CN110699080A - Ultra-small scandium oxide based up-conversion luminescent material and preparation method thereof - Google Patents

Ultra-small scandium oxide based up-conversion luminescent material and preparation method thereof Download PDF

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CN110699080A
CN110699080A CN201911092373.5A CN201911092373A CN110699080A CN 110699080 A CN110699080 A CN 110699080A CN 201911092373 A CN201911092373 A CN 201911092373A CN 110699080 A CN110699080 A CN 110699080A
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李静
秦慧连
陈力
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Changchun University of Technology
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Abstract

The invention relates to an ultra-small scandium oxide based up-conversion luminescent material and a preparation method thereof, belonging to the technical field of luminescent materials. The technical problems of large size and poor dispersibility of the scandium oxide-based up-conversion luminescent material prepared in the prior art are solved. The Yb is obtained by a solvothermal method with octadecene as a solvent and oleic acid as a complexing agent3+/Er3+Co-doped ultra Small Sc2O3The material is nano-scale, has uniform spherical particles, has the minimum size of less than 10nm, has good dispersibility, and can emit light by red up-conversion. The up-conversion luminescent material prepared by the invention can observe 650nm red light emission under the excitation of near infrared light with the wavelength of 980 nm. Compared with the scandium oxide-based up-conversion luminescent material prepared by the traditional high-temperature solid phase method and the aqueous phase method, the scandium oxide-based up-conversion luminescent material has smaller size and more dispersionGood results are obtained.

Description

Ultra-small scandium oxide based up-conversion luminescent material and preparation method thereof
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a near-infrared light excited ultra-small scandium oxide based up-conversion luminescent material with the minimum size of less than 10nm and a preparation method thereof.
Background
Upconversion luminescence is a nonlinear optical process characterized in that ground state electrons absorb two or more photons of longer wavelength, and then undergo transition emission of photons of shorter wavelength after being populated to a higher excited state by mechanisms such as excited state absorption. The fluorescent material has good application prospect in many aspects due to the specific optical property, and particularly has good application prospect in the fields of biosensors, infrared detection, biological imaging, fluorescence anti-counterfeiting, fluorescent probes, optical display, solar cells, photocatalysis and the like.
Compared with the traditional fluorescent probe (organic dye, quantum dot and the like), the rare earth doped up-conversion luminescence can effectively reduce the recession of matrix materials caused by photoionization, and has the advantages of good chemical stability, certain tunability of output wavelength, wide application range and the like. Meanwhile, under the excitation condition of long-wave-near infrared light (800-. The rare earth up-conversion luminescent materials can be classified into fluorides, oxides, halides, sulfides, and the like, depending on the composition of the host. Among these host materials, fluoride is the most efficient host material recognized at present, but its disadvantages such as poor chemical stability, harsh manufacturing conditions, difficult control, difficult integration, etc. are very prominent, thus limiting its application to some extent. Although the energy of the oxide is slightly higher than that of the fluoride phonon, the preparation process is simple, the requirement on environmental conditions is lower, the solubility of rare earth ions is high, and the mechanical strength and the chemical stability are good. Thus, oxides are widely used host materials. However, the synthesis temperature of the up-conversion luminescent material using oxide as the host material is generally higher and the size is larger.
Cubic system sesquioxide material Sc2O3It is receiving attention because of its unique structure. The sesqui-oxygen compound has physical properties of lower phonon energy, large Stokes energy level splitting, stable chemical property, good heat conduction property and the like. However, sesquioxides generally have one major drawback: the preparation of samples requires very high temperatures and is therefore usually carried out by conventional high-temperature solid-phase methods. For Sc2O3The temperature of the material can only reach 1600 DEG CA pure phase can form. However, when the temperature reaches 1600 ℃, the prepared luminescent material is a massive body with a large number of spheroids adhered together due to the overhigh temperature, and has large size and poor dispersity. Thus obtaining small size Sc at low temperature2O3Materials are a problem to be solved.
Disclosure of Invention
The invention aims to solve the technical problems of large size and poor dispersibility of a scandium oxide-based up-conversion luminescent material prepared in the prior art, and provides a super-small scandium oxide-based up-conversion luminescent material which can be excited by near infrared light and has a minimum size of less than 10nm and a preparation method thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a preparation method of an ultra-small scandia-based up-conversion luminescent material, which comprises the following steps:
the chemical formula of the ultra-small scandium oxide based up-conversion luminescent material is as follows: sc (Sc)2(1-x-y)O3：Er3+ 2x，Yb3+ 2y(ii) a Wherein x and y are element mole fractions, and the value range is as follows: x is more than or equal to 0.0001 and less than or equal to 0.10, and y is more than or equal to 0.0001 and less than or equal to 0.20;
step 1, adding NaOH solid into a three-neck flask, adding oleic acid, octadecene and oleylamine into the three-neck flask, and heating under the condition of nitrogen or inert gas to form a solution A;
step 2, weighing Sc according to the stoichiometric ratio of each element in the chemical formula3+Compound of (b) containing Yb3+And Er contained in the compound (a)3+Adding the compound (A) into the solution A in the step (1), and heating to 100-180 ℃ for 50-80 minutes under the condition of nitrogen or inert gas to form a solution B;
step 3, continuously heating the solution B to 290-310 ℃ under the condition of nitrogen or inert gas, and keeping the temperature for 1-3 hours;
step 4, cooling the reaction liquid obtained in the step 3 to room temperature, firstly carrying out centrifugal cleaning for 3-5 times by using ethanol, and then carrying out centrifugal cleaning for 3-5 times by using deionized water; then placing the mixture into an oven, and drying the mixture for 15 to 24 hours at the constant temperature of between 40 and 80 ℃ to obtain a reactant precursor precipitate;
and 5, placing the reactant precursor precipitate obtained in the step 4 into a corundum crucible, covering, placing the corundum crucible into a high-temperature furnace, roasting at the roasting temperature of 500-1000 ℃ for 1-3 hours, taking out, and grinding to obtain the final product, namely the ultra-small scandium oxide-based up-conversion luminescent material.
In the above technical solution, preferably, step 1 specifically includes the following steps: 0.0376g of NaOH solid was charged into a three-necked flask, and then oleic acid, octadecene and oleylamine were added to the three-necked flask in a volume ratio of 1:10:3, heated to 110 ℃ under nitrogen or an inert gas for 60 minutes, and then cooled to 50 ℃ to form a solution A.
In the technical scheme, the heating temperature in the step 2 is preferably 110-160 ℃ and the holding time is preferably 60 minutes.
In the above-mentioned embodiment, it is preferable that Sc is contained in step 23+Compound of (b) containing Yb3+And Er contained in the compound (a)3+The compounds of (A) are all chloride or acetate salts of the corresponding ions.
In the above technical means, the drying temperature in step 4 is preferably 50 ℃ for 24 hours.
In the technical scheme, the heating temperature in the step 3 is preferably 300-305 ℃ and the holding time is preferably 1 hour, and the roasting temperature in the step 5 is preferably 500-800 ℃ and the time is preferably 2 hours.
In the above technical solution, it is further preferable that the calcination temperature in step 5 is 500 ℃ and the time is 2 hours.
The invention also provides the ultra-small scandium oxide-based up-conversion luminescent material prepared by the preparation method, which is in a nano-order of magnitude, uniform in particle and similar to a sphere, and has an average diameter of 1-40 nm.
In the above technical solution, it is further preferable that the average diameter of the ultra-small scandia-based up-conversion luminescent material is 1 to 30 nm.
In the above technical solution, it is most preferable that the average diameter of the ultra-small scandia-based up-conversion luminescent material is 1-10 nm.
The invention has the beneficial effects that:
the invention adopts a solvothermal method which takes octadecene as a solvent and oleic acid as a complexing agent to obtain Yb3+/Er3+Co-doped ultra Small Sc2O3The material is nano-scale, has uniform spherical particles, has the minimum size of less than 10nm, has good dispersibility, and can emit light by red up-conversion. Compared with the scandium oxide-based up-conversion luminescent material prepared by the traditional method, the particle size is small, and the process is simple.
The up-conversion luminescent material prepared by the invention can observe 650nm red light emission under the excitation of near infrared light with the wavelength of 980 nm. Compared with the scandium oxide-based up-conversion luminescent material prepared by the traditional high-temperature solid phase method and the aqueous phase method, the scandium oxide-based up-conversion luminescent material has smaller size and better dispersion.
The preparation method of the scandium oxide-based up-conversion luminescent material provided by the invention adopts a method combining solvothermal and annealing, and has the advantages of simple synthesis method, lower reaction temperature, low requirement on equipment and the like.
In the preparation process, the sintering only needs to reach 500 ℃, and when the temperature is 500 ℃, the spheroidal scandium oxide based up-conversion luminescent material with good dispersibility and small particle size can be prepared. As shown in a transmission electron micrograph 1, the synthesized nano spheroidal particles have the diameter distribution range of 1-10nm, the average diameter of 3.75nm and good dispersibility.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 shows Sc prepared in example 1 of the present invention1.88O3:Er3+ 0.02，Yb3+ 0.1Transmission electron micrograph (c).
FIG. 2 shows Sc prepared in example 1 of the present invention1.88O3:Er3+ 0.02，Yb3+ 0.1Upconversion emission spectrum under 980nm excitation.
FIG. 3 shows Sc prepared in example 1 of the present invention1.88O3:Er3+ 0.02，Yb3+ 0.1XRD diffractogram of.
FIG. 4 shows Sc prepared in example 1 of the present invention1.88O3:Er3+ 0.02，Yb3+ 0.1Particle size diagram (c).
FIG. 5 shows Sc prepared in example 2 of the present invention1.88O3:Er3+ 0.02，Yb3+ 0.1Transmission electron micrograph (c).
FIG. 6 shows Sc prepared in example 2 of the present invention1.88O3:Er3+ 0.02，Yb3+ 0.1Upconversion emission spectrum under 980nm excitation.
FIG. 7 shows Sc prepared in example 2 of the present invention1.88O3:Er3+ 0.02，Yb3+ 0.1XRD diffractogram of.
FIG. 8 shows Sc prepared in example 3 of the present invention1.76O3:Er3+ 0.04，Yb3+ 0.2Transmission electron micrograph (c).
FIG. 9 shows Sc prepared in example 3 of the present invention1.76O3:Er3+ 0.04，Yb3+ 0.2Upconversion emission spectrum under 980nm excitation.
FIG. 10 shows Sc prepared in example 4 of the present invention1.76O3:Er3+ 0.04，Yb3+ 0.2Transmission electron micrograph (c).
FIG. 11 shows Sc prepared in example 4 of the present invention1.76O3:Er3+ 0.04，Yb3+ 0.2Upconversion emission spectrum under 980nm excitation.
FIG. 12 shows Sc prepared in example 5 of the present invention1.88O3:Er3+ 0.02，Yb3+ 0.1Transmission electron micrograph (c).
Detailed Description
The invention provides a preparation method of an ultra-small scandia-based up-conversion luminescent material, which adopts a solvothermal method with octadecene as a solvent and oleic acid as a complexing agent to obtain Yb3+/Er3+Co-doped ultra Small Sc2O3A material. The method has the advantages of lower reaction temperatureLow cost, easy operation and no environmental pollution.
The preparation method specifically comprises the following steps:
the chemical formula of the ultra-small scandium oxide based up-conversion luminescent material is as follows: sc (Sc)2(1-x-y)O3：Er3+ 2x，Yb3+ 2y(ii) a Wherein x and y are element mole fractions, and the value range is as follows: x is more than or equal to 0.0001 and less than or equal to 0.10, and y is more than or equal to 0.0001 and less than or equal to 0.20;
step 1, adding 0.0376g of NaOH solid into a three-neck flask, adding oleic acid, octadecene and oleylamine into the three-neck flask according to the volume ratio of 1:10:3, heating to 110 ℃ for 60 minutes under the condition of nitrogen or inert gas, and then cooling to 50 ℃ to form a solution A;
step 2, respectively weighing Sc according to the stoichiometric ratio of each element in the chemical formula3+Compound of (b) containing Yb3+And Er contained in the compound (a)3+Adding the compound into a three-neck flask, heating to 100-180 ℃ under the condition of nitrogen or inert gas, and keeping for 50-80 minutes to form a solution B; preferably, the heating temperature is 110-160 ℃, and the holding time is 60 minutes;
step 3, continuously heating the solution B at 290-310 ℃ for 1-3 hours under the condition of nitrogen or inert gas; preferably, the heating temperature is 300-305 ℃, and the holding time is 1 hour;
step 4, cooling the reaction liquid obtained in the step 3 to room temperature, firstly carrying out centrifugal cleaning for 3-5 times by using ethanol, and then carrying out centrifugal cleaning for 3-5 times by using deionized water; then placing the mixture into an oven, and drying the mixture for 15 to 24 hours at the constant temperature of between 40 and 80 ℃ to obtain a reactant precursor precipitate; preferably, the drying temperature is 50 ℃ for 24 hours;
step 5, putting the reactant precursor precipitate obtained in the step 4 into a corundum crucible, covering, putting into a high-temperature furnace, roasting at the roasting temperature of 500-1000 ℃ for 1-3 hours, taking out, and grinding to obtain a final product, namely the scandium oxide up-conversion luminescent material; preferably, the roasting temperature is 500-800 ℃, and the time is 2 hours; it is further preferable that the calcination temperature in step 5 is 500 ℃ and the time is 2 hours.
Wherein, you areThe component containing Sc described in step 13+Compound of (b) containing Yb3+And Er contained in the compound (a)3+The compounds of (A) are all chloride or acetate salts containing corresponding ions.
The invention also provides an ultra-small scandia-based up-conversion luminescent material prepared by the preparation method, which is a compound with the following chemical formula: sc (Sc)2(1-x-y)O3：Er3+ 2x，Yb3+ 2y(ii) a Wherein x and y are element mole fractions, and the value range is as follows: x is more than or equal to 0.0001 and less than or equal to 0.10, and y is more than or equal to 0.0001 and less than or equal to 0.20. The ultra-small scandium oxide based up-conversion luminescent material is in a nanometer order of magnitude, has uniform particles like a sphere, and has an average diameter of 1-40 nm. Further preferably the average diameter is 1 to 30nm, most preferably the average diameter is 1 to 10 nm. The ultra-small scandium oxide-based up-conversion luminescent material is cubic system sesquioxide Sc2O3. The ultra-small scandium oxide-based up-conversion luminescent material can emit 650nm red light under the excitation of near infrared light.
Example 1
0.0376g of NaOH was charged into a three-necked flask, and then 1mL of oleic acid, 10mL of octadecene and 3mL of oleylamine were added to the three-necked flask, heated to 110 ℃ for 1 hour under nitrogen or an inert gas, and then cooled to 50 ℃. According to Sc1.88O3:Er3+ 0.02，Yb3+ 0.1The stoichiometric ratio of each element in the mixture is 0.1218g of ScCl3·6H2O、0.0096gYbCl3·6H2O、0.0019gErCl3·6H2O solid powder is added into a three-neck flask and heated to 110 ℃ for 1h under the condition of nitrogen or inert gas. The solution was heated to 305 ℃ for 1h under nitrogen or inert gas. Then the obtained reaction solution is cooled to room temperature, and is centrifugally washed for 3 times by ethanol and then by deionized water for 3 times. Then putting the mixture into an oven, and drying the mixture for 24 hours at the constant temperature of 50 ℃ to obtain a reactant precursor precipitate; putting the reactant precursor precipitate into a corundum crucible, covering, placing in a high-temperature furnace, roasting at 500 ℃ for 2 hours, taking out, and grinding to obtain the infrared light-excited spheroidal nano-particlesSc-level scandium oxide-based up-conversion luminescent material1.88O3:Er3+ 0.02，Yb3+ 0.1。
The morphology, upconversion spectrum, and XRD scans of the sample of this example were:
the transmission electron microscope picture is shown in figure 1, the diameter distribution range of the synthesized nano-scale spheroidal particles is 1-10nm, the average diameter is 3.75nm, and the dispersibility is good;
the up-conversion emission spectrum under 980nm excitation is shown in FIG. 2, and the excitation power density is 7mW/mm2When the red is excited at 980nm, 650nm red up-conversion luminescence can be observed by naked eyes.
XRD diffraction pattern is shown in FIG. 3, together with Sc2O3The standard diffraction spectra (JCPDS card 05-0629) are consistent, and the half-peak width of the diffraction peak is larger, which indicates that the particle size is smaller; (with impurity NaCl in the figure)
The particle size diagram is shown in figure 4, the diameter distribution range of the synthesized nano-scale spheroidal particles is 1-10nm, and the average diameter is 3.75 nm.
Example 2
0.0376g of NaOH are placed in a three-necked flask, 1mL of oleic acid, 10mL of octadecene and 3mL of oleylamine are added to the three-necked flask, heated to 110 ℃ under nitrogen or inert gas for 1 hour, cooled to 50 ℃ and then treated with Sc1.88O3:Er3+ 0.1，Yb3+ 0.02The stoichiometric ratio of each element in the mixture is 0.1218g of ScCl3·6H2O、0.0096gYbCl3·6H2O、0.0019gErCl3·6H2O solid powder is added into a three-neck flask and heated to 160 ℃ for 1h under the condition of nitrogen or inert gas. The solution was heated to 305 ℃ for 1h under nitrogen or inert gas. Then cooling the obtained reaction solution to room temperature, firstly centrifugally cleaning for 3 times by using ethanol, and then centrifugally cleaning for 3 times by using deionized water; then putting the mixture into an oven, and drying the mixture for 24 hours at the constant temperature of 50 ℃ to obtain a reactant precursor precipitate; putting the reactant precursor precipitate into a corundum crucible, covering, putting into a high-temperature furnace, roasting at 500 ℃ for 2 hours, taking out, and grinding to obtain the infrared laserLuminescent Sc-like spherical nano scandium oxide based up-conversion luminescent material1.88O3:Er3+ 0.02，Yb3+ 0.1。
The morphology, upconversion spectrum, and XRD scans of the sample of this example were:
the transmission electron microscope picture is shown in figure 5, the diameter distribution range of the synthesized nano-scale spheroidal particles is 1-10nm, and the dispersibility is good;
the up-conversion emission spectrum under 980nm excitation is shown in FIG. 6, and the excitation power density is 7mW/mm2When the red is excited at 980nm, 650nm red up-conversion luminescence can be observed by naked eyes.
XRD diffraction pattern is shown in FIG. 7, together with Sc2O3The standard diffraction spectra (JCPDS card 05-0629) are consistent with a larger half-width of the diffraction peak, indicating a smaller particle size.
Example 3
0.0376g of NaOH are placed in a three-necked flask, 1mL of oleic acid, 10mL of octadecene and 3mL of oleylamine are added to the three-necked flask, heated to 110 ℃ under nitrogen or inert gas for 1 hour, cooled to 50 ℃ and then treated with Sc1.76O3:Er3+ 0.04，Yb3+ 0.2The stoichiometric ratio of each element in the mixture is 0.1141g of ScCl3·6H2O、0.0194gYbCl3·6H2O、0.0038gErCl3·6H2O solid powder is added into a three-neck flask and heated to 110 ℃ for 1h under the condition of nitrogen or inert gas. The solution was heated to 305 ℃ for 1h under nitrogen or inert gas. Then cooling the obtained reaction solution to room temperature, firstly centrifugally cleaning for 3 times by using ethanol, and then centrifugally cleaning for 3 times by using deionized water; then putting the mixture into an oven, and drying the mixture for 24 hours at the constant temperature of 50 ℃ to obtain a reactant precursor precipitate; putting the reactant precursor precipitate into a corundum crucible, covering the corundum crucible, putting the corundum crucible into a high-temperature furnace, roasting at the roasting temperature of 600 ℃ for 2 hours, taking out the corundum precursor precipitate, and grinding the corundum precursor precipitate to obtain the infrared light-excited spheroidal and nanoscale scandium oxide-based up-conversion luminescent material Sc1.76O3:Er3+ 0.04，Yb3+ 0.2。
The morphology, upconversion spectrum, and XRD scans of the sample of this example were:
the transmission electron microscope picture is shown in figure 8, the diameter distribution range of the synthesized nano-scale spheroidal particles is 1-30nm, and the dispersibility is good;
the up-conversion emission spectrum under 980nm excitation is shown in FIG. 9, and the excitation power density is 7mW/mm2When the red is excited at 980nm, 650nm red up-conversion luminescence can be observed by naked eyes.
Example 4
0.0376g of NaOH are placed in a three-necked flask, 1mL of oleic acid, 10mL of octadecene and 3mL of oleylamine are added to the three-necked flask, the mixture is heated to 110 ℃ for 1 hour under nitrogen or inert gas, and then cooled to 50 ℃ according to Sc1.76O3:Er3+ 0.04，Yb3+ 0.2The stoichiometric ratio of each element in the mixture is 0.1141g of ScCl3·6H2O、0.0194gYbCl3·6H2O、0.0038gErCl3·6H2O solid powder is added into a three-neck flask and heated to 110 ℃ for 1h under the condition of nitrogen or inert gas. The solution was heated to 305 ℃ for 1h under nitrogen or inert gas. Then cooling the obtained reaction solution to room temperature, firstly centrifugally cleaning for 3 times by using ethanol, and then centrifugally cleaning for 3 times by using deionized water; then putting the mixture into an oven, and drying the mixture for 24 hours at the constant temperature of 50 ℃ to obtain a reactant precursor precipitate; putting the reactant precursor precipitate into a corundum crucible, covering the corundum crucible, putting the corundum crucible into a high-temperature furnace, roasting at 800 ℃ for 2 hours, taking out and grinding to obtain the infrared light-excited spheroidal and nanoscale scandium oxide-based up-conversion luminescent material Sc1.76O3:Er3+ 0.04，Yb3+ 0.2。
The transmission electron microscope picture is shown in figure 10, the diameter distribution range of the synthesized nano-scale spheroidal particles is 10-40 nm, and the dispersibility is good;
the up-conversion emission spectrum under 980nm excitation is shown in FIG. 11, and the excitation power density is 7mW/mm2When the red is excited at 980nm, 650nm red up-conversion luminescence can be observed by naked eyes.
Example 5
0.0376g of NaOH are placed in a three-necked flask, 1mL of oleic acid, 10mL of octadecene and 3mL of oleylamine are added to the three-necked flask, the mixture is heated to 110 ℃ for 1 hour under nitrogen or inert gas, and then cooled to 50 ℃ according to Sc1.88O3:Er3+ 0.1，Yb3+ 0.02The stoichiometric ratio of each element in the mixture is 0.1218g of ScCl3·6H2O、0.0096gYbCl3·6H2O、0.0019gErCl3·6H2O solid powder is added into a three-neck flask and heated to 110 ℃ for 1h under the condition of nitrogen or inert gas. The solution is heated to 300 ℃ for 1h under nitrogen or inert gas. Then cooling the obtained reaction solution to room temperature, firstly centrifugally cleaning for 3 times by using ethanol, and then centrifugally cleaning for 3 times by using deionized water; then putting the mixture into an oven, and drying the mixture for 24 hours at the constant temperature of 50 ℃ to obtain a reactant precursor precipitate; putting the reactant precursor precipitate into a corundum crucible, covering the corundum crucible, putting the corundum crucible into a high-temperature furnace, roasting at 500 ℃ for 2 hours, taking out and grinding to obtain the infrared light-excited spheroidal and nanoscale scandium oxide-based up-conversion luminescent material Sc1.88O3:Er3+ 0.02，Yb3+ 0.1。
The morphology and XRD scan of the sample of this example are:
the transmission electron micrograph is shown in figure 12, the diameter distribution range of the synthesized nano-scale spheroidal particles is 1-10nm, and the dispersibility is good.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (10)

1. A preparation method of an ultra-small scandium oxide based up-conversion luminescent material is characterized by comprising the following steps:
the chemical formula of the ultra-small scandium oxide based up-conversion luminescent material is as follows: sc (Sc)2(1-x-y)O3：Er3+ 2x，Yb3+ 2y(ii) a Wherein x and y are element mole fractions, and the value range is as follows: x is more than or equal to 0.0001 and less than or equal to 0.10, and y is more than or equal to 0.0001 and less than or equal to 0.20;
step 1, adding NaOH solid into a three-neck flask, adding oleic acid, octadecene and oleylamine into the three-neck flask, and heating under the condition of nitrogen or inert gas to form a solution A;
step 2, weighing Sc according to the stoichiometric ratio of each element in the chemical formula3+Compound of (b) containing Yb3+And Er contained in the compound (a)3+Adding the compound (A) into the solution A in the step (1), and heating to 100-180 ℃ for 50-80 minutes under the condition of nitrogen or inert gas to form a solution B;
step 3, continuously heating the solution B to 290-310 ℃ under the condition of nitrogen or inert gas, and keeping the temperature for 1-3 hours;
step 4, cooling the reaction liquid obtained in the step 3 to room temperature, firstly carrying out centrifugal cleaning for 3-5 times by using ethanol, and then carrying out centrifugal cleaning for 3-5 times by using deionized water; then placing the mixture into an oven, and drying the mixture for 15 to 24 hours at the constant temperature of between 40 and 80 ℃ to obtain a reactant precursor precipitate;
and 5, placing the reactant precursor precipitate obtained in the step 4 into a corundum crucible, covering, placing the corundum crucible into a high-temperature furnace, roasting at the roasting temperature of 500-1000 ℃ for 1-3 hours, taking out, and grinding to obtain the final product, namely the ultra-small scandium oxide-based up-conversion luminescent material.
2. The preparation method according to claim 1, wherein the step 1 specifically comprises the steps of: 0.0376g of NaOH solid was added to a three-necked flask, and then oleic acid, octadecene and oleylamine were added to the three-necked flask in a volume ratio of 1:10:3, heated to 110 ℃ under nitrogen or an inert gas for 60 minutes, and then cooled to 50 ℃ to form a solution A.
3. The method according to claim 1, wherein the heating temperature in step 2 is 110 to 160 ℃ and the holding time is 60 minutes.
4. The method according to claim 1, wherein the Sc is contained in the step 23+Compound of (b) containing Yb3+And Er contained in the compound (a)3+The compounds of (A) are all chloride or acetate salts of the corresponding ions.
5. The method according to claim 1, wherein the drying temperature in step 4 is 50 ℃ for 24 hours.
6. The method according to any one of claims 1 to 6, wherein the heating temperature in step 3 is 300 to 305 ℃ and the holding time is 1 hour, and the baking temperature in step 5 is 500 to 800 ℃ and the holding time is 2 hours.
7. The method according to claim 6, wherein the calcination temperature in the step 5 is 500 ℃ and the calcination time is 2 hours.
8. An ultra-small scandia-based up-conversion luminescent material prepared by the preparation method of claim 1, which is in the order of nanometers, has a uniform particle, is spheroidal, and has an average diameter of 1-40 nm.
9. The ultra-small scandia-based up-conversion luminescent material according to claim 8, having an average diameter of 1-30 nm.
10. An ultra-small scandia-based up-conversion luminescent material according to claim 8, having an average diameter of 1-10 nm.
CN201911092373.5A 2019-11-11 2019-11-11 Ultra-small scandium oxide based up-conversion luminescent material and preparation method thereof Pending CN110699080A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108659838A (en) * 2018-05-02 2018-10-16 长春工业大学 A kind of nanoscale near-spherical scandium oxide base up-conversion luminescent material and preparation method thereof
CN109810707A (en) * 2017-11-22 2019-05-28 中国科学院宁波材料技术与工程研究所 A kind of nano material and preparation method thereof of near-infrared fluorescent transmitting

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109810707A (en) * 2017-11-22 2019-05-28 中国科学院宁波材料技术与工程研究所 A kind of nano material and preparation method thereof of near-infrared fluorescent transmitting
CN108659838A (en) * 2018-05-02 2018-10-16 长春工业大学 A kind of nanoscale near-spherical scandium oxide base up-conversion luminescent material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JENS ADAM等: "Light Emission Intensities of Luminescent Y2O3:Eu and Gd2O3:Eu Particles of Various Sizes", 《NANOMATERIALS》 *
刘大玖: "稀土掺杂超小氧化钪纳米晶的可控制备、发光物理及其应用研究", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》 *

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