CN117887459A - Red light emitting fluorescent material and preparation method thereof - Google Patents
Red light emitting fluorescent material and preparation method thereof Download PDFInfo
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- CN117887459A CN117887459A CN202410034899.2A CN202410034899A CN117887459A CN 117887459 A CN117887459 A CN 117887459A CN 202410034899 A CN202410034899 A CN 202410034899A CN 117887459 A CN117887459 A CN 117887459A
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- red light
- fluorescent material
- emitting fluorescent
- light emitting
- ethyl alcohol
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- 239000000463 material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 20
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims 4
- 238000000695 excitation spectrum Methods 0.000 abstract description 6
- 230000003595 spectral effect Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 238000005424 photoluminescence Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000011812 mixed powder Substances 0.000 description 18
- 239000004570 mortar (masonry) Substances 0.000 description 17
- 229910052593 corundum Inorganic materials 0.000 description 16
- 239000010431 corundum Substances 0.000 description 16
- 230000005284 excitation Effects 0.000 description 13
- 238000005245 sintering Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 9
- 229910052724 xenon Inorganic materials 0.000 description 9
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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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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- Luminescent Compositions (AREA)
Abstract
The invention discloses a red light emitting fluorescent material and a preparation method thereof, belonging to the technical field of visible light photoluminescence fluorescence. The red light emitting fluorescent material is Bi 3+ and Ln 3+ co-doped Ca 5Ga6O14, and the chemical formula is Ca 5‑x‑yGa6O14：xBi3+,yLn3+, wherein x is more than 0 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.03, and Ln 3+ is Pr 3+、Dy3+、Sm3+ or Tb 3+. The solid phase method is adopted, no strong acid solvent polluting the environment and no harmful waste are generated, the synthesized sample does not need further purification, the obtained red light emitting fluorescent material has good crystallinity and good stability to light, heat and humidity, and the excitation spectrum of the obtained red light emitting fluorescent material is positioned in an n-UV region; thus, spectral overlap can be effectively avoided.
Description
Technical Field
The invention belongs to the technical field of visible light photoluminescence fluorescence, and particularly relates to a red light emitting fluorescent material and a preparation method thereof.
Background
Conventional activator doped phosphors have some inherent problems due to their luminescence characteristics. For Eu 2+ longer wavelength phosphors, eu 2+ is typically located at a higher covalent crystal site, such as a nitride or oxynitride, around which the strong crystal field splits further into 5d energy levels, resulting in red emission. The extension of the 5d energy level extends the excitation to the red spectral range. Longer wavelength excitation inevitably results in reabsorption of the emission produced by the device, thus reducing the luminous efficiency of the device. These problems stem from the luminescent transition properties of these phosphors, which cannot be resolved under the traditional dopant-based phosphor framework. This limits the future development of phosphor conversion technology.
In recent years, bi 3+ activated fluorescent powder has been widely studied due to its unique luminescence property, and the excitation spectrum is located in the n-UV region, so that spectral overlap can be effectively avoided. However, bi 3+ ions typically emit blue and green light, and rarely emit red light.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a red light emitting fluorescent material and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a red light emitting fluorescent material is Bi 3+ and Ln 3+ co-doped Ca 5Ga6O14, and has a chemical formula of Ca 5-x-yGa6O14xBi3+,yLn3+, wherein x is more than 0 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.03, and Ln 3+ is Pr 3+Dy3+Sm3+ or Tb 3+.
The invention also claims a preparation method of the red light emitting fluorescent material, which comprises the following steps: weighing CaCO 3Ga2O3Bi2O3 and oxidized Ln according to the stoichiometric ratio of a chemical formula, mixing, adding absolute ethyl alcohol, grinding, and calcining to obtain the red light emitting fluorescent material.
As a preferred embodiment of the invention, the molar ratio of CaCO 3Ga2O3Bi2O3 to oxidized Ln is calculated according to Ca 5-x- yGa6O14xBi3+,yLn3+ stoichiometric ratio.
Oxidized Ln is Pr 6O11Dy2O3Sm2O3 or Tb 4O7.
As a preferred embodiment of the present invention, the volume ratio of the total mass of CaCO 3Ga2O3Bi2O3 and oxidized Ln to absolute ethanol is 1 g/(4-7) ml.
As a preferred embodiment of the invention, the calcination temperature is 1100-1300 , the time is 5-10h, and the temperature rising rate is 5 /min.
As a preferred embodiment of the present invention, the milling time is 20 to 60 minutes.
According to the invention, an adaptive crystal structure is constructed by introducing Pr 3+Dy3+Sm3+ or Tb 3+, and oxygen vacancies around Bi 3+ ions are regulated and controlled, so that electrons around Bi 3+ ions are localized, and red light or orange-red light emission of Bi 3+ ions is realized.
Compared with the prior art, the invention has the beneficial effects that: the red light emitting fluorescent material has good crystallinity and light, heat and humidity stability. The solid phase method is adopted, so that no strong acid solvent polluting the environment, no harmful waste and further purification of synthesized samples are needed, and the excitation spectrum of the obtained red light emitting fluorescent material is positioned in an n-UV region; thus, spectral overlap can be effectively avoided.
Drawings
FIG. 1 is a graph showing the emission spectrum of the red light-emitting fluorescent material prepared in example 1 of the present invention after excitation with a xenon lamp having a wavelength of 365nm at room temperature.
FIG. 2 is a graph showing the excitation spectrum of the red light-emitting fluorescent material prepared in example 1 of the present invention.
FIG. 3 is a graph showing the emission spectrum of the fluorescent material of comparative example 1 after excitation at room temperature with a xenon lamp having a wavelength of 286 nm.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The purity of CaCO 3Ga2O3Bi2O3 and Pr 6O11 in both examples and comparative examples was 99.99%.
Example 1
The red light emitting fluorescent material is prepared by weighing CaCO 3498mol,Ga2O3300mol,Bi2O3 according to the following proportion: 0.5mol and Pr 6O11: and (3) placing the mixed powder in an agate mortar after 0.167mol mixing, dripping absolute ethyl alcohol, grinding for 30min (the mass of the mixed powder and the volume ratio of the absolute ethyl alcohol are 1g to 4 mL), grinding until the materials are powdery, transferring the materials to a corundum crucible, placing the corundum crucible into a box furnace at 1300 for high-temperature sintering for 6h, wherein the heating rate is 5 /min, and finally naturally cooling to room temperature to obtain the red light emitting fluorescent material.
The emission spectrum of the red light-emitting fluorescent material prepared in example 1 was measured using an F7000 fluorescence spectrophotometer at room temperature, and the xenon lamp light source was selected to be 365nm, and as a result, as seen in fig. 1, it can be seen from fig. 1 that the material has broadband emission in the 500-800nm region under excitation of the 365nm xenon lamp, and the emission peak center is located at 610nm, thereby emitting red light.
Further, by detecting the wavelength of 610nm, the excitation spectrum (PLE) of the red light emitting fluorescent material was measured, and as a result, as shown in FIG. 2, four excitation peaks of 345nm, 451nm, 472nm and 486nm were seen from the excitation spectrum.
Example 2
The red light emitting fluorescent material is prepared by weighing CaCO 3492mol,Ga2O3300mol,Bi2O3 according to the following proportion: 2.5mol and Pr 6O11: and (3) placing the mixed powder after 0.5mol mixing in an agate mortar, dripping absolute ethyl alcohol, grinding for 30min (the mass of the mixed powder and the volume ratio of the absolute ethyl alcohol are 1g:7 mL), grinding until the materials are powdery, transferring the materials to a corundum crucible, placing the corundum crucible into a box furnace at 1100 for high-temperature sintering, sintering for 10h, wherein the heating rate is 5 /min, and finally naturally cooling to room temperature to obtain the red light emitting fluorescent material.
The red light-emitting fluorescent material prepared in example 2 has broadband emission in the 500-800nm region under excitation of 365nm xenon lamp, and the center of emission peak is located at 610nm, so as to emit red light.
Example 3
The red light emitting fluorescent material is prepared by weighing CaCO 3484mol,Ga2O3300mol,Bi2O3 according to the following proportion: 0.05mol and Pr 6O11: and (3) placing the mixed powder in an agate mortar after 0.01mol of the mixed powder is mixed, dripping absolute ethyl alcohol, grinding for 30min (the mass of the mixed powder and the volume ratio of the absolute ethyl alcohol are 1g to 5 mL), grinding until the materials are in powder form, transferring the materials to a corundum crucible, placing the corundum crucible into a box-type furnace with 1200 for high-temperature sintering for 5h, wherein the heating rate is 5 /min, and finally naturally cooling to room temperature to obtain the red light emitting fluorescent material.
The red light-emitting fluorescent material prepared in example 3 has broadband emission in the 500-800nm region under excitation of 365nm xenon lamp, and the center of emission peak is located at 610nm, so as to emit red light.
Example 4
The red light emitting fluorescent material is prepared by weighing CaCO 3492mol,Ga2O3300mol,Bi2O3 according to the following proportion: 2.5mol and Dy 2O3: 1.5mol of mixed powder is placed in an agate mortar, absolute ethyl alcohol is dripped into the mortar, the mortar is ground for 30min (the mass of the mixed powder and the volume ratio of the absolute ethyl alcohol are 1g to 7 mL), the mortar is ground until the material is in a powder shape, the material is transferred to a corundum crucible, the corundum crucible is placed in a box furnace at 1100 for high-temperature sintering, the sintering is carried out for 10h, the heating rate is 5 /min, and finally, the red light emitting fluorescent material is obtained after natural cooling to room temperature.
The red light-emitting fluorescent material prepared in example 4 has broadband emission at 500-800nm under excitation of 365nm xenon lamp, and the emission peak center is at 578nm, so that orange red light is emitted.
Example 5
The red light emitting fluorescent material is prepared by weighing CaCO 3492mol,Ga2O3300mol,Bi2O3 according to the following proportion: 2.5mol and Sm 2O3: 1.5mol of mixed powder is placed in an agate mortar, absolute ethyl alcohol is dripped into the mortar, the mortar is ground for 30min (the mass of the mixed powder and the volume ratio of the absolute ethyl alcohol are 1g to 7 mL), the mortar is ground until the material is in a powder shape, the material is transferred to a corundum crucible, the corundum crucible is placed in a box furnace at 1100 for high-temperature sintering, the sintering is carried out for 10h, the heating rate is 5 /min, and finally, the red light emitting fluorescent material is obtained after natural cooling to room temperature.
The red light-emitting fluorescent material prepared in example 5 has broadband emission in the 500-800nm region under excitation of 365nm xenon lamp, and the center of emission peak is 607nm, so as to emit red light.
Example 6
The red light emitting fluorescent material is prepared by weighing CaCO 3492mol,Ga2O3300mol,Bi2O3 according to the following proportion: 2.5mol and Tb 4O7: and (3) placing the mixed powder after 0.75mol mixing in an agate mortar, dripping absolute ethyl alcohol, grinding for 30min (the mass of the mixed powder and the volume ratio of the absolute ethyl alcohol are 1g:7 mL), grinding until the materials are powdery, transferring the materials to a corundum crucible, placing the corundum crucible into a box furnace at 1100 for high-temperature sintering, sintering for 10h, wherein the heating rate is 5 /min, and finally naturally cooling to room temperature to obtain the red light emitting fluorescent material.
The red light-emitting fluorescent material prepared in example 6 has broadband emission in the 500-800nm region under excitation of a 365nm xenon lamp, and the center of the emission peak is located at 598nm, so that orange-red light is emitted.
Comparative example 1
The fluorescent material is prepared by weighing CaCO 3499mol,Ga2O3300mol,Bi2O3 according to the following proportion: and (3) after 0.5mol of the mixed powder is mixed, the mixed powder is placed in an agate mortar, absolute ethyl alcohol is dripped into the mortar, the mortar is ground for 30min (the volume ratio of the mixed powder to the absolute ethyl alcohol is 1g:4 mL), the mortar is ground until the material is in a powder state, the material is transferred to a corundum crucible, the corundum crucible is placed into a box furnace at 1300 for high-temperature sintering for 6h, the heating rate is 5 /min, and finally the fluorescent material is obtained after natural cooling to room temperature.
As can be seen from FIG. 1, the fluorescent material obtained in comparative example 1 has the strongest emission peak at 373nm under excitation of 286nm light, and does not emit red or orange-red light.
Comparative example 2
The fluorescent material is prepared by weighing CaCO 3498mol,Ga2O3 according to the following proportion: 300mol and Pr 6O11: mixing 0.167mol, placing the mixed powder into an agate mortar, dripping absolute ethyl alcohol, grinding for 30min (the mass of the mixed powder and the volume ratio of the absolute ethyl alcohol are 1g to 4 mL), grinding until the materials are powdery, transferring the materials to a corundum crucible, placing the corundum crucible into a box furnace at 1300 for high-temperature sintering for 6h, heating to 5 /min, and naturally cooling to room temperature to obtain the fluorescent material.
The fluorescent material obtained in comparative example 2 had the strongest emission peak at 630nm under 365nm excitation, but red luminescence was significantly weaker than in examples 1-6. The fluorescent material prepared in comparative example 2 was Pr ion-emitting and was narrow-band-based, whereas the red-emitting fluorescent material of the present invention was Pr ion-influencing electrons around Bi ions, so that Bi ions were used as the luminescence center for broadband emission, and red or orange-red light was emitted.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (5)
1. A red light emitting fluorescent material is characterized in that the red light emitting fluorescent material is Bi 3+ and Ln 3+ co-doped Ca 5Ga6O14, the chemical formula of the red light emitting fluorescent material is Ca 5-x-yGa6O14xBi3+,yLn3+, wherein x is more than 0 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.03, and Ln 3+ is Pr 3+Dy3+Sm3+ or Tb 3+.
2. The method for preparing a red light-emitting fluorescent material according to claim 1, comprising: mixing CaCO 3Ga2O3Bi2O3 and oxidized Ln, adding absolute ethyl alcohol, grinding, and calcining to obtain the red light emitting fluorescent material.
3. The method for preparing a red light-emitting fluorescent material according to claim 2, wherein the volume ratio of the total mass of CaCO 3Ga2O3Bi2O3 and oxidized Ln to absolute ethyl alcohol is 1g: (4-7) ml.
4. The method for preparing a red light-emitting fluorescent material according to claim 2, wherein the calcination temperature is 1100-1300 , the time is 5-10 hours, and the heating rate is 5 /min.
5. The method for preparing a red light-emitting fluorescent material according to claim 2, wherein the grinding time is 20 to 60 minutes.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202410034899.2A CN117887459A (en) | 2024-01-10 | 2024-01-10 | Red light emitting fluorescent material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202410034899.2A CN117887459A (en) | 2024-01-10 | 2024-01-10 | Red light emitting fluorescent material and preparation method thereof |
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| CN117887459A true CN117887459A (en) | 2024-04-16 |
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