ions of the Yb/Tm nano material under the excitation of 980 nm light. As can be seen from the figure, it is,1I6→3H6，3F4、1D2→3H6the transition of (a) corresponds to the ultraviolet light,1D2→3F4，1G4→3H6the transition of (a) corresponds to blue light,1G4→3F4the transition of (a) corresponds to red light,3H4→3H6the transition of (d) corresponds to near infrared light. The resulting material appeared blue under excitation by 980 nm light.
Respectively adjusting the volume ratio of oleic acid to oleylamine to octadecene in the step (1) to 1:1:2 and the volume ratio of oleylamine to octadecene in the step (2: 1: 2), and preparing the mixture according to the steps to obtain the rare earth doped Cs synthesized by different solvent ratios2NaYF6And (3) nano materials. The results of the measurements on the three materials are shown in FIGS. 4 to 5. As can be seen from FIG. 5, the rare earth doped Cs synthesized by different solvent ratios2NaYF6The average particle diameters of the nanometer materials are respectively (17.6 +/-2.3) nm, (19.6 +/-3.4) nm and (25.4 +/-3.2) nm.
Example 2
Rare earth acetate and sodium oleate are used as raw materialsPreparation of oil-soluble Cs by high temperature coprecipitation2NaYF618% Yb/2% Er nanocrystalline:
(1) preparing a metal ion precursor solution: 0.40 mmol of yttrium acetate (Y (CH) was weighed3COO)3·6H2O), 0.09 mmol of ytterbium acetate (Yb (CH)3COO)3·6H2O) and 0.01 mmol of erbium acetate (Er (CH)3COO)3·6H2O), 0.50 mmol of sodium oleate, 8 mL of oleic acid, 4 mL of oleylamine and 8 mL of octadecene were placed in a two-necked flask, and a thermo-well tube and a straight suction adapter were attached to the flask. Opening a gas bottle, exhausting air in the flask by using nitrogen, stirring at room temperature by using a magnetic stirrer, simultaneously heating the mixed solution to 120 ℃ by using a heating sleeve, keeping the temperature for 30 min, exhausting water molecules generated after the metal acetate hydrate is dissolved in the flask until the oily solution becomes clear and transparent, and then cooling to room temperature, wherein the solution is used as a metal ion precursor solution for later use.
(2) Adding a methanol solution containing cesium fluoride: weighing 4 mmol of cesium fluoride, ultrasonically dissolving the cesium fluoride into 5 mL of methanol until the solution is clear and transparent and no obvious particulate matter exists, slowly dropwise adding the cesium fluoride into the metal ion precursor solution prepared in the step (1), and stirring at room temperature for 30 min to fully and uniformly stir the solution.
(3) The high-temperature coprecipitation preparation of the rare earth fluoride elpasolite structure nano material comprises the following steps: the mixed solution obtained in the step (2) is carried out at 7 ℃ for min under the protection of nitrogen-1Heating to 320 ℃, exhausting methanol and water in the flask, carrying out heat preservation reaction for 0.5-2 h, enabling the nano material to grow and crystallize in the oily solution through high temperature, and then finishing the reaction at 5 ℃ for min-1Slowly cooled to room temperature.
(4) Purifying and separating the rare earth fluoride elpasolite structure nano material: adding 10 mL of methyl acetate into the oily solution obtained by the reaction in the step (3), stirring for 30 min to uniformly mix the methyl acetate, transferring the mixture into a centrifuge tube, performing centrifugal separation to collect precipitate, performing ultrasonic dispersion on the precipitate by using cyclohexane, performing sedimentation and centrifugation by using methyl acetate, washing the obtained precipitate for multiple times by using methyl acetate, and re-dispersing the precipitateIn cyclohexane, rare earth doped Cs can be obtained2NaYF6Colloidal solutions of nanomaterials.
FIG. 6 shows the obtained Cs2NaYF6An up-conversion luminescence spectrum of Er ions of the Yb/Er nano material under the excitation of 980 nm light. As can be seen from the figure, it is,4G11/2→4I15/2the transition of (a) corresponds to the ultraviolet light,2H9/2→4I15/2the transition of (a) corresponds to blue light,2H11/2→4I15/2、4S3/2→4I15/2the transition of (a) corresponds to green light,4F9/2→4I15/2the transition of (d) corresponds to red light. The resulting material appeared yellow under 980 nm light excitation.
Example 3
Preparing oil-soluble Cs by using rare earth acetate and sodium oleate as raw materials through high-temperature coprecipitation method2NaYF65% Ce/5% Tb nanocrystal:
(1) preparing a metal ion precursor solution: 0.45 mmol of yttrium acetate (Y (CH)3COO)3·6H2O), 0.025 mmol of cerium acetate (Ce (CH)3COO)3·6H2O) and 0.025 mmol of terbium acetate (Tb (CH)3COO)3·6H2O), 0.50 mmol of sodium oleate, 4 mL of oleic acid, 8 mL of oleylamine and 8 mL of octadecene were placed in a two-necked flask, and a thermo-well tube and a straight suction adapter were attached to the flask. Opening a gas bottle, exhausting air in the flask by using nitrogen, stirring at room temperature by using a magnetic stirrer, simultaneously heating the mixed solution to 120 ℃ by using a heating sleeve, keeping the temperature for 30 min, exhausting water molecules generated after the metal acetate hydrate is dissolved in the flask until the oily solution becomes clear and transparent, and then cooling to room temperature, wherein the solution is used as a metal ion precursor solution for later use.
(2) Adding a methanol solution containing cesium fluoride: weighing 5 mmol of cesium fluoride, ultrasonically dissolving the cesium fluoride into 5 mL of methanol until the solution is clear and transparent and no obvious particulate matter exists, slowly dropwise adding the cesium fluoride into the metal ion precursor solution prepared in the step (1), and stirring at room temperature for 30 min to fully and uniformly stir the solution.
(3) The high-temperature coprecipitation preparation of the rare earth fluoride elpasolite structure nano material comprises the following steps: the mixed solution obtained in the step (2) is carried out at 7 ℃ for min under the protection of nitrogen-1Heating to 320 ℃, exhausting methanol and water in the flask, carrying out heat preservation reaction for 0.5-2 h, enabling the nano material to grow and crystallize in the oily solution through high temperature, and then finishing the reaction at 5 ℃ for min-1Slowly cooled to room temperature.
(4) Purifying and separating the rare earth fluoride elpasolite structure nano material: adding 10 mL of ethyl acetate into the oily solution obtained by the reaction in the step (3), stirring for 30 min to uniformly mix the mixture, transferring the mixture into a centrifuge tube, performing centrifugal separation to collect precipitate, performing ultrasonic dispersion on the precipitate by using normal hexane, performing sedimentation and centrifugation by using ethyl acetate, washing the obtained precipitate for multiple times by using ethyl acetate, and re-dispersing the precipitate in the normal hexane to obtain the rare earth doped Cs2NaYF6Colloidal solutions of nanomaterials.
FIG. 7 shows the obtained Cs2NaYF6An excitation spectrum (225-400 nm) collected by the Ce/Tb nano material when the emission wavelength is 543 nm; FIG. 8 shows the obtained Cs2NaYF6The lower transfer luminescence emission spectrum (300-650 nm) of the Ce/Tb nano material under the excitation wavelength of 290 nm. As can be seen from the figure, Ce3+Absorbing ultraviolet light is excited from 4f orbit to 5d orbit, and then energy is transferred to Tb3+Is generated from5D4Is transmitted. The resulting material appeared green under 290 nm light excitation.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (7)

1. Rare earth doped Cs2NaYF6The preparation method of the nano luminescent material is characterized in that cesium fluoride is used as a cesium source, and the rare earth doped Cs is prepared by a high-temperature coprecipitation method2NaYF6The preparation method of the nano luminescent material comprises the following steps:
s1, dissolving sodium salt and rare earth salt in a solvent;
s2, mixing the solution obtained in the step S1 with cesium fluoride;
s3, carrying out heating reaction on the mixed solution obtained in the step S2, then carrying out centrifugal separation, and collecting precipitates;
s4, ultrasonically dispersing the precipitate obtained in the step S3 by using a dispersing agent, settling, centrifuging and washing the precipitating agent to obtain the rare earth doped Cs2NaYF6A nano luminescent material.
2. The method according to claim 1, wherein in step S1, the molar ratio of the sodium salt to the rare earth salt is (0.5-2): 1;
the sodium salt is sodium chloride, sodium oleate, sodium hydroxide, sodium sulfate or sodium acetate; the rare earth salt is hydrochloride, sulfate or acetate of one or more rare earth elements; the solvent is one or more of oleic acid, oleylamine and octadecene.
3. The preparation method according to claim 1, wherein the step S1 further comprises heating the solution to 100-200 ℃, and keeping the temperature for 10-60 minutes to fully dissolve the raw materials; the heating is carried out under the protection of inert gas.
4. The method according to claim 1, wherein in step S2, the ratio of the molar amount of cesium fluoride to the total molar amount of sodium salt and rare earth salt is (3-6): 1.
5. The method according to claim 1, wherein in step S3, the heating reaction is performed under the protection of inert gas, the reaction temperature is 280-360 ℃, and the reaction time is 20-180 minutes.
6. The preparation method according to claim 1, wherein in step S4, the dispersant is one or more of cyclohexane, n-hexane and toluene, the precipitant is one or more of ethanol, methyl acetate and ethyl acetate, and the time t of the ultrasonic treatment is 0< t ≦ 15 min.
7. Rare earth doped Cs prepared by the method of claims 1-62NaYF6The nanometer luminescent material is characterized in that: obtained rare earth doped Cs2NaYF6The nanometer luminescent material is hexagonal, uniform in size, oil-soluble, and colloidal in dispersion liquid; under the excitation of 980 nm light, the nano luminescent material can realize the up-conversion luminescence of rare earth, thereby emitting blue, green and yellow lights or the mixed light of any two or more of the lights, and under the excitation of a xenon lamp, the nano luminescent material can also realize the down-conversion luminescence of the rare earth.
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