CN114479839B - Multi-element rare earth sulfide luminescent material and preparation method thereof - Google Patents
Multi-element rare earth sulfide luminescent material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a multi-element rare earth sulfide luminescent material, the chemical expression of which is shown as the formula I：A a Sr 1‑1/2a S is bLn, cM formula I; wherein A is selected from one or more of Li, na and K, ln is selected from one or more of Ce, eu and Dy, M is selected from one or more of Ca, mg, cl, br, a, b and c are A, ln and M is used as the mole percentage of the corresponding doping ion of the doping ion relative to the S atom. The luminescent material can be excited by ultraviolet and visible light to emit adjustable spectrum, and can be used in the fields of LED illumination and display. The invention also provides a preparation method of the multi-element rare earth sulfide luminescent material, which is a high-temperature solid-phase synthesis method, and has the advantages of simple process, low raw material cost and easy realization of industrialization.
Description
Technical Field
The invention relates to the technical field of rare earth luminescent materials, in particular to a multi-element rare earth sulfide luminescent material and a preparation method thereof.
Background
Compared with the traditional illumination light, the white light LED has the advantages of energy conservation, environmental protection, long service life, good color rendering property, good response speed and the like. Regarding the energy consumption, the energy consumption of a white light LED is only one tenth of that of an incandescent lamp, and about one fourth of that of an energy-saving lamp. Therefore, the white light LED is more suitable for illumination in daily life of people and has a very large application prospect. The existing rare earth sulfide luminescent material has the defects of limited preparation method, complex and difficult preparation process, low yield and accompanying pollution gas generation and danger.
Therefore, the rare earth sulfide luminescent material is required to be improved on the basis of the existing rare earth sulfide luminescent material, and has the advantages of high luminous efficiency, high color purity, high color rendering index, good luminous stability and easy spectrum regulation and control.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a multi-element rare earth sulfide luminescent material which has high luminous efficiency and color purity, and can be spectrally regulated by regulating rare earth doping.
The second object of the present invention is to provide a method for preparing the above-mentioned multi-element rare earth sulfide luminescent material.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention relates to a multi-element rare earth sulfide luminescent material, the chemical expression of which is shown in formula I:
A a Sr 1-1/2a s is bLn, cM formula I;
wherein, A is selected from one or more of Li, na and K, ln is selected from one or more of Ce, eu and Dy, and M is selected from one or more of Ca, mg, cl, br;
a=0 to 0.1, b=0.001 to 0.2, c=0 to 0.2, preferably a=0 to 0.035, b=0.0005 to 0.04, c=0 to 0.035.
In the above formula I, A, ln and M are both doping ions, and a, b and c are mole percentage coefficients of the corresponding doping ions relative to the S atom.
The matrix material of the rare earth visible luminescent material provided by the invention is strontium sulfide, and after the matrix material absorbs energy, the energy is transferred to the visible light luminescent center ion, namely rare earth ion, and visible light is emitted, so that the visible light luminescent intensity is higher, and the luminescent efficiency is higher. The experimental results show that: when the rare earth visible luminescent material provided by the invention is excited by 276nm ultraviolet light and 430nm blue-green light, different rare earth ions are doped, and the wavelength of the maximum emission intensity of the material is different. When cerium ions are doped, the wavelength of the maximum emission intensity of the material is respectively located near 495 nm; when doped with europium ions, the wavelength of the maximum emission intensity of the material is located near 620nm, and the half-peak width reaches 78nm.
The invention also relates to a preparation method of the multi-element rare earth sulfide luminescent material, which comprises the following steps:
(1) Mixing a Sr-containing compound, an A-containing compound, an M-containing compound, a sulfur source and an Ln-containing compound to obtain a first mixture;
(2) Wrapping the first mixture with a second mixture, sintering, and removing a wrapping layer to obtain the multi-element rare earth sulfide luminescent material;
the second mixture includes one or more of an a-containing compound, silica, silicate, alumina, zirconia, a sulfur source, carbon powder, and an Ln-containing compound.
Preferably, when M is selected from one or more of Ca and Mg,
the selected Sr-containing compound is selected from one or more of Sr-containing carbonate, sr-containing sulfate, sr-containing oxalate, sr-containing acetate and Sr-containing hydroxide;
the compound containing A is selected from one or more of carbonate containing A, sulfide containing A, oxide containing A and hydroxide containing A;
the M-containing compound is selected from one or more of an M-containing oxide, an M-containing carbonate, an M-containing oxalate, an M-containing nitrate, an M-containing sulfate and an M-containing acetate;
the sulfur source is selected from one or more of sulfur powder, ammonium thiocyanate and thiourea;
the Ln compound is selected from one or more of Ln-containing carbonate, ln-containing oxide and Ln-containing sulfate.
Preferably, when M is selected from one or more of Cl and Br,
the selected Sr-containing compound is selected from one or more of Sr-containing carbonate, sr-containing sulfate, sr-containing oxalate, sr-containing acetate and Sr-containing hydroxide;
the compound containing A is selected from one or more of carbonate containing A, sulfide containing A, oxide containing A, hydroxide containing A and halide containing A;
the M-containing compound is selected from one or more of an M-containing oxide, an M-containing carbonate, an M-containing oxalate, an M-containing halide, an M-containing nitrate, an M-containing sulfate and an M-containing acetate;
the sulfur source is selected from one or more of sulfur powder, ammonium thiocyanate and thiourea;
the Ln compound is selected from one or more of Ln-containing carbonate, ln-containing oxide, ln-containing sulfate and Ln-containing halide;
at least one of the A-containing compound, the M-containing compound and the Ln compound is a halide.
Preferably, the mass ratio of the Sr-containing compound, the A-containing compound, the M-containing compound, the sulfur source and the Ln-containing compound in the first mixture is the metering ratio of each element in the compound shown in the formula I, namely (0.95-1): (0-0.1): (0-0.2): (2-3): (0.001-0.2).
Preferably, the second mixture has a mass ratio of (0-0.1): 0-0.2): 2-3): 0.001-0.2 of the a-containing compound, the M-containing compound, the sulfur source and the Ln-containing compound.
Preferably, the mass ratio of the second mixture to the first mixture is preferably 0.2 to 5:1, more preferably 0.5 to 4:1.
The present invention preferably sinters the first mixture and the second mixture in a crucible. Part of the second mixture can be put into the bottom of the crucible for tiling, the first mixture is covered on the upper part of the second mixture, and finally the rest of the second mixture is covered on the upper part of the first mixture for sintering. According to the invention, the second mixture is used as a wrapping raw material, and a wrapping layer is formed during sintering, so that the saturated vapor pressure of the first mixture can be increased, the ion diffusion speed can be accelerated, and the first mixture can be prevented from melting or sublimating during sintering.
Preferably, the sintering temperature is 600-1500 ℃, more preferably 900-1300 ℃; the sintering time is 1 to 20 hours, more preferably 2 to 4 hours; the sintering atmosphere is an air atmosphere.
After sintering is completed, the obtained sintered product is removed from the coating. Because the cooled coating layer has loose texture, the coating layer is easy to peel off, and the upper and lower coating layers can be removed by pinching the upper and lower coating layers by hands. And grinding the sintered product with the coating removed to obtain the multi-element rare earth sulfide luminescent material.
The luminescent material can be excited by ultraviolet and visible light to emit adjustable spectrum, and can be used in the fields of LED illumination and display.
The invention has the beneficial effects that:
the invention provides a multi-element rare earth sulfide luminescent material, the chemical expression of which is shown as formula I: a is that a Sr 1-1/ 2a S is bLn, cM formula I; wherein A is selected from one or more of Li, na and K, ln is selected from one or more of Ce, eu and Dy, M is selected from one or more of Ca, mg, cl, br, a, b and c are A, ln and M is correspondingly doped as doping ionsThe mole percentage of hetero ions relative to the S atom. The luminescent material can be excited by ultraviolet and visible light to emit adjustable spectrum, and can be used in the fields of LED illumination and display.
The invention also provides a preparation method of the multi-element rare earth sulfide luminescent material, which is a high-temperature solid-phase synthesis method, and has the advantages of simple process, low raw material cost and easy realization of industrialization.
Drawings
FIG. 1 is Na 0.24 Sr 0.88 XRD data for S0.005 Ce,0.01 Mn.
FIG. 2 is Na 0.28 Sr 0.86 S is 0.01Ce excitation spectrum and emission spectrum.
FIG. 3 is Li 0.6 Sr 0.7 S is 0.01Eu, and excitation spectrum and emission spectrum of 0.001Ca.
FIG. 4 is sample Na 0.28 Sr 0.86 S0.01 Ce and Li 0.6 Sr 0.7 S is 0.01Eu and 0.001Ca is packaged into the fluorescence spectrum of the LED.
FIG. 5 shows excitation spectra and emission spectra of SrS:0.01Eu,0.01Ce, and 0.01 Ca.
FIG. 6 is K 0.16 Sr 0.92 S is 0.02Cu and 0.01 Al.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
Example 1
According to chemical formula Na 0.24 Sr 0.88 S, 0.005Ce and 0.01Mn, accurately weighing sodium carbonate, strontium oxide, cerium oxide and manganese oxide, mixing completely, and adding Al 2 O 3 Sulfur powder and carbon particles are used as coating layers. The Al mentioned above 2 O 3 The mass ratio of the sulfur powder to the carbon particles is 0.01:1:0.5, and the carbon isThe mass ratio of the mixture of sodium acid, strontium oxide, cerium oxide and manganese oxide to the coating layer is 1:1. Sintering for 2 hours in air at 1300 ℃, cooling to room temperature, taking out, removing the wrapping layer, and fully grinding the sintering product with the wrapping layer removed to obtain the rare earth sulfide luminescent material. The invention uses Empyrean X-ray powder diffractometer to test the phase structure of the obtained rare earth sulfide luminescent material, and the test result is shown in figure 1. Fig. 1 is an X-ray diffraction pattern of the visible light emitting material prepared in example 1 of the present invention. As can be seen from fig. 1, the main phase of the luminescent material prepared in example 1 of the present invention is SrS.
Example 2
According to chemical formula Na 0.28 Sr 0.86 S, accurately weighing the proportion of the substances of each element in 0.01Ce, fully and uniformly mixing sodium carbonate, strontium carbonate and cerium carbonate, and using ZrO 2 The ZrO, sulfur powder and carbon particles are used as coating layers 2 The mass ratio of the sulfur powder to the carbon particles is 0.01:1:0.4, and the mass ratio of the mixture of sodium carbonate, strontium carbonate and cerium carbonate to the coating layer is 1:0.5. Sintering for 2 hours in air at 900 ℃, cooling to room temperature, taking out, removing the wrapping layer, and fully grinding the sintering product with the wrapping layer removed to obtain the rare earth sulfide luminescent material.
The invention tests the phase structure of the obtained rare earth sulfide luminescent material by using an Empyrean type X-ray powder diffractometer, and the X-ray diffraction diagram is similar to that of figure 1, so that the main phase of the luminescent material prepared in the embodiment 2 of the invention is SrS.
The present invention uses Edinburgh FLS980 to perform fluorescence spectrum test on the obtained rare earth sulfide luminescent material, as shown in FIG. 2. When the ultraviolet light with the wavelength of 276nm is adopted for excitation, the wavelength of the maximum emission intensity of the rare earth sulfide luminescent material is positioned near 495 nm; with 536nm green emission, the intensities of the maximum excitation intensities of the rare earth sulfide luminescent materials were located near 275nm and 430nm, respectively.
Example 3
According to chemical formula Li 0.6 Sr 0.7 S, 0.01Eu and 0.001Ca, accurately weighing lithium hydroxideMixing strontium sulfate, europium oxide and calcium oxide completely, and mixing with SiO 2 The SiO is coated with sulfur powder and carbon particles 2 The mass ratio of the sulfur powder to the carbon particles is 0.02:1:0.5, and the mass ratio of the mixture of lithium hydroxide, strontium sulfate, europium oxide and calcium oxide to the coating layer is 1:2. Sintering for 2 hours in air at 1050 ℃, cooling to room temperature, taking out, removing the wrapping layer, and fully grinding the sintering product with the wrapping layer removed to obtain the rare earth sulfide luminescent material.
The invention tests the phase structure of the obtained rare earth sulfide luminescent material by using an Empyrean type X-ray powder diffractometer, and the X-ray diffraction diagram is similar to that of figure 1, so that the main phase of the luminescent material prepared in the embodiment 3 of the invention is SrS.
The present invention uses Edinburgh FLS980 to perform fluorescence spectrum test on the obtained rare earth sulfide luminescent material, as shown in FIG. 3. When the invention is excited by blue light with the wavelength of 430nm, the wavelength of the maximum emission intensity of the rare earth sulfide luminescent material is near 620nm, and the half-peak width reaches 78nm; with 617nm red emission, the intensities of the maximum excitation intensities of the rare earth sulfide luminescent materials are located near 275nm and 430nm, respectively.
The present invention uses remote HAAS-2000 to test chromaticity and luminosity index of LED devices on the resulting rare earth sulfide luminescent material, as shown in fig. 4. The invention adopts organic silica gel: na (Na) 0.28 Sr 0.86 S:0.01Ce:Li 0.6 Sr 0.7 S0.01 Eu, 0.001Ca=10:1:2, and was coated on a 430nm blue chip, cured at 100℃for 1 hour, and tested. In FIG. 4, peak positions around 430nm are assigned to blue chips; peak positions around 490-550 nm are attributed to Na 0.28 Sr 0.86 S is 0.01Ce; peak position around 640nm is attributed to Li 0.6 Sr 0.7 S:0.01Eu,0.001Ca。
Example 4
Accurately weighing strontium carbonate, europium oxide, cerium carbonate and calcium hydroxide according to the mass proportion of each element in the chemical formulas SrS of 0.01Eu,0.01Ce and 0.01Ca, fully and uniformly mixing, and then adding CaSiO 3 The coating layer is composed of sulfur powder and carbon particles, and the CaSiO 3 The mass ratio of the sulfur powder to the carbon particles is 0.015:1:0.6, and the mass ratio of the mixture of strontium carbonate, europium oxide, cerium carbonate and calcium hydroxide to the coating layer is 1:3. Sintering for 2 hours in air at 1000 ℃, cooling to room temperature, taking out, removing the wrapping layer, and fully grinding the sintering product with the wrapping layer removed to obtain the rare earth sulfide luminescent material.
The invention tests the phase structure of the obtained rare earth sulfide luminescent material by using an Empyrean type X-ray powder diffractometer, and the X-ray diffraction diagram is similar to that of figure 1, so that the main phase of the luminescent material prepared in the embodiment 4 of the invention is SrS.
The present invention uses Edinburgh FLS980 to perform fluorescence spectrum test on the obtained rare earth sulfide luminescent material, as shown in FIG. 5. When the invention adopts blue light excitation of 430nm, the wavelength of the maximum emission intensity of the rare earth sulfide luminescent material is positioned near 480nm and 620 nm; with 617nm red emission, the intensities of the maximum excitation intensities of the rare earth sulfide luminescent materials are located near 275nm and 430nm, respectively.
Comparative example 1
According to chemical formula Na 0.44 Sr 0.78 S, 0.01Cr and 0.002Ca, accurately weighing sodium hydroxide, strontium carbonate, chromium sulfate and calcium sulfate, mixing completely, and adding ZrO 2 The ZrO is prepared by taking sulfur powder and carbon particles as coating layers 2 The mass ratio of the sulfur powder to the carbon particles is 0.02:1:0.45, and the mass ratio of the mixture of sodium hydroxide, strontium carbonate, chromium sulfate and calcium sulfate to the coating layer is 1:1.5. Sintering for 2 hours in air at 1300 ℃, cooling to room temperature, taking out, removing the wrapping layer, and fully grinding the sintering product with the wrapping layer removed to obtain the rare earth sulfide luminescent material.
The invention tests the phase structure of the obtained rare earth sulfide luminescent material by using an Empyrean type X-ray powder diffractometer, and the X-ray diffraction diagram is similar to that of figure 1, so that the main phase of the luminescent material prepared in comparative example 1 is SrS.
Comparative example 2
According to the proportion of the amounts of substances of each element in the chemical formulas SrS, 0.015Cu and 0.05CaWeighing strontium sulfate, copper oxide and calcium hydroxide, mixing completely, mixing with Al 2 O 3 The Al is coated with sulfur powder and carbon particles 2 O 3 The mass ratio of the sulfur powder to the carbon particles is 0.005:1:0.4, and the mass ratio of the mixture of strontium sulfate, copper oxide and calcium hydroxide to the coating layer is 1:2. Sintering for 2 hours in air at 1200 ℃, cooling to room temperature, taking out, removing the wrapping layer, and fully grinding the sintering product with the wrapping layer removed to obtain the rare earth sulfide luminescent material.
The invention tests the phase structure of the obtained rare earth sulfide luminescent material by using an Empyrean type X-ray powder diffractometer, and the X-ray diffraction diagram is similar to that of figure 1, so that the main phase of the luminescent material prepared in comparative example 2 of the invention is SrS.
Comparative example 3
According to chemical formula K 0.16 Sr 0.92 S is 0.02Cu and 0.01Al, accurately weighing the mass ratio of the elements in the potassium carbonate, the strontium oxide, the copper sulfate and the aluminum oxide, fully and uniformly mixing, taking sulfur powder and carbon particles as coating layers, wherein the mass ratio of the sulfur powder to the carbon particles is 1:0.45, and the mass ratio of the mixture of the potassium carbonate, the strontium oxide, the copper sulfate and the aluminum oxide to the coating layers is 1:3. Sintering for 2 hours in air at 1000 ℃, cooling to room temperature, taking out, removing the wrapping layer, and fully grinding the sintering product with the wrapping layer removed to obtain the rare earth sulfide luminescent material.
The invention tests the phase structure of the obtained rare earth sulfide luminescent material by using an Empyrean type X-ray powder diffractometer, and the X-ray diffraction diagram is similar to that of figure 1, so that the main phase of the luminescent material prepared in comparative example 3 of the invention is SrS.
The invention uses JSM-7900F field emission scanning electron microscope to test morphology image of the obtained rare earth sulfide luminescent material, as shown in figure 6. Fig. 6 is a morphology image of the sulfide light emitting material prepared in comparative example 3 of the present invention, and it can be seen from fig. 6 that the powder prepared in comparative example 3 of the present invention has an irregular shape and a particle size of 5 to 30 μm.
Comparative example 4
According to chemical formula K 0.4 Sr 0.8 S 0.8 The proportion of the mass of each element in 0.4Cl and 0.1Mn is accurately weighed, fully and evenly mixed with potassium chloride, strontium carbonate and manganese oxide, and then is prepared by SiO 2 The SiO is coated with sulfur powder and carbon particles 2 The mass ratio of the sulfur powder to the carbon particles is 0.02:1:0.6, and the mass ratio of the mixture of the potassium chloride, the strontium carbonate and the manganese oxide to the coating layer is 1:1. Sintering for 2 hours in air at 1500 ℃, cooling to room temperature, taking out, removing the wrapping layer, and fully grinding the sintering product with the wrapping layer removed to obtain the rare earth sulfide luminescent material.
According to the invention, the obtained rare earth sulfide luminescent material is subjected to phase structure test by using an Empyrean type X-ray powder diffractometer, the X-ray diffraction diagram of the rare earth sulfide luminescent material is similar to that of FIG. 1, and the main phase of the luminescent material prepared in the embodiment 8 of the invention is SrS.
The multi-element rare earth sulfide luminescent material provided by the invention has higher luminous intensity and luminous efficiency. When excited by ultraviolet light and visible light with different wavelengths, the material doped with different rare earth ions has different wavelengths of maximum emission intensity. Taking europium ion as an example, the wavelength of the maximum emission intensity of the material is located near 620nm, and the half-peak width reaches 78nm. Most red phosphors, such as manganese-based materials, have a half-width of no more than 10nm. The red fluorescent powder plays roles in adjusting color temperature, improving color rendering property and color saturation in the white light LED device, and can realize wide-color-gamut illumination and display.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (3)
1. A method for preparing a multi-element rare earth sulfide luminescent material, which is characterized by comprising the following steps:
(1) Mixing a Sr-containing compound, an A-containing compound, an M-containing compound, a sulfur source and an Ln-containing compound to obtain a first mixture;
(2) Wrapping the first mixture with a second mixture, sintering, and removing a wrapping layer to obtain the multi-element rare earth sulfide luminescent material;
the second mixture comprises one or more of a compound containing a, silica, silicate, alumina, zirconia, a sulfur source, carbon powder and a compound containing Ln;
when M is selected from one or more of Ca and Mg,
the selected Sr-containing compound is selected from one or more of Sr-containing carbonate, sr-containing sulfate, sr-containing oxalate, sr-containing acetate and Sr-containing hydroxide;
the compound containing A is selected from one or more of carbonate containing A, sulfide containing A, oxide containing A and hydroxide containing A;
the M-containing compound is selected from one or more of an M-containing oxide, an M-containing carbonate, an M-containing oxalate, an M-containing nitrate, an M-containing sulfate and an M-containing acetate;
the sulfur source is selected from one or more of sulfur powder, ammonium thiocyanate and thiourea;
the Ln compound is selected from one or more of Ln-containing carbonate, ln-containing oxide and Ln-containing sulfate;
when M is selected from one or more of Cl and Br,
the selected Sr-containing compound is selected from one or more of Sr-containing carbonate, sr-containing sulfate, sr-containing oxalate, sr-containing acetate and Sr-containing hydroxide;
the compound containing A is selected from one or more of carbonate containing A, sulfide containing A, oxide containing A, hydroxide containing A and halide containing A;
the M-containing compound is selected from one or more of an M-containing oxide, an M-containing carbonate, an M-containing oxalate, an M-containing halide, an M-containing nitrate, an M-containing sulfate and an M-containing acetate;
the sulfur source is selected from one or more of sulfur powder, ammonium thiocyanate and thiourea;
the Ln compound is selected from one or more of Ln-containing carbonate, ln-containing oxide, ln-containing sulfate and Ln-containing halide;
at least one of the A-containing compound, the M-containing compound and the Ln compound is a halide;
the mass ratio of the Sr-containing compound to the A-containing compound to the M-containing compound to the sulfur source to the Ln-containing compound in the first mixture is (0.95-1): 0-0.1): 0-0.2): 2-3): 0.001-0.2;
the mass ratio of the second mixture to the first mixture is 0.2-5:1;
the chemical expression of the multi-element rare earth sulfide luminescent material is shown as a formula I:
A a Sr 1-1/2a s is bLn, cM formula I;
wherein, A is selected from one or more of Li, na and K, ln is selected from one or more of Ce, eu and Dy, and M is selected from one or more of Ca, mg, cl, br;
a=0~0.1，b=0.001~0.2，c=0~0.2。
2. the method for preparing a multi-element rare earth sulfide luminescent material according to claim 1, wherein the mass ratio of the second mixture to the first mixture is 0.5-4:1.
3. The method for preparing a multi-element rare earth sulfide light emitting material according to claim 1, wherein a=0 to 0.035, b=0.0005 to 0.04, and c=0 to 0.035.
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