CN115322781A - Novel white luminescent material and preparation method thereof - Google Patents
Novel white luminescent material and preparation method thereof Download PDFInfo
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- 229910001631 strontium chloride Inorganic materials 0.000 description 1
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- 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
- C09K11/7709—Phosphates
- C09K11/771—Phosphates with alkaline earth metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention provides a novel white luminescent material and a preparation method thereof, and the novel white luminescent material comprises CaSr 2 (PO 4 ) 2 The white luminescent material has the advantages of pure phase, high luminescent purity, high intensity and the like, and is an environment-friendly inorganic luminescent material. Meanwhile, the white luminescent material has the advantages of simple preparation process, high repeatability, green and environment-friendly preparation process, large-scale production and good application prospect, and can be used as fluorescent powder for white LEDs.
Description
Technical Field
The invention belongs to the technical field of inorganic luminescent materials, and particularly relates to Dy 3+ ,Li + Codoped CaSr 2 (PO 4 ) 2 The novel white luminescent material and the preparation method thereof.
Background
In recent years, as an energy-saving energy source widely used in society, white light emitting diodes (w-LEDs) have advantages of high energy conversion efficiency, small size, low starting voltage, long durability, good color rendering, and the like, and are called as fourth generation lighting sources. At present, the most mature white light LED implementation method is a phosphor conversion method, and the phosphor, as an important component of the white light LED, directly affects the development and application of the white light LED, and thus is receiving attention of researchers in various countries.
Some researchers believe that combining near ultraviolet LED chips with red, green, and blue phosphors can result in a white LED. However, red and green phosphors can reabsorb blue emission light, resulting in low blue emission efficiency, and the mixing of multiple phosphors often results in color imbalance and instability at high temperature, and the white LED has a low color rendering index, effectively limiting their applications. Therefore, one of the main problems in the research and development of the fluorescent powder for the white light LED is the lack of the single-phase fluorescent powder which emits white light under the excitation of near ultraviolet light and has high efficiency, no pollution, stable performance, environmental protection.
Disclosure of Invention
Based on the above technical background, the present inventors have made a keen search and, as a result, have found that: with CaSr 2 (PO 4 ) 2 As a matrix, trivalent lanthanide ions are used as an activator and calcined at a specific temperature to prepare the white luminescent material, and the white luminescent material has the advantages of pure phase, high luminescent purity, high intensity and the like. On the basis, the charge balancing agent is added, so that the luminous performance of the white luminous material can be further improved, and the stability of the white luminous material is greatly improved. The preparation process of the material is simple, the repeatability is high, the preparation process is green and environment-friendly, and industrial production can be carried out.
The first aspect of the present invention is to provide a novel white luminescent material comprising CaSr 2 (PO 4 ) 2 The activator is selected from one or more of trivalent lanthanide ions.
In a second aspect, the present invention provides a method for preparing the novel white light emitting material according to the first aspect, wherein the method comprises the following steps:
step 1, mixing and grinding raw materials including a calcium source, a strontium source, a phosphate and a compound containing M element;
and 3, grinding the materials after the heat treatment to obtain the novel white luminescent material.
In a third aspect, the present invention provides a use of the novel white luminescent material according to the first aspect or the novel white luminescent material prepared by the preparation method according to the second aspect, which can be used as a fluorescent powder in a white LED.
The novel white luminescent material and the preparation method thereof provided by the invention have the following advantages:
(1) The white luminescent material emits white light, has the advantages of high luminescent purity, high intensity and stable performance, and is an environment-friendly inorganic luminescent material;
(2) The preparation method of the white luminescent material is simple and efficient, has low preparation cost, has no pollution emission in the preparation process, is green and environment-friendly, and can be applied to large-scale production.
Drawings
FIG. 1 shows XRD patterns of white luminescent materials obtained in examples 1 to 8 of the present invention;
FIG. 2 shows XRD spectra of white luminescent materials obtained in examples 9 to 16 of the present invention;
FIG. 3 is a PL spectrum of a white light-emitting material obtained in examples 1 to 8 of the present invention;
FIG. 4 shows a CIE diagram of a white light emitting material obtained in example 3 of the present invention.
Detailed Description
The present invention will be described in detail below, and features and advantages of the present invention will become more apparent and apparent with reference to the following description.
The first aspect of the present invention is to provide a novel white luminescent material comprising CaSr 2 (PO 4 ) 2 The activator is selected from one or more of trivalent lanthanide ions.
CaSr 2 (PO 4 ) 2 Belongs to dolomite and has excellent luminescenceCan be used as a host material for a light-emitting material.
Preferably, the activator is selected from Eu 3+ 、Sm 3+ 、Dy 3+ More preferably, the activator is Dy 3+ 。
The transition of lanthanide between 5d → 4f and 4f → 4f produces tunable polychromatic luminescence in the uv-vis-nir spectrum with the advantages of long radiative lifetimes and narrow absorption and emission bands, and thus, the lanthanide has important applications in the display and lighting fields. Under the excitation of near ultraviolet light, dy 3+ Respectively, consists of blue (470-500 nm) and yellow (560-600 nm) emission bands, the blue region corresponding to 4 F 9/2 - 6 H 13/2 Electronic transition of energy level, yellow region corresponding to 4 F 9/2 - 6 H 15/2 The electronic transition of energy level can reach the emission close to white light by adjusting the ratio of the yellow to blue light emission intensity.
In order to obtain a fluorescent material emitting white light, caSr is used 2 (PO 4 ) 2 On the basis of the host material, the inventors doped trivalent lanthanide, and found that trivalent lanthanide is used as the luminescence center, and CaSr is used 2 (PO 4 ) 2 The luminescent material prepared from the host material has the advantage of high luminescent purity, and is radiation-resistant, nontoxic and pollution-free to the environment.
The chemical formula of the white luminescent material is CaSr 2-1.5x (PO 4 ) 2 :xM 3+ Wherein, M is 3+ Represents a luminescence center (activator), and x is 0.001 to 0.4, preferably 0.005 to 0.3, and more preferably 0.01 to 0.2.
However, it has been found that when the divalent strontium ion is substituted by trivalent lanthanide, the valence charge is not balanced, resulting in poor performance stability of the luminescent material and reduced luminescence intensity.
According to a preferred embodiment of the present invention, the light-emitting material further includes a charge balance agent. The charge balancing agent is one or more selected from monovalent metal ions, preferably selected from Li + 、Na + And K + More preferably Li + 。
Tests show that the charge balancing agent is added to avoid charge imbalance and vacancy formation in the prepared luminescent material, and the luminescent material obtained by regulating the addition of the charge balancing agent has excellent luminescent performance and better luminescent stability. In particular, monovalent metal ions are added as a charge balancing agent, so that the crystal structure of the prepared material is more stable.
According to a preferred embodiment of the present invention, after adding the charge balancing agent, the chemical formula of the novel white luminescent material is: caSr 2-2x (PO 4 ) 2 :xM 3+ ,xA + Wherein M is 3+ Denotes a luminescence center (activator), A + Represents a charge balancing agent.
In the above formula, x is 0.001 to 0.5, preferably 0.005 to 0.4, and more preferably 0.01 to 0.3.
The addition amount of the charge balance agent and the activator affects the luminous intensity of the prepared white luminous material, the luminous intensity of the luminous material is gradually increased along with the increase of the charge balance agent and the activator, but if the addition amount is too large, the luminous intensity is rather reduced, and tests show that the prepared white luminous material has more excellent luminous intensity when x is in the range.
The novel white luminescent material emits blue light with main peaks positioned at 486nm and yellow light with main peaks positioned at 578nm under the excitation of 351nm ultraviolet light, displays white light after the colors are overlapped, and can be applied to white light LEDs.
In the present invention, as the novel white light emitting material of the present invention is prepared, it is prepared by a method comprising the steps of:
step 1, mixing and grinding raw materials including a calcium source, a strontium source, phosphate and a compound containing M element;
and 3, grinding the heat-treated materials to obtain the novel white luminescent material.
A second aspect of the present invention is to provide a method for preparing the novel white light emitting material according to the first aspect of the present invention, the method comprising the steps of:
step 1, mixing and grinding raw materials including a calcium source, a strontium source, phosphate and a compound containing M element;
and 3, grinding the materials after the heat treatment to obtain the novel white luminescent material.
This step is specifically described and illustrated below.
Step 1, mixing and grinding raw materials including a calcium source, a strontium source, phosphate and a compound containing M element.
The grinding is preferably carried out by dispersing the raw materials in a dispersing agent and then mixing and grinding, and the dispersing agent is preferably absolute ethyl alcohol.
The particle size of the ground raw material is 15 to 80 μm, preferably 15 to 50 μm, and more preferably 15 μm. The more uniformly the raw materials with the particle size of 15 μm after grinding are mixed, the more uniformly the raw materials are mixed, the more favorable the solid phase reaction is.
The calcium source is selected from one or more of oxides, hydroxides, carbonates and nitrates of calcium-containing elements, preferably one or two of calcium oxide and carbonates of calcium-containing elements, and more preferably calcium carbonate.
The strontium source is selected from one or more of strontium oxide, strontium carbonate, strontium sulfate, strontium chloride and strontium acetate, preferably selected from one or more of strontium oxide, strontium carbonate and strontium acetate, and more preferably selected from strontium carbonate.
The phosphate is selected from one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate and sodium phosphate, preferably selected from one or two of diammonium hydrogen phosphate and ammonium dihydrogen phosphate, and more preferably diammonium hydrogen phosphate. By adopting diammonium hydrogen phosphate as a reaction raw material, the introduction of impurity elements can be avoided, the impurity removal process is omitted, and the preparation process is simplified.
The molar ratio of calcium element in the calcium source, strontium element in the strontium source and phosphorus element in the phosphate is 1: (1-3): (0.5 to 4), preferably in a molar ratio of 1: (1.2-2): (1 to 3), more preferably 1: (1.4-2) 2.
The M-containing compound is selected from trivalent lanthanide ion-containing compounds, preferably Dy-containing compounds 3+ More preferably one or more selected from fluoride, chloride and oxide, and more preferably Dy-containing compounds 3+ An oxide of (a).
The compound containing M element is added in the process of preparing the white luminescent material, so that the prepared luminescent material can emit white light and has the advantage of high luminescent purity.
The molar ratio of the M element in the M element-containing compound to the calcium element in the calcium source is (0.001-0.5): 1, preferably (0.005-0.4): 1, more preferably (0.01-0.3): 1.
the present inventors have found that the emission intensity of the white light emitting material is related to the amount of the compound containing the element M, and that the white light emitting material obtained by using the above amount has a high emission intensity.
In the invention, the raw material also comprises an A element-containing compound, wherein the A element-containing compound is selected from one or more of an A element-containing oxide, a hydroxide and an inorganic acid salt, preferably from one or more of an A element-containing oxide, a carbonate and a sulfate, and more preferably is an A element-containing carbonate.
The A element is one or more selected from monovalent metal ions, preferably Li + 、Na + And K + More preferably Li + 。
The molar ratio of the element A in the element A-containing compound to the element calcium in the calcium source is (0.001-0.5): 1, preferably (0.005-0.4): 1, more preferably (0.01-0.3): 1.
the compound containing the element A is added in the preparation process, so that the charge imbalance phenomenon after doping with trivalent lanthanide ions can be balanced, the generation of vacancies is avoided, and the prepared luminescent material has higher luminous intensity and better luminous stability.
And 2, carrying out heat treatment on the mixed materials.
According to the present invention, the heat treatment includes pre-firing and high-temperature calcination. The pre-sintering is carried out to remove moisture and gas in the raw materials, so that the high-temperature calcination in the later period is more facilitated, and the performance of the luminescent material can be further improved.
The pre-sintering is preferably carried out in a muffle furnace, more preferably in an air atmosphere, and the pre-sintering temperature is 600 to 1000 ℃, preferably 700 to 900 ℃, more preferably 800 ℃.
The pre-sintering time is 30 to 90min, preferably 45 to 75min, and more preferably 60min. The presintering temperature and the presintering time can influence the presintering effect, and further influence the performance of the finally prepared white luminescent material. For the raw materials in the invention, the presintering temperature is lower than 600 ℃, the presintering time is lower than 30min, moisture and gas in the raw materials are not completely removed, and the luminescence performance of the prepared white luminescent material is reduced.
After the pre-sintering, the mixture is naturally cooled to room temperature, then grinding is carried out, the materials are uniformly ground, and the particle size of the ground materials is 20-100 μm, preferably 20-50 μm, and more preferably 20 μm. Grinding is carried out after pre-burning, so that the particle size of the materials can be further reduced, and the materials are mixed more uniformly.
The high-temperature calcination is preferably performed in a tube furnace, and more preferably in an air atmosphere.
The high-temperature calcination temperature is 1000 to 1350 ℃, preferably 1200 to 1300 ℃, and more preferably 1250 ℃.
The high-temperature calcination time is 3 to 8 hours, preferably 4 to 7 hours, and more preferably 5 hours.
The luminescent property of the luminescent material is related to the purity of the substrate as well as the doped trivalent lanthanide ions and the charge balancing agent, and the pure-phase substrate material can provide a proper crystal field environment for the trivalent lanthanide ions to cause the trivalent lanthanide ions to generate matched energy level splitting, so that the electron transition in the lanthanide ions emits light with characteristic color. The purity of the matrix is related to the high-temperature calcination temperature and the calcination time, and the inventor finds that if the calcination temperature is too low and the calcination time is too short, a pure phase cannot be obtained, and if the temperature is higher, the phase of the prepared up-conversion luminescent material is very pure, the crystallinity is better, and at 1250 ℃, the phase purity is high, the luminescence performance is good, and if the calcination temperature is too high, for example, a sample prepared at 1350 ℃ is sintered with a crucible, which is not favorable for obtaining a product.
And 3, grinding the materials after the heat treatment to obtain the novel white luminescent material.
And (3) cooling the heat-treated material to room temperature, grinding the material again, and grinding to obtain the novel white luminescent material.
The particle size of the novel white light emitting material is 25 to 120 μm, preferably 25 to 60 μm, and more preferably 25 μm. The larger particle size is not beneficial to light absorption and emission of a luminescence center, and the dispersion is difficult to be uniform and stable in the preparation process, so that the up-conversion luminescence intensity is reduced, therefore, the inventor selects a luminescent material with the smaller particle size, and the fluorescent powder has larger luminescence intensity.
The novel white luminescent material prepared by the invention emits blue light with main peak at 486nm and yellow light with main peak at 578nm under the excitation of 351nm ultraviolet light, displays white light after color superposition, has the advantages of high purity of emitted light, high intensity, stable performance and the like, is an environment-friendly inorganic luminescent material, and can be applied to white light LEDs.
The third aspect of the present invention provides a use of the novel white luminescent material according to the first aspect of the present invention or the novel white luminescent material prepared by the preparation method according to the second aspect of the present invention, which can be used as a fluorescent powder in a white LED.
The invention has the following beneficial effects:
(1) The invention adopts a high-temperature solid phase method, has simple preparation process, can realize large-scale production and has good market application prospect;
(2) The novel white luminescent material of the invention uses CaSr 2 (PO 4 ) 2 The material is a substrate, trivalent lanthanide ions are taken as a luminescence center, monovalent metal ions are taken as a charge balancing agent, blue light with the main peak positioned at 486nm and yellow light with the main peak positioned at 578nm can be emitted under the excitation of 351nm ultraviolet light, white light is displayed after color superposition, and the material has good physical and chemical stability and stable performance, is an environment-friendly inorganic luminescent material, and can be applied to a white light LED;
(3) The raw materials for preparing the novel white luminescent material are abundant in natural world, low in price and production cost, and the prepared sample is pure in phase;
(4) The preparation method of the novel white luminescent material has the advantages of high production efficiency, good repeatability and the like, and no pollutant is discharged in the preparation process.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting to the scope of the invention.
Example 1
According to CaSr 2-2x (PO 4 ) 2 :xDy 3+ ,xLi + (x = 0.01) stoichiometric ratio of each element in the chemical formula, and weighing CaCO 3 、SrCO 3 、(NH 4 ) 2 HPO 4 、Dy 2 O 3 And Li 2 CO 3 Placing the raw materials in a mortar, grinding with anhydrous ethanol as dispersant to obtain a raw material with an average particle diameter of 15 μm, placing the raw material into a muffle furnace, pre-sintering at 800 deg.C for 1 hr in air atmosphere, and removing water and gas from the raw material. After pre-sintering, naturally cooling to room temperature, grinding uniformly again until the particle size is 20 μm, then transferring into a tube furnace, calcining at 1250 ℃ for 5h in air atmosphere, cooling to room temperature in the tube furnace, and grinding again to obtain CaSr 1.98 (PO 4 ) 2 :0.01Dy 3+ ,0.01Li + The average particle size was 25 μm.
Example 2
A white light emitting material was prepared in a similar manner to example 1 except that: according to CaSr 2-2x (PO 4 ) 2 :xDy 3+ ,xLi + (x = 0.03) stoichiometric ratio of each element in the chemical formula, and weighing CaCO 3 、SrCO 3 、(NH 4 ) 2 HPO 4 、Dy 2 O 3 And Li 2 CO 3 And the like.
Example 3
A white light emitting material was prepared in a similar manner to example 1 except that: according to CaSr 2-2x (PO 4 ) 2 :xDy 3+ ,xLi + (x = 0.06) stoichiometric ratio of each element in the chemical formula, weighing CaCO 3 、SrCO 3 、(NH 4 ) 2 HPO 4 、Dy 2 O 3 And Li 2 CO 3 And the like.
Example 4
A white light emitting material was prepared in a similar manner to example 1 except that: according to CaSr 2-2x (PO 4 ) 2 :xDy 3+ ,xLi + (x = 0.12) stoichiometric ratio of each element in the chemical formula, and weighing CaCO 3 、SrCO 3 、(NH 4 ) 2 HPO 4 、Dy 2 O 3 And Li 2 CO 3 And the like.
Example 5
A white light emitting material was prepared in a similar manner to example 1 except that: according to CaSr 2-2x (PO 4 ) 2 :xDy 3+ ,xLi + (x = 0.18) stoichiometric ratio of each element in the chemical formula, and weighing CaCO 3 、SrCO 3 、(NH 4 ) 2 HPO 4 、Dy 2 O 3 And Li 2 CO 3 And the like.
Example 6
A white light emitting material was prepared in a similar manner to example 1 except that: according to CaSr 2-2x (PO 4 ) 2 :xDy 3+ ,xLi + (x = 0.24) stoichiometric ratio of each element in the chemical formula, and weighing CaCO 3 、SrCO 3 、(NH 4 ) 2 HPO 4 、Dy 2 O 3 And Li 2 CO 3 And the like.
Example 7
A white light emitting material was prepared in a similar manner to example 1 except that: according to CaSr 2-2x (PO 4 ) 2 :xDy 3+ ,xLi + (x = 0.27) stoichiometric ratio of each element in the chemical formula, caCO was weighed 3 、SrCO 3 、(NH 4 ) 2 HPO 4 、Dy 2 O 3 And Li 2 CO 3 And the like.
Example 8
A white light emitting material was prepared in a similar manner to example 1 except that: according to CaSr 2-2x (PO 4 ) 2 :xDy 3+ ,xLi + (x = 0.3) stoichiometric ratio of each element in the chemical formula, and weighing CaCO 3 、SrCO 3 、(NH 4 ) 2 HPO 4 、Dy 2 O 3 And Li 2 CO 3 And the like.
Example 9
A white light emitting material was prepared in a similar manner to example 1 except that: doping only lanthanide ions Dy 3+ Without introduction of charge balancing agents, according to CaSr 2-1.5x (PO 4 ) 2 :xDy 3+ (x = 0.01) stoichiometric ratio of each element in the chemical formula, and weighing CaCO 3 、SrCO 3 、(NH 4 ) 2 HPO 4 And Dy 2 O 3 And the like.
Example 10
A white light emitting material was prepared in a similar manner to example 1 except that: doping only lanthanide ions Dy 3+ Without introduction of charge-balancing agents, according to CaSr 2-1.5x (PO 4 ) 2 :xDy 3+ (x = 0.03) stoichiometric ratio of each element in the chemical formula, and weighing CaCO 3 、SrCO 3 、(NH 4 ) 2 HPO 4 And Dy 2 O 3 And the like.
Example 11
A white light emitting material was prepared in a similar manner to example 1 except that: doping only lanthanide ions Dy 3+ Without introduction of charge balancing agents, according to CaSr 2-1.5x (PO 4 ) 2 :xDy 3+ (x = 0.05) stoichiometric ratio of each element in the chemical formula, weighing CaCO 3 、SrCO 3 、(NH 4 ) 2 HPO 4 And Dy 2 O 3 And the like.
Example 12
A white luminescent material, region, was prepared in a similar manner to example 1The difference is that: doping only lanthanide ions Dy 3+ Without introduction of charge balancing agents, according to CaSr 2-1.5x (PO 4 ) 2 :xDy 3+ (x = 0.07) stoichiometric ratio of each element in the chemical formula, and weighing CaCO 3 、SrCO 3 、(NH 4 ) 2 HPO 4 And Dy 2 O 3 And the like.
Example 13
A white light emitting material was prepared in a similar manner to example 1 except that: doping only lanthanide ions Dy 3+ Without introduction of charge-balancing agents, according to CaSr 2-1.5x (PO 4 ) 2 :xDy 3+ (x = 0.09) stoichiometric ratio of each element in the chemical formula, and weighing CaCO 3 、SrCO 3 、(NH 4 ) 2 HPO 4 And Dy 2 O 3 And the like.
Example 14
A white light emitting material was prepared in a similar manner to example 1 except that: doping only lanthanide ions Dy 3+ Without introduction of charge balancing agents, according to CaSr 2-1.5x (PO 4 ) 2 :xDy 3+ (x = 0.12) stoichiometric ratio of each element in the chemical formula, and weighing CaCO 3 、SrCO 3 、(NH 4 ) 2 HPO 4 And Dy 2 O 3 And the like.
Example 15
A white light emitting material was prepared in a similar manner to example 1 except that: doping only lanthanide ions Dy 3+ Without introduction of charge-balancing agents, according to CaSr 2-1.5x (PO 4 ) 2 :xDy 3+ (x = 0.15) stoichiometric ratio of each element in the chemical formula, and weighing CaCO 3 、SrCO 3 、(NH 4 ) 2 HPO 4 And Dy 2 O 3 And the like.
Example 16
A white light emitting material was prepared in a similar manner to example 1 except that: doping only lanthanide ions Dy 3+ Without introduction of charge-balancing agents, according to CaSr 2-1.5x (PO 4 ) 2 :xDy 3+ (x = 0.18) stoichiometric ratio of each element in the chemical formula, and weighing CaCO 3 、SrCO 3 、(NH 4 ) 2 HPO 4 And Dy 2 O 3 Raw materials.
Examples of the experiments
Experimental example 1XRD test
XRD tests were performed on the white luminescent materials obtained in examples 1 to 8 of the present invention, and the results are shown in FIG. 1, and XRD tests were performed on the white luminescent materials obtained in examples 9 to 16, and the results are shown in FIG. 2.
As can be seen from FIGS. 1 and 2, the diffraction spectra shown in FIGS. 1 and 2 are both very good for Ca belonging to trigonal system 3 (PO 4 ) 2 The standard patterns of (JCPDS Nos. 09-0169) are matched, and the space group is R3C (161). This shows that the white luminescent materials prepared by the invention are all single-phase crystals. The XRD spectrum shows that the diffraction peaks are all shifted by a small 2 theta angle, which is mainly 30344, bivalent calcium ions are replaced by bivalent cesium ions with larger ion radius, and Dy is obtained under different doping amounts 3+ And Li + Doped ion pair matrix CaSr 2 (PO 4 ) 2 The structure of (a) has no significant effect. The samples prepared by the invention are all pure phases.
Experimental example 2 measurement of luminescent Property of sample
PL spectra of the white light emitting materials obtained in examples 1 to 8 were measured under excitation at an excitation wavelength of 351nm, and the results are shown in FIG. 3.
As shown in FIG. 3, the obtained white light-emitting material showed emission intensities at 486nm and 578nm, and Dy 3+ /Li + The doping concentrations are related and all PL spectra show similar morphologies, with two typical Dy' s 3+ The emission peak, emission band position or shape is not significantly changed. It can also be seen from the figure that the white luminescent material of the present invention has the emission intensity of 486nm and 578nm and Dy 3+ In addition, the emission intensity at 578nm is stronger, and the emission intensities at 486 and 578nm follow Dy first 3+ The concentration of ions increases when Dy 3+ At a concentration of 0.06, the emission intensity reaches a maximum,Dy 3+ after the concentration of (2) exceeds 0.06, it follows Dy 3+ The content is further increased and decreased, which corresponds to a concentration quenching effect.
Experimental example 3CIE test
The chromaticity diagram and the international commission on illumination (CIE) coordinates are very important because they indicate the exact emission color and color purity of the sample, and the CIE test was performed on the white luminescent material prepared in example 3, and the test result is shown in fig. 4.
FIG. 4 shows CIE chromaticity coordinates and digital images of a white light emitting phosphor prepared in example 3 under excitation at an excitation wavelength of 351 nm. Calculated from fig. 4, the CIE chromaticity coordinates of the white light emitting material obtained in example 3 were (0.3450, 0.3787), which was located in the white region, which was consistent with the emission color of the phosphor observed under excitation at 351 nm. Therefore, the white light emitting material prepared in example 3 can be applied to w-LEDs as a white phosphor in solid state lighting applications.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A novel white luminescent material is characterized in that the white luminescent material comprises CaSr 2 (PO 4 ) 2 The activator is selected from one or more of trivalent lanthanide ions.
2. A novel white light-emitting material according to claim 1, wherein said light-emitting material further comprises a charge balancing agent selected from one or more monovalent metal ions.
3. The novel white light-emitting material according to claim 2,
the chemical formula of the novel white luminescent material is CaSr 2-2x (PO 4 ) 2 :xM 3+ ,xA + Wherein, M is 3+ Denotes an activator, A + Represents a charge balancing agent, and x is 0.001 to 0.5.
4. A novel white luminescent material as claimed in claim 1,
the white luminescent material emits blue light with main peaks at 486nm and yellow light with main peaks at 578nm under the excitation of 351nm ultraviolet light, and white light is displayed after colors are superposed.
5. A method for preparing a novel white luminescent material is characterized by comprising the following steps:
step 1, mixing and grinding raw materials including a calcium source, a strontium source, a phosphate and a compound containing M element;
step 2, carrying out heat treatment on the mixed materials;
and 3, grinding the heat-treated materials to obtain the novel white luminescent material.
6. The production method according to claim 5, wherein, in step 1,
the molar ratio of calcium element in the calcium source to strontium element in the strontium source to phosphorus element in the phosphate is 1: (1-3): (0.5 to 4);
the molar ratio of the M element in the M element-containing compound to the calcium element in the calcium source is (0.001-0.5): 1.
7. The production method according to claim 5, wherein, in step 1,
the raw material also comprises a compound containing an element A, wherein the element A is selected from one or more of monovalent metal ions;
the molar ratio of the element A in the element A-containing compound to the element calcium in the calcium source is (0.001-0.5): 1.
8. The method according to claim 5, wherein in step 2, the heat treatment comprises pre-firing and high-temperature calcination;
the presintering temperature is 600-1000 ℃, and the presintering time is 30-90 min.
9. The method according to claim 8, wherein the high-temperature calcination temperature in step 2 is 1000 to 1350 ℃ and the high-temperature calcination time is 3 to 8 hours.
10. Use of the novel white light emitting material according to one of claims 1 to 4 or the novel white light emitting material produced by the production method according to one of claims 5 to 9 as a phosphor for white light LEDs.
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Inventor after: Guo Qingfeng Inventor after: Shuai Pengfei Inventor after: Liao Libing Inventor after: Mei Lefu Inventor after: Zhang Yuanyuan Inventor before: Guo Qingfeng Inventor before: Shuai Pengfei Inventor before: Liao Libing Inventor before: Mei Lefu |
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Application publication date: 20221111 |