CN114540013B - Lifting CaO-Eu 2+ Method for preparing near infrared fluorescent powder with luminous intensity and thermal stability and application thereof - Google Patents
Lifting CaO-Eu 2+ Method for preparing near infrared fluorescent powder with luminous intensity and thermal stability and application thereof Download PDFInfo
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- -1 Rare earth ion Chemical class 0.000 description 1
- 229910003564 SiAlON Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
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- 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
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with alkaline earth metals
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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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7735—Germanates
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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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- Luminescent Compositions (AREA)
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Abstract
The application belongs to the technical field of inorganic luminescent materials, and in particular relates to a method for improving CaO: eu 2+ A method for the luminous intensity and the thermal stability of near infrared fluorescent powder and application thereof. The method uses CaO to Eu 2+ Based on near infrared emitting fluorescent powder by adding GeO 2 、SnO 2 Or PbO 2 Additive for compensating CaO and Eu 2+ Oxygen defects generated in the sintering process of the reducing atmosphere are overcome, so that the luminous intensity of the fluorescent powder is enhanced, and the thermal stability is improved. The near infrared fluorescent powder prepared by the application has the excellent characteristics of high luminous intensity and high thermal stability, and is expected to be used for a high-power near infrared LED device of a blue light chip pump.
Description
Technical Field
The application belongs to the technical field of inorganic luminescent materials, and relates to a near infrared fluorescent material CaO: eu 2+ Method for improving luminescence performance and thermal stability and application of method in near-infrared LED luminescence device, more specifically low-quality CaO: eu with low internal quantum efficiency and poor thermal stability 2+ The fluorescent powder has improved luminous performance and heat stability.
Background
Near infrared light is a non-visible light region which is found by people earlier, and because the early technical level is not high, the spectrum is overlapped and the analysis is complex due to the influence of frequency multiplication and frequency combination, so that the research and the application of near infrared light are limited to a certain extent. Until the 60 s of the 20 th century, the advent of commercial instruments and a great deal of work by Norris et al put forward the theory that the content of substances and absorption peaks at a plurality of different wavelength points in the near infrared region are in linear relation, and the NIR diffuse reflection technology is utilized to measure the components such as moisture, protein, fat and the like in agricultural products, so that the near infrared spectrum technology is widely applied to agricultural and sideline product analysis. In recent years, near infrared light sources have gained great attention in the context of rapid development of various emerging demands. For example, in the face recognition field, an infrared light source is used as an active light source to irradiate a face, and then the face is imaged by a camera, so that the influence of different ambient lights on imaging can be overcome. And infrared light human eyes are invisible, interference to human eyes is avoided, and user comfort is not reduced. Therefore, the infrared light face recognition technology becomes a mainstream scheme of the face recognition technology. In addition, by utilizing the characteristic that human tissues have different absorption capacities for infrared light with different wavelengths, heartbeat, blood oxygen concentration and the like can be detected by utilizing infrared light.
Currently, the near infrared light sources commonly used in the market mainly include halogen lamps, infrared light emitting diodes, etc., however, they all have inherent defects: halogen lamps have the disadvantages of short service life, huge volume, slow response, high energy consumption, low efficiency and the like; the infrared light-emitting diode has narrower emission band, unstable peak wavelength and serious decrease of luminous intensity at high temperature, and can not be widely applied to near infrared technology. In recent years, white light LED technology has been greatly developed, and scientists have realized broadband near infrared light emission by constructing a fluorescence conversion type LED light source by exciting near infrared fluorescent powder by using an LED chip. The novel near infrared light source prepared by the scheme of the LED chip and the near infrared fluorescent material has the advantages of low cost, wide and adjustable spectrum, high thermal stability, high power, energy conservation, environmental protection, small volume, quick response and the like, and becomes the most effective way for solving the problem of lacking a miniaturized and quick-response broadband near infrared light source.
Among the inorganic phosphors are ions capable of generating near infrared emission mainly: pr (Pr) 3+ ,Nd 3+ ,Tm 3+ ,Yb 3+ Rare earth ion and Cr 3+ ,Ni 2+ ,Mn 4+ Transition metal ions. Wherein Pr is 3+ ,Nd 3+ ,Tm 3+ ,Yb 3+ ,Mn 4+ Ions are emitted in sharp lines, so that the wide application of a near infrared light source is difficult to meet; ni (Ni) 2+ The ions have a broad near infrared emission peak but have low luminous efficiency, severely limiting their use as near infrared light sources. In recent years, cr 3+ Because the emission spectrum of the material has adjustability, the material doped with boride, oxide and the like shows better near infrared luminescence performance and potential application prospect. Cr (Cr) 3+ Ions are widely used as luminescent dopants and luminescent sensitizers in various materials, and have become an important point of many optical spectra and luminescent material studies. However, cr 3+ The unavoidable presence of Cr in the ion-doped phosphor 6+ Ion to Cr 3+ The luminescence of the ions causes severe quenching, resulting in low luminescence efficiency;although some minority Cr 3+ Doped phosphors such as: ca (Ca) 3 Sc 2 Si 3 O 12 :Cr 3+ Literature (Jia, Z.et al light: science)&Applications,2020,9,86) and Na 3 ScF 6 :Cr 3+ (He, F.et al advanced Functional Materials,2021,31,2103743) achieves an internal quantum efficiency of greater than 90%, but due to Cr 3+ The forbidden transition of the ion 3d-3d leads to the fluorescent powder with low absorption coefficient and low external quantum efficiency, which hinders the commercialization process.
Eu 2+ Ions are a well-known activator ion, and phosphors prepared by doping the ions have been widely used in the fields of illumination and display, such as: baMgAl 10 O 17 :Eu 2+ Blue powder, beta-SiAlON: eu 2+ Green powder, sr [ LiAl ] 3 N 4 ]:Eu 2+ Red powder, etc. But due to Eu 2+ The 5d-4f transition of ions is largely dependent on the crystal field environment of the matrix, and it is difficult to achieve a large Stokes shift, so Eu is observed only in a few matrices 2+ The near Infrared light source has the problems of low luminous efficiency and poor thermal stability, so that the comprehensive performance of the near Infrared light source is greatly reduced, and further the commercial application of the near Infrared light source is limited (Qiao, J.et al, differential fluorescent-injected-emittingphosphor for light-injecting diodes.Nat.Commun.2019,10,5267;Yang,Z.et al.Giant Red-Shifted Emission in (Sr, ba) Y2O4: eu2+ PhosphorToward Broadband Near-Infrared fluorescent lamp. Adv. Function. Mater, 2021,2103927). Based on this, for the existing Eu 2+ The performance of the doped near infrared fluorescent powder is optimized, so that the novel near infrared fluorescent powder with excellent luminous efficiency and thermal stability and a device thereof are obtained, and the method has important guiding significance for the production of related system products.
At present, many reports on improving the comprehensive performance of fluorescent materials by methods such as matrix regulation (cation doping/anion substitution and the like) and preparation process improvement (step synthesis method, coprecipitation method and the like) are provided, but the problem that the luminous performance of the existing near infrared fluorescent materials is difficult to improve is not solved. By adding specific additives, e.g. GeO, to the fluorescent material 2 、SnO 2 Or PbO 2 To reduceMethods for improving luminescence properties and improving thermal stability by reducing oxygen vacancies have not been similarly reported.
Disclosure of Invention
Aiming at the defects of the prior art, the application aims to provide a low-quality CaO: eu 2+ The fluorescent powder optimizing scheme solves the problem of non-ideal luminous efficiency and heat stability of near infrared fluorescent powder in the prior art. And further packaging the optimized fluorescent powder with an InGaN or GaN blue light chip to obtain the high-performance near-infrared LED device.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
lifting CaO-Eu 2+ The method for the luminous intensity and the thermal stability of the near infrared fluorescent powder comprises the following steps: with CaO: eu 2+ Based on near infrared fluorescent powder, by adding specific additive GeO 2 、SnO 2 Or PbO 2 To reduce oxygen vacancies in the CaO lattice and thereby promote CaO: eu 2+ The luminous intensity of the near infrared fluorescent powder and the heat stability of the near infrared fluorescent powder are improved.
The method is realized by the following steps:
(1) According to the chemical general formula CaO xEu 2+ ,yMO 2 Weighing raw materials, fully grinding and uniformly mixing to obtain a raw material mixture;
(2) Placing the raw material mixture obtained in the step (1) in an alumina crucible or a graphite crucible, and calcining in a high-temperature furnace in a reducing atmosphere to obtain a sintered body;
(3) Grinding the sintered body obtained in the step (2) into powder to obtain the CaO-Eu with optimized performance 2+ Near infrared fluorescent powder.
Further, the raw materials in the step (1) are oxides, carbonates, sulfates, phosphates or nitrates of calcium, germanium, tin, lead and europium, and other suitable salts. Wherein the raw materials of the additive are oxides, carbonates, sulfates, phosphates and nitrates of germanium, tin and lead and other salts which can be converted into the oxides of germanium, tin and lead.
Further, the reducing atmosphere in the step (2) is CO or H 2 And N 2 Is (80% N) 2 /20％H 2 )。
Further, the calcining temperature in the step (2) is 1300-1500 ℃, and the calcining time is 1-10 h.
Further, the grinding time in the step (3) is 15-30 min.
The near infrared fluorescent powder with optimized performance prepared by the preparation method has the chemical general formula of CaO: xEu 2 + ,yMO 2 Wherein 0 is<x≤1％,0<y is less than or equal to 8%, M is one of Ge, sn and Pb, and Eu is used 2+ Is the luminescence center.
The application also provides application of the near infrared fluorescent powder with optimized performance in a near infrared LED light-emitting device. The near infrared LED light-emitting device comprises a packaging substrate, an LED chip and fluorescent powder capable of effectively absorbing light emitted by the LED chip and releasing near infrared light.
Further, the fluorescent powder is CaO: eu with optimized performance obtained by the preparation method 2+ Near infrared fluorescent powder.
Further, the LED chip is an InGaN or GaN semiconductor chip.
The preparation flow of the near infrared LED light-emitting device is as follows: mixing the near infrared fluorescent powder with broadband emission characteristics with glue to obtain glue containing the fluorescent powder, coating the glue containing the fluorescent powder on an LED chip, and curing to obtain the near infrared LED light-emitting device.
Further, the glue is epoxy resin or silica gel.
Compared with the prior art, the application has the following beneficial effects:
(1) The application adds GeO 2 、SnO 2 、PbO 2 CaO, eu, as additive and near infrared fluorescent powder 2+ The mixed sintering realizes the excellent performance of high luminous intensity and high thermal stability of the near infrared fluorescent powder. When GeO 2 When the mass percentage is added to be 2%, the luminous intensity is improved to be 2.7 times of the original intensity, and the thermal stability is improved from 47% to 85% at 150 ℃.
(2) CaO: eu with optimized performance based on the present application 2+ The near infrared LED device manufactured by packaging the near infrared fluorescent powder and the blue light chip realizes 319.52mW optical power output under the drive current of 100mA, not only can be applied to the fields of night vision monitoring, medical treatment and the like, but also avoids the defects of other infrared light acquisition modes. The near infrared LED light-emitting device has high light-emitting efficiency and low cost, and can be applied to various types of equipment.
(3) The method has the advantages of simple implementation process, lower cost, obvious effect, easy popularization and application and capability of encouraging more people to focus on Eu 2+ And (5) exploring the performance optimization of the doped fluorescent powder.
Drawings
FIG. 1 is a near infrared fluorescent material CaO:0.2% Eu prepared in comparative example 1 2+ And the performance-optimized near infrared fluorescent material CaO prepared in example 1, 0.2% Eu 2+ ,2％GeO 2 X-ray diffraction pattern of the powder;
FIG. 2 is a near infrared fluorescent material CaO:0.2% Eu prepared in comparative example 1 2+ And the performance-optimized near infrared fluorescent material CaO prepared in example 1, 0.2% Eu 2+ ,2％GeO 2 Excitation and emission spectra of the powder;
FIG. 3 is a near infrared fluorescent material CaO:0.2% Eu prepared in comparative example 1 2+ And the performance-optimized near infrared fluorescent material CaO prepared in example 1, 0.2% Eu 2+ ,2％GeO 2 A luminous integral intensity graph of the powder with temperature;
FIG. 4 is a diagram showing the near infrared fluorescent material CaO:0.2% Eu prepared in comparative example 1 2+ And the near infrared fluorescent material CaO with optimized performance prepared in example 2, 0.2 percent Eu 2+ ,1％SnO 2 Powder X-ray diffraction pattern of (2);
FIG. 5 is a near infrared fluorescent material CaO:0.2% Eu prepared in comparative example 1 2+ And the near infrared fluorescent material CaO with optimized performance prepared in example 2, 0.2 percent Eu 2+ ,1％SnO 2 Is a contrast plot of excitation and emission spectra of (a);
FIG. 6 is a diagram showing the near infrared fluorescent material CaO:0.2% Eu prepared in comparative example 1 2+ And the near infrared fluorescent material CaO with optimized performance prepared in example 2, 0.2 percent Eu 2+ ,1％SnO 2 A graph of integrated luminous intensity as a function of temperature;
fig. 7 is a spectrum chart of the near infrared LED light emitting device manufactured in example 4.
Detailed Description
The present application is further illustrated in the accompanying drawings and detailed description which are to be understood as being merely illustrative of the application and not limiting of its scope, and various modifications to the application, which are equivalent to those skilled in the art, will fall within the scope of the application as defined in the appended claims after reading the application.
Comparative example 1
In this example, the chemical composition formula of the near infrared phosphor for comparison was CaO:0.2% Eu 2+ . 2g CaCO is accurately weighed according to the stoichiometric ratio of each element in the chemical formula 3 (purity 99.9%), 0.006g Eu 2 O 3 The powder raw material (purity 99.99%) was ground in an agate mortar for 30 minutes to mix the raw materials sufficiently and uniformly. Transferring the mixed raw materials into an alumina crucible, and capping and placing in a reducing atmosphere (80% N) 2 /20％H 2 ) Sintering at 1400 deg.c in high temperature reactor for 4 hr, cooling naturally, taking out, grinding again for 20 min to obtain CaO 0.2% Eu 2+ Fluorescent powder.
Example 1
The chemical composition formula of the near infrared fluorescent powder of the embodiment is CaO, 0.2% Eu 2+ ,2％GeO 2 . 2g CaCO is accurately weighed according to the stoichiometric ratio of each element in the chemical formula 3 (purity 99.9%), 0.02g GeO 2 (purity 99.99%), 0.006g Eu 2 O 3 The powder raw material (purity 99.99%) was ground in an agate mortar for 30 minutes to mix the raw materials sufficiently and uniformly. Transferring the mixed raw materials into an alumina crucible, and capping and placing in a reducing atmosphere (80% N) 2 /20％H 2 ) Sintering at 1400 deg.c in high temperature reactor for 4 hr, cooling naturally, taking out, grinding again for 20 min to obtain CaO 0.2% Eu 2+ ,2％GeO 2 Fluorescent powder.
XRD diffraction spectra of the phosphors obtained in comparative example 1 and example 1 are shown in FIG. 1, caO:0.2% Eu 2+ ,2％GeO 2 And CaO 0.2% Eu 2+ The diffraction patterns of (2) are not different, the diffraction peak is consistent with the standard card JCPDS-48-1467 of CaO, and the introduction of 2% GeO is shown 2 The additives of (2) do not introduce a hetero-phase. As shown in FIG. 2, the phosphors obtained in comparative example 1 and example 1 have excitation and emission spectra of the same shape, except that CaO is 0.2% Eu 2+ ,2％GeO 2 Luminous intensity ratio CaO of 0.2% Eu 2+ The improvement is about 2.7 times. And compared with CaO, 0.2% Eu 2+ Fluorescent powder, caO 0.2% Eu at 150 DEG C 2+ ,2％GeO 2 The thermal stability of (a) was improved from 47% to 85%, as shown in fig. 3. The method can achieve the purpose of improving CaO: eu 2+ The near infrared fluorescent powder has high luminous intensity and thermal stability.
Example 2
The chemical composition formula of the near infrared fluorescent powder of the embodiment is CaO, 0.2% Eu 2+ ,1％SnO 2 . 2g CaCO is accurately weighed according to the stoichiometric ratio of each element in the chemical formula 3 (purity 99.9%), 0.015g SnO 2 (purity 99.99%), 0.006g Eu 2 O 3 The powder raw material (purity 99.99%) was ground in an agate mortar for 30 minutes to mix the raw materials sufficiently and uniformly. Transferring the mixed raw materials into an alumina crucible, and capping and placing in a reducing atmosphere (80% N) 2 /20％H 2 ) Sintering at 1400 deg.c in high temperature reactor for 4 hr, cooling naturally, taking out, grinding again for 20 min to obtain CaO 0.2% Eu 2+ ,1％SnO 2 Fluorescent powder.
As shown in FIG. 4, the XRD diffraction spectrum of the phosphor powder is CaO 0.2% Eu 2+ ,1％SnO 2 And CaO 0.2% Eu 2+ The diffraction pattern of (2) is not different, and the diffraction peak is consistent with that of a standard card JCPDS-48-1467 of CaO, which shows that 1 percent of SnO 2 Is not incorporated with a hetero-phase; the two phosphors have the same shape of excitation and emission spectra, as shown in FIG. 5, with the difference that CaO is 0.2% Eu 2+ ,1％SnO 2 Luminous intensity ratio CaO of 0.2% Eu 2+ About 1.6 times higher; and compared with CaO, 0.2% Eu 2+ Fluorescent powder, caO 0.2% Eu at 150 DEG C 2+ ,1％SnO 2 Is thermally stable in (a)The sex was increased from 47% to 73% as shown in fig. 6.
Example 3
The chemical composition formula of the near infrared fluorescent powder of the embodiment is CaO, 0.2 percent Eu 2+ ,1％PbO 2 . 2g CaCO is accurately weighed according to the stoichiometric ratio of each element in the chemical formula 3 (purity 99.9%), 0.022g PbO 2 (purity 99.99%), 0.006g Eu 2 O 3 The powder raw material (purity 99.99%) was ground in an agate mortar for 30 minutes to mix the raw materials sufficiently and uniformly. Transferring the mixed raw materials into an alumina crucible, and capping and placing in a reducing atmosphere (80% N) 2 /20％H 2 ) Sintering at 1400 deg.c in high temperature reactor for 4 hr, cooling naturally, taking out, grinding again for 20 min to obtain CaO 0.2% Eu 2+ ,1％PbO 2 Fluorescent powder.
Likewise, pbO 2 The additives do not introduce a hetero-phase. CaO 0.2% Eu 2+ ,1％PbO 2 Phosphor powder and 0.2% Eu 2+ The fluorescent powder has excitation and emission spectra with the same shape, and is different in that CaO is 0.2 percent Eu 2+ ,1％PbO 2 Luminous intensity ratio CaO of 0.2% Eu 2+ About 1.3 times higher; and compared with CaO, 0.2% Eu 2+ Fluorescent powder, caO 0.2% Eu at 150 DEG C 2+ ,1％PbO 2 The thermal stability of (C) is improved from 47% to 68%.
Example 4
A near infrared LED light emitting device was prepared as follows.
The near infrared LED light-emitting device comprises a packaging substrate, an LED chip and fluorescent powder capable of effectively absorbing light emitted by the LED chip and releasing near infrared light. Wherein the phosphor is the near-red phosphor CaO with optimized performance prepared in the above example 1, 0.2% Eu 2+ ,2％GeO 2 As shown in fig. 2, the near infrared phosphor has a wide excitation spectrum and a wide near infrared emission spectrum. The LED chip is a near ultraviolet and blue light InGaN semiconductor chip, and the light-emitting peak wavelengths of the LED chip are 390-400 nm and 445-475 nm respectively.
The preparation method of the near infrared LED light-emitting device comprises the following specific steps: and uniformly dispersing the near infrared fluorescent powder in silica gel to obtain glue containing the fluorescent powder, covering the glue on the LED chip in a coating mode, and welding a circuit to obtain the near infrared LED light-emitting device. The light emission spectrum is shown in fig. 7, and the output power of the prepared near infrared LED device is as high as 319.52mW under the drive of 100mA current and 13.6V voltage.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application are included in the protection scope of the present application.
Claims (9)
1. Lifting CaO-Eu 2+ A method for preparing near infrared fluorescent powder with luminous intensity and thermal stability is characterized by that it uses CaO: eu 2+ GeO is introduced into near infrared fluorescent powder 2 、SnO 2 Or PbO 2 The material additive compensates oxygen vacancies formed by CaO lattice structures in the high-temperature reduction sintering process, thereby improving the luminous intensity and the thermal stability of the fluorescent powder;
the method specifically comprises the following steps:
(1) According to the chemical general formula CaO xEu 2+ ,yMO 2 Weighing raw materials, fully grinding and uniformly mixing to obtain a raw material mixture; wherein 0 is<x≤1％,0<y is less than or equal to 8%, M is one of Ge, sn and Pb, and Eu is used 2+ Is a luminous center;
(2) Placing the raw material mixture obtained in the step (1) in an alumina crucible or a graphite crucible, and calcining in a high-temperature furnace in a reducing atmosphere to obtain a sintered body;
(3) Grinding the sintered body obtained in the step (2) into powder to obtain the near infrared fluorescent powder with optimized performance.
2. A lifting CaO: eu according to claim 1 2+ The method for the luminous intensity and the thermal stability of the near infrared fluorescent powder is characterized in that the raw materials of the additive in the step (1) are oxides, carbonates, sulfates, phosphates, nitrates of germanium, tin and lead and other materials which can be converted into germanium and tinSalts of lead oxides.
3. A lifting CaO, eu, according to claim 2 2+ The method for the luminous intensity and the thermal stability of the near infrared fluorescent powder is characterized in that the reducing atmosphere in the step (2) is CO or H 2 And N 2 Is a mixed gas of (a) and (b).
4. A lifting CaO, eu, according to claim 2 2+ The method for the luminous intensity and the thermal stability of the near infrared fluorescent powder is characterized in that the calcining temperature in the step (2) is 1300-1500 ℃, and the calcining time is 1-10 h.
5. A lifting CaO, eu, according to claim 2 2+ The method for the luminous intensity and the thermal stability of the near infrared fluorescent powder is characterized in that the grinding time in the step (3) is 15-30 min.
6. A near infrared phosphor having optimized properties, which is obtained by the method according to any one of claims 1 to 5, wherein the phosphor has a chemical formula of CaO: xEu 2+ ,yMO 2 Wherein 0 is<x≤1％,0<y is less than or equal to 8%, M is one of Ge, sn and Pb, and Eu is used 2+ Is the luminescence center.
7. The use of a performance optimized near infrared phosphor of claim 6 in a near infrared LED lighting device.
8. The use of the performance-optimized near infrared phosphor of claim 7 in a near infrared LED lighting device, wherein the near infrared LED lighting device comprises a package substrate, an LED chip, and prepared performance-optimized CaO: eu 2+ Near infrared fluorescent powder.
9. The use of the performance optimized near infrared phosphor of claim 8 in a near infrared LED lighting device, wherein the LED chip is an InGaN or GaN semiconductor chip.
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| Coexistence of the Eu2+ and Eu3+ Centers in the CaO : Eu Powder Phosphor;N. Yamashita;J. Electrochem. Soc;第140卷;第840-843页 * |
| Effect of nano-sized SiO2 on the optical properties of YVO4:Eu3+ phosphors;Seyed Mahdi Rafiaei等;Composite Interfaces;第1-15页 * |
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