CN113621365B - Preparation method of europium-doped red silicate fluorescent material with high luminous intensity - Google Patents
Preparation method of europium-doped red silicate fluorescent material with high luminous intensity Download PDFInfo
- Publication number
- CN113621365B CN113621365B CN202111062792.1A CN202111062792A CN113621365B CN 113621365 B CN113621365 B CN 113621365B CN 202111062792 A CN202111062792 A CN 202111062792A CN 113621365 B CN113621365 B CN 113621365B
- Authority
- CN
- China
- Prior art keywords
- luminous intensity
- zno
- sio
- baco
- europium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77342—Silicates
-
- 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7734—Aluminates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
A preparation method of a europium-doped red silicate fluorescent material with high luminous intensity comprises the following steps: in BaCO 3 、ZnO、H 2 SiO 3 And Eu 2 O 3 As raw material powder, according to the molecular formula Ba 1‑ x Eu x ZnSiO 4 The stoichiometric ratio of the corresponding elements in the raw materials is that each raw material is weighed, wherein x is Eu 3+ Doped Ba 2+ The molar ratio of the position is more than or equal to 0.005 and less than or equal to 0.10; mixing the above raw materials with TiO 2 Fully grinding and uniformly mixing the mixture in a mortar to obtain mixed powder; placing the mixed powder into a crucible, presintering for 2-5 hours at 700-900 ℃, cooling, fully grinding again, and tabletting the sample; sintering the pressed product at 1000-1150 deg.c for 2-4 hr, and cooling to room temperature to obtain the fluorescent material. The method is simple, the raw materials are cheap, and the prepared material has the advantages of high color rendering index and high luminous intensity.
Description
Technical Field
The invention relates to the technical field of fluorescent powder materials, in particular to a preparation method of a europium-doped red silicate fluorescent material with high luminous intensity.
Background
In recent years, light emitting diodes (W-LEDs) have been attracting attention as a next-generation solid-state light source because of their advantages of energy saving, high luminous efficiency, good stability, no toxicity, and the like. Commercial W-LEDs are made of blue InGaN-based LEDs and yellow light emitting Y 3 Al 5 O 12 :Ce 3+ (YAG:Ce 3+ ) Fluorescent powder. Due to insufficient red light emission in the visible spectrum, such white LEDs have low Color Rendering Index (CRI) and high Correlated Color Temperature (CCT). Since white light generated in this way is different from natural light, its main application is limited. To solve this problem, it has been proposed to use three-color (RGB) phosphors, high performance blue, green and red phosphors that can be excited by near uv chips (350 nm-420 nm).
Eu in a plurality of fluorescent materials 3+ The red fluorescent powder for the white light LED taking the doped silicate as the matrix has the advantages of rich raw materials, low cost, simple synthesis process, various compositions, adjustable luminescence and the like, and is a hot spot of current research. In general, eu in a matrix 3+ Reduction to Eu 2+ In a reducing atmosphere such as H 2 、H 2 /N 2 Preparation in mixed gas or CO, however Eu is prepared under air condition 3+ Also some will be reduced to Eu 2+ This is called self-reduction phenomenon. Self-reduction phenomenon reduces Eu in matrix 3+ The red component of the phosphor is reduced, which is extremely disadvantageous for preparing a red phosphor having a high color rendering index and a high brightness.
Disclosure of Invention
The invention aims to provide a preparation method of a europium-doped red silicate fluorescent material with high luminous intensity, which is simple, and the raw materials are cheap, and the prepared material has the advantages of high color rendering index and high luminous intensity.
In order to achieve the above purpose, the invention adopts the following technical scheme: a preparation method of a europium-doped red silicate fluorescent material with high luminous intensity comprises the following steps:
(1) In BaCO 3 、ZnO、H 2 SiO 3 And Eu 2 O 3 As raw material powder, according to the molecular formula Ba 1-x Eu x ZnSiO 4 The stoichiometric ratio of the corresponding elements in the raw materials is that each raw material is weighed, wherein x is Eu 3+ Doped Ba 2+ The molar ratio of the position is more than or equal to 0.005 and less than or equal to 0.10;
(2) Mixing the above raw materials with TiO 2 Fully grinding the mixture in an agate mortar for 30-80 min after blending, and uniformly mixing to obtain mixed powder;
(3) Placing the mixed powder into a corundum crucible, presintering for 2-5 h at 700-900 ℃, cooling, fully grinding for 20-40 min again, and tabletting the sample;
(4) Sintering the pressed product at 1000-1150 deg.c for 2-4 hr, and cooling to room temperature to obtain europium doped red silicate fluorescent material with high luminous intensity.
Preferably, tiO 2 Molar mass of (A) based on BaCO 3 、ZnO、H 2 SiO 3 5 to 30 percent of the total molar weight.
Preferably, in step (1), the BaCO 3 ZnO and H 2 SiO 3 The particle size of the powder is 50-70 nm, and the purity is over 99.99%.
Preferably, in the step (3), the mixed powder is put into a corundum crucible and presintered for 4 hours at 750 ℃.
Preferably, in the step (4), the tabletted product is sintered at 1050 ℃ for 4 hours.
In the invention, baZnSiO is adopted as the fluorescent material 4 Eu as a matrix material 3+ TiO as activator ion 2 As an auxiliary agent, ti 4+ Around Eu 3+ Around the periphery, the number of the luminous centers is increased, thereby greatly improving the luminous intensity, and simultaneously, the TiO 2 As a fluxing agent, the crystal grains can be refined, so that the crystal grain size is uniform, and the crystal grains are spheroidized. With TiO 2 Increase of the addition amount of Ti 4+ And O 2- The concentration of (c) will increase, the diffusion coefficient will also increase,plays a role in reducing the reaction temperature to a certain extent; at the same time, tiO 2 Is reduced in effective amount of sample and Eu 2+ With Eu 3+ Energy transfer between the two, inhibit self-reduction phenomenon and promote Eu 3+ Is a light-emitting intensity of the light-emitting element.
Compared with the prior art, the invention has the following advantages:
(1) The red fluorescent powder prepared by the invention emits bright narrow-band red light near 614nm under the excitation of an ultraviolet excitation light source with the excitation wavelength near 394nm, the luminous intensity is 1.9-5.0a.u., and the color rendering index is 80-90; the invention is realized by preparing the TiO 2 Control of the addition amount such that Eu 3+ The luminous intensity of the LED/LDs light-emitting diode is improved by 40-250% on the original basis, and the color rendering index is improved by 6-20% on the original basis, so that the LED/LDs light-emitting diode can be applied to high-power LED/LDs devices;
(2) TiO in the invention 2 As a fluxing agent, the crystal grains can be refined, so that the crystal grains are uniform in size and spheroidized; in addition, with TiO 2 Increase of the addition amount of Ti 4+ And O 2- The concentration of the catalyst is increased, the diffusion coefficient is also increased, and the effect of reducing the reaction temperature is achieved to a certain extent, so that the sintering temperature is reduced from 1300 ℃ to about 1000 ℃.
The invention fully utilizes Eu 3+ Doping BaZnSiO 4 The ultraviolet/near ultraviolet light is used as an excitation light source as the unique advantage of the luminescent material, so that the adverse effect caused by unstable luminescence excited by blue light is overcome, meanwhile, the red fluorescent powder with high brightness and low sintering temperature is prepared, and the application value of the device is greatly improved; the invention has the advantages of cheap raw materials, simple preparation method and easy realization of industrial production.
Drawings
FIG. 1 shows a sample Ba prepared according to an embodiment of the invention 0.96 Eu 0.04 ZnSiO 4 ，TiO 2 Mole fraction of BaCO 3 、ZnO、H 2 SiO 3 An emission spectrum diagram of the fluorescent powder at 0.2 of total molar quantity;
FIG. 2 shows a comparative example, example one to example six (TiO 2 Molar amounts of (a) respectively account for BaCO 3 、ZnO、H 2 SiO 3 0%, 5%, 10%, 15%, 20%, 25%, 30% of the total molar amount of sample Ba prepared 0.96 Eu 0.04 ZnSiO 4 Is a graph of luminous intensity;
FIG. 3 shows a comparative example, example one to example six (TiO 2 Molar amounts of (a) respectively account for BaCO 3 、ZnO、H 2 SiO 3 0%, 5%, 10%, 15%, 20%, 25%, 30% of the total molar amount of sample Ba prepared 0.96 Eu 0.04 ZnSiO 4 Is a color rendering index graph of (c).
Detailed Description
The invention is described in further detail below with reference to the drawings and the specific examples.
Comparison group: no additive TiO is added in the preparation process 2
Preparation of Ba 0.96 Eu 0.04 ZnSiO 4 : according to chemical formula Ba 0.96 Eu 0.04 ZnSiO 4 The stoichiometric ratio of each element is respectively weighing BaCO with the purity of 99.99 percent 3 16.2526g、ZnO 13.96346g、H 2 SiO 3 6.70034g and Eu 2 O 3 0.60384g，BaCO 3 ZnO and H 2 SiO 3 The three materials have the particle size of 60nm, are fully ground in an agate mortar for 50min after being blended and uniformly mixed, a uniformly mixed sample is put in a corundum crucible, presintering is carried out for 4h at 750 ℃, the sample is subjected to tabletting treatment after being cooled and fully ground for 25min again, the product after tabletting is sintered for 2-4 h at 1050 ℃ at constant temperature, and the product is cooled to room temperature along with a furnace, thus obtaining Eu 3+ Activated red phosphor. As can be seen from fig. 1 and 2, the color rendering index of the fluorescence produced by the comparative group is only 75, and the luminous intensity is 1.42a.u..
Example 1
Preparation of Ba 0.96 Eu 0.04 ZnSiO 4 : according to chemical formula Ba 0.96 Eu 0.04 ZnSiO 4 The stoichiometric ratio of each element is respectively weighing BaCO with the purity of 99.99 percent 3 16.2526g(0.082mol)、ZnO 13.96346g(0.172mol)、H 2 SiO 3 6.70034g (0.086 mol) and Eu 2 O 3 0.60384g，BaCO 3 ZnO and H 2 SiO 3 The particle size of the three materials is 60nm, and TiO as fluxing agent is weighed 2 5.4332g(0.016mol)，TiO 2 Molar mass of (A) based on BaCO 3 、ZnO、H 2 SiO 3 20% of the total molar amount of BaCO 3 、ZnO、H 2 SiO 3 Mixing, fully grinding in an agate mortar for 50min, uniformly mixing, placing a uniformly mixed sample into a corundum crucible, presintering for 4h at 750 ℃, cooling, fully grinding for 25min again, tabletting, sintering the tabletting product at 1050 ℃ for 4h at constant temperature, and cooling to room temperature along with a furnace to obtain the europium-doped red silicate fluorescent material.
FIG. 1 is a sample Ba prepared in this example 0.96 Eu 0.04 ZnSiO 4 As can be seen from the graph, the sample prepared in this example emits 614nm narrow-band red light when excited by an ultraviolet LED chip having a wavelength of 394 nm.
FIGS. 2 and 3 are respectively a sample Ba prepared in this example 0.96 Eu 0.04 ZnSiO 4 As can be seen from the graph, the sample emits a narrow-band red light near 614nm under excitation of an ultraviolet LED chip near 394nm, the luminous intensity is 4.97a.u., and the color rendering index is 90. Compared with undoped TiO 2 The luminous intensity of the auxiliary agent at 614nm is improved by 250%, and the display index is improved by 20%.
Example two
Preparation of Ba 0.96 Eu 0.04 ZnSiO 4 : according to chemical formula Ba 0.96 Eu 0.04 ZnSiO 4 The stoichiometric ratio of each element is respectively weighing BaCO with the purity of 99.99 percent 3 16.2526g(0.082mol)、ZnO 13.96346g(0.172mol)、H 2 SiO 3 6.70034g (0.086 mol) and Eu 2 O 3 0.60384g，BaCO 3 ZnO and H 2 SiO 3 The particle size of the three is 50nm, and TiO as an auxiliary agent is weighed 2 1.3583g(0.004mol)，TiO 2 Molar mass of (A) based on BaCO 3 、ZnO、H 2 SiO 3 Total mole of5% of the amount of BaCO 3 、ZnO、H 2 SiO 3 Mixing, fully grinding in an agate mortar for 30min, uniformly mixing, placing a uniformly mixed sample into a corundum crucible, presintering at 700 ℃ for 5h, cooling, fully grinding for 20min again, tabletting, sintering the tabletting product at 1150 ℃ for 2h at constant temperature, and cooling to room temperature along with a furnace to obtain the europium-doped red silicate fluorescent material.
FIGS. 2 and 3 are respectively a sample Ba prepared in this example 0.96 Eu 0.04 ZnSiO 4 From the graph, it can be seen that the sample emits 614nm narrow-band red light under excitation of 394nm ultraviolet LED chip, the luminous intensity is 1.988a.u., the color rendering index is 80, compared with undoped TiO 2 The luminous intensity of the auxiliary agent at 614nm is improved by 40%, and the display index is improved by 6%.
Example III
Preparation of Ba 0.96 Eu 0.04 ZnSiO 4 : according to chemical formula Ba 0.96 Eu 0.04 ZnSiO 4 The stoichiometric ratio of each element is respectively weighing BaCO with the purity of 99.99 percent 3 16.2526g(0.082mol)、ZnO 13.96346g(0.172mol)、H 2 SiO 3 6.70034g (0.086 mol) and Eu 2 O 3 0.60384g，BaCO 3 ZnO and H 2 SiO 3 The particle diameter of the three is 65nm, and TiO as an auxiliary agent is weighed 2 2.1766g，TiO 2 Molar mass of (A) based on BaCO 3 、ZnO、H 2 SiO 3 10% of the total molar amount of BaCO 3 、ZnO、H 2 SiO 3 And (3) fully grinding the mixture in an agate mortar for 40min to uniformly mix the mixture, placing the uniformly mixed sample into a corundum crucible, presintering the mixture for 3h at 750 ℃, cooling the mixture, fully grinding the mixture for 25min again, tabletting the sample, sintering the tabletting product at 1150 ℃ for 2h at constant temperature, and cooling the tabletting product to room temperature along with a furnace to obtain the europium-doped red silicate fluorescent material.
FIGS. 2 and 3 are respectively a sample Ba prepared in this example 0.96 Eu 0.04 ZnSiO 4 And a display index graph, as can be seen from the graph,the sample emits 614nm narrow-band red light under the excitation of 394nm ultraviolet LED chip, the luminous intensity is 2.272a. U., the color rendering index is 83, compared with undoped TiO 2 The luminous intensity of the auxiliary agent at 614nm is improved by 60%, and the display index is improved by 11%.
Example IV
Preparation of Ba 0.96 Eu 0.04 ZnSiO 4 : according to chemical formula Ba 0.96 Eu 0.04 ZnSiO 4 The stoichiometric ratio of each element is respectively weighing BaCO with the purity of 99.99 percent 3 16.2526g(0.082mol)、ZnO 13.96346g(0.172mol)、H 2 SiO 3 6.70034g (0.086 mol) and Eu 2 O 3 0.60384g，BaCO 3 ZnO and H 2 SiO 3 The particle size of the three is 55nm, and TiO as an auxiliary agent is weighed 2 3.26495g(0.012mol)，TiO 2 Molar mass of (A) based on BaCO 3 、ZnO、H 2 SiO 3 15% of the total molar amount of BaCO 3 、ZnO、H 2 SiO 3 Mixing, fully grinding in an agate mortar for 75min, uniformly mixing, placing a uniformly mixed sample into a corundum crucible, presintering for 4h at 800 ℃, cooling, fully grinding for 30min again, tabletting, sintering the tabletting product at 1050 ℃ for 3h at constant temperature, cooling to room temperature along with a furnace, and obtaining the europium-doped red silicate fluorescent material, wherein the europium-doped red silicate fluorescent material emits 614nm narrow-band red light under excitation of an ultraviolet LED chip near 394 nm.
FIGS. 2 and 3 are respectively a sample Ba prepared in this example 0.96 Eu 0.04 ZnSiO 4 From the graph, it can be seen that the sample emits 614nm narrow-band red light under excitation of 394nm ultraviolet LED chip, the luminous intensity is 3.5a.u., the color rendering index is 87, compared with undoped TiO 2 The luminous intensity of the auxiliary agent at 614nm is improved by 150%, and the display index is improved by 16%.
Example five
Preparation of Ba 0.96 Eu 0.04 ZnSiO 4 : according to chemical formula Ba 0.96 Eu 0.04 ZnSiO 4 Stoichiometric ratio of each elementBaCO with the purity of 99.99 percent is respectively weighed 3 16.2526g(0.082mol)、ZnO 13.96346g(0.172mol)、H 2 SiO 3 6.70034g (0.086 mol) and Eu 2 O 3 0.60384g，BaCO 3 ZnO and H 2 SiO 3 The particle size of the three is 70nm, and TiO as an auxiliary agent is weighed 2 5.4415g(0.020mol)，TiO 2 Molar mass of (A) based on BaCO 3 、ZnO、H 2 SiO 3 25% of the total molar amount of BaCO 3 、ZnO、H 2 SiO 3 And (3) fully grinding the mixture in an agate mortar for 60min to uniformly mix, putting a uniformly mixed sample into a corundum crucible, presintering for 3h at 750 ℃, cooling, fully grinding for 35min again, tabletting the sample, sintering the tabletting product at 1050 ℃ for 4h at constant temperature, and cooling to room temperature along with a furnace to obtain the europium-doped red silicate fluorescent material.
FIGS. 2 and 3 are respectively a sample Ba prepared in this example 0.96 Eu 0.04 ZnSiO 4 From the graph, it can be seen that the sample emits 614nm narrow-band red light under excitation of 394nm ultraviolet LED chip, the luminous intensity is 4.118a.u., the color rendering index is 88, compared with undoped TiO 2 The luminous intensity of the auxiliary agent at 614nm is improved by 190%, and the display index is improved by 17%.
Example six
Preparation of Ba 0.96 Eu 0.04 ZnSiO 4 : according to chemical formula Ba 0.96 Eu 0.04 ZnSiO 4 The stoichiometric ratio of each element is respectively weighing BaCO with the purity of 99.99 percent 3 16.2526g(0.082mol)、ZnO 13.96346g(0.172mol)、H 2 SiO 3 6.70034g (0.086 mol) and Eu 2 O 3 0.60384g，BaCO 3 ZnO and H 2 SiO 3 The particle size of the three is 58nm, and TiO as an auxiliary agent is weighed 2 6.5298g(0.024mol)，TiO 2 Molar mass of (A) based on BaCO 3 、ZnO、H 2 SiO 3 30% of the total molar amount of BaCO 3 、ZnO、H 2 SiO 3 Mixing, grinding in agate mortar for 80min, mixing, and packagingAfter being put into a corundum crucible, presintering for 2 hours at 900 ℃, fully grinding for 40 minutes after cooling, tabletting the sample, sintering the tabletting product at 1000 ℃ for 4 hours at constant temperature, cooling to room temperature along with a furnace to obtain the europium-doped red silicate fluorescent material, and under excitation of an ultraviolet LED chip near 394nm, the europium-doped red silicate fluorescent material emits narrow-band red light near 614nm, the luminous intensity is 2.8411 a.u., and the color rendering index is 82, compared with undoped TiO 2 The luminous intensity of the auxiliary agent at 614nm is increased to 200%, and the display index is increased by 9%.
FIGS. 2 and 3 are respectively a sample Ba prepared in this example 0.96 Eu 0.04 ZnSiO 4 From the graph, it can be seen that the sample emits 614nm narrow-band red light under excitation of 394nm ultraviolet LED chip, the luminous intensity is 2.8411 a.u., the color rendering index is 82, compared with undoped TiO 2 The luminous intensity of the auxiliary agent at 614nm is improved by 100%, and the display index is improved by 9%.
Example seven
Preparation of Ba 0.995 Eu 0.005 ZnSiO 4 : according to chemical formula Ba 0.995 Eu 0.005 ZnSiO 4 The stoichiometric ratio of each element is respectively weighing BaCO with the purity of 99.99 percent 3 16.84514g (0.085 mol), znO 13.96346g (0.172 mol) and H 2 SiO 3 6.70034g (0.086 mol), and Eu 2 O 3 0.07548g，BaCO 3 ZnO and H 2 SiO 3 The particle size of the three is 60nm, and TiO as an auxiliary agent is weighed 2 5.4332g，TiO 2 Molar mass of (A) based on BaCO 3 、ZnO、H 2 SiO 3 20% of the total molar amount of BaCO 3 、ZnO、H 2 SiO 3 Mixing, fully grinding in agate mortar for 50min, mixing, placing the mixed sample into corundum crucible, presintering at 750deg.C for 4h, cooling, fully grinding for 25min, tabletting, sintering at 1050 deg.C for 4h, cooling to room temperature to obtain europium-doped red silicate fluorescent material, and exciting by ultraviolet LED chip at about 394nm to obtain red light with narrow band red light emission intensity of 4.534a.u at 614nmColor index 85, compared to undoped TiO 2 The luminous intensity of the auxiliary agent at 614nm is improved by 219%, and the display index is improved by 14%.
Example eight
Preparation of Ba 0.9 Eu 0.10 ZnSiO 4 : according to chemical formula Ba 0.9 Eu 0.10 ZnSiO 4 The stoichiometric ratio of each element is respectively weighing BaCO with the purity of 99.99 percent 3 15.23681g(0.077mol)、ZnO 13.96346g(0.172mol)、H 2 SiO 3 6.70034g (0.086 mol) and Eu 2 O 3 1.50959g，BaCO 3 ZnO and H 2 SiO 3 The particle size of the three is 60nm, and TiO as an auxiliary agent is weighed 2 5.4332g(0.016mol)，TiO 2 Molar mass of (A) based on BaCO 3 、ZnO、H 2 SiO 3 20% of the total molar amount of BaCO 3 、ZnO、H 2 SiO 3 Mixing, fully grinding in an agate mortar for 50min, uniformly mixing, placing a uniformly mixed sample into a corundum crucible, presintering for 4h at 750 ℃, cooling, fully grinding for 25min again, tabletting, sintering the tabletting product at 1050 ℃ for 4h at constant temperature, cooling to room temperature along with a furnace to obtain the europium-doped red silicate fluorescent material, and under excitation of an ultraviolet LED chip near 394nm, emitting a narrow-band red light with the luminous intensity of 4.463a.u. near 614nm and the color rendering index of 86, compared with undoped TiO 2 The luminous intensity of the auxiliary agent at 614nm is improved by 214%, and the display index is improved by 15%.
Claims (5)
1. The preparation method of the europium-doped red silicate fluorescent material with high luminous intensity is characterized by comprising the following steps of:
(1) In BaCO 3 、ZnO、H 2 SiO 3 And Eu 2 O 3 As raw material powder, according to the molecular formula Ba 1-x Eu x ZnSiO 4 The stoichiometric ratio of the corresponding elements in the raw materials is that each raw material is weighed, wherein x is Eu 3+ Doped Ba 2+ The molar ratio of the position is more than or equal to 0.005 and less than or equal to 0.10;
(2) Mixing the above raw materials with TiO 2 After blendingFully grinding the mixture in an agate mortar for 30-80 min, and uniformly mixing the mixture to obtain mixed powder;
(3) Placing the mixed powder into a corundum crucible, presintering for 2-5 h at 700-900 ℃, cooling, fully grinding for 20-40 min again, and tabletting the sample;
(4) Sintering the pressed product at 1000-1150 deg.c for 2-4 hr, and cooling to room temperature to obtain europium doped red silicate fluorescent material with high luminous intensity.
2. The method for preparing a europium-doped red silicate fluorescent material with high luminous intensity according to claim 1, wherein in step (2), tiO 2 Molar mass of (A) based on BaCO 3 、ZnO、H 2 SiO 3 5 to 30 percent of the total molar weight.
3. The method according to claim 1 or 2, wherein in the step (1), the BaCO 3 ZnO and H 2 SiO 3 The particle size of the powder is 50-70 nm, and the purity is over 99.99%.
4. The method of preparing a europium-doped red silicate fluorescent material with high luminous intensity according to claim 1 or 2, wherein in step (3), the mixed powder is put into a corundum crucible and then pre-sintered for 4 hours at 750 ℃.
5. The method according to claim 1 or 2, wherein in the step (4), the pressed product is sintered at 1050 ℃ for 4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111062792.1A CN113621365B (en) | 2021-09-10 | 2021-09-10 | Preparation method of europium-doped red silicate fluorescent material with high luminous intensity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111062792.1A CN113621365B (en) | 2021-09-10 | 2021-09-10 | Preparation method of europium-doped red silicate fluorescent material with high luminous intensity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113621365A CN113621365A (en) | 2021-11-09 |
| CN113621365B true CN113621365B (en) | 2023-06-23 |
Family
ID=78389759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111062792.1A Active CN113621365B (en) | 2021-09-10 | 2021-09-10 | Preparation method of europium-doped red silicate fluorescent material with high luminous intensity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113621365B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486908A (en) * | 2009-02-04 | 2009-07-22 | 昆明理工大学 | Red long afterglow luminous material and preparing process thereof |
| CN102585820A (en) * | 2012-02-16 | 2012-07-18 | 安徽天阳光源材料有限公司 | Red-emitting fluorescent powder and preparation method thereof |
-
2021
- 2021-09-10 CN CN202111062792.1A patent/CN113621365B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| Enhanced Eu3+ emission in Ca2LaTaO6:Eu3+ phosphors by codoping Bi3+;zhang le et al.;《Journal of Materials Science》;第31卷;第9160-9166页 * |
| 高功率密度激发荧光材料的反常热猝灭效应;张乐等;《发光学报》;第42卷;第1458-1481页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113621365A (en) | 2021-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100666211B1 (en) | Composition of silicates phosphor for uv and long-wavelength excitation | |
| JP4625496B2 (en) | Novel silicate yellow-green phosphor | |
| KR101475497B1 (en) | Aluminum-silicate based orange-red phosphors with mixed divalent and trivalent cations | |
| EP2447338B1 (en) | Borophosphate phosphor and light source | |
| JP2013539490A (en) | Oxynitride light emitting material, method for preparing the same, and illumination light source manufactured thereby | |
| KR101088996B1 (en) | Silicon-containing phosphor for led, its preparation and the light emitting devices using the same | |
| CN113249125B (en) | Ce 3+ Doped silicate-based green fluorescent powder and preparation method and application thereof | |
| KR100697822B1 (en) | Strontium magnesium silicate blue phosphor for UV LED and preparation method thereby | |
| CN108998025B (en) | Silicate-based red fluorescent powder for LED and preparation method thereof | |
| KR20040069547A (en) | Composition and Preparation method of yellow silicates phosphor for long-wavelength UV excitation | |
| CN113201342A (en) | Ce3+Activated silicate broadband green fluorescent powder and preparation method and application thereof | |
| JP5361736B2 (en) | Phosphor, coating phosphor composition, phosphor production method, and light emitting device | |
| JP5818109B2 (en) | (Halo) silicate phosphor and method for producing the same | |
| CN103045266A (en) | Red phosphor, preparation method thereof and light-emitting device with red phosphor | |
| CN112608742A (en) | beta-Al activated by europium2O3Defect structure blue fluorescent powder and preparation method thereof | |
| CN114574206B (en) | Fluorescent powder for white light-emitting diode and synthesis method and application thereof | |
| CN113621365B (en) | Preparation method of europium-doped red silicate fluorescent material with high luminous intensity | |
| CN107163943B (en) | Spectrum-adjustable fluorescent powder suitable for near ultraviolet excitation and preparation method thereof | |
| CN109233832B (en) | Blue/green fluorescent powder for white light LED and preparation method and application thereof | |
| CN110129041B (en) | Green nitrogen oxide fluorescent material and manufacturing method thereof | |
| JP2013144794A (en) | Oxynitride-based phosphor and light-emitting device using the same | |
| CN112980442A (en) | Dy (Dy)3+Ion activated lutecium salt white fluorescent powder and preparation method thereof | |
| CN112940724A (en) | Eu (Eu)3+Ion activated borate red fluorescent material and preparation method thereof | |
| KR101190719B1 (en) | Green emitting calcium borate silicate based phosphor | |
| KR20070121508A (en) | Thullium containing fluorescent substance for white light emitting diode and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |