CN114540013A - Lifting CaO Eu2+Method for luminous intensity and thermal stability of near-infrared fluorescent powder and application thereof - Google Patents
Lifting CaO Eu2+Method for luminous intensity and thermal stability of near-infrared fluorescent powder and application thereof Download PDFInfo
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- 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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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
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Abstract
The invention belongs to the technical field of inorganic luminescent materials, and particularly relates to a method for increasing CaO to Eu2+A method for luminous intensity and thermal stability of near-infrared fluorescent powder and application thereof. The method uses CaO Eu as the raw material2+Based on near infrared emission fluorescent powder, by adding GeO2、SnO2Or PbO2Additive for compensating CaO and Eu2+Oxygen defects are generated in the sintering process of the reducing atmosphere, 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 invention 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 pumped by a blue light chip.
Description
Technical Field
The invention belongs to the technical field of inorganic luminescent materials, and relates to a near-infrared fluorescent material CaO Eu2+A method for improving the luminous performance and the thermal stability and the application thereof in a near infrared LED luminous device, in particular to a method for improving the luminous performance and the thermal stability of a low-quality CaO Eu to low-internal quantum efficiency and poor thermal stability2+A method for improving the luminous performance and the thermal stability of fluorescent powder.
Background
Near-infrared light is a non-visible light region discovered earlier by people, and due to the fact that the early technical level is not high, spectrum overlapping and analysis are complex due to the influence of frequency doubling and frequency combination, research and application of the near-infrared light are limited to a certain extent. Until the 60 s in the 20 th century, the appearance of commercial instruments and a great deal of work done by Norris and other people put forward the theory that the content of substances and absorption peaks of a plurality of different wavelength points in a near infrared region are in a linear relation, and the NIR diffuse reflection technology is utilized to measure components such as moisture, protein, fat and the like in agricultural products, so that the near infrared spectrum technology is widely applied to the analysis of agricultural and sideline products. In recent years, near-infrared light sources have gained great attention in the context of rapid development of various emerging needs. For example, in the field of face recognition, an infrared light source is used as an active light source to irradiate a face, and then imaging is performed through a camera, so that the influence of different ambient light on imaging can be overcome. And the infrared light is invisible to human eyes, so that the interference to the human eyes is avoided, and the comfort level of a user 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 to infrared light with different wavelengths, the heartbeat, the blood oxygen concentration and the like can be detected by utilizing the infrared light.
At present, the common near-infrared light sources on the market mainly comprise halogen lamps, infrared light-emitting diodes and the like, however, the common near-infrared light sources have the inherent defects that: the halogen lamp has the defects of short service life, large volume, slow response, high energy consumption, low efficiency and the like; the infrared light emitting diode has a narrow emission band, unstable peak wavelength and serious reduction of luminous intensity at high temperature, and cannot be widely applied to the near infrared technology. In recent years, white light LED technology has been greatly developed, and scientists have realized the emission of broadband near-infrared light by adopting LED chips to excite near-infrared fluorescent powder to construct a fluorescence conversion type LED light source. 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 of a miniaturized and quick-response broadband near-infrared light source.
The ions capable of generating near infrared emission in the inorganic fluorescent powder are mainly as follows: pr (Pr)3+,Nd3+,Tm3+,Yb3+Rare earth ion and Cr3+,Ni2+,Mn4+A transition metal ion. Wherein, Pr3+,Nd3+,Tm3+,Yb3+,Mn4+Ions are emitted in sharp lines, so that the wide application of a near-infrared light source is difficult to meet; ni2+The ion has a wide near infrared emission peak, but has low luminous efficiency, and the ion is severely limited to be used as a near infrared light source. In recent years, Cr3+Due to the adjustability of the emission spectrum, the doped near-infrared luminescent material shows better near-infrared luminescent performance in boride, oxide and other materials and shows potential application prospects. Cr (chromium) component3+Ions are widely used as luminescent dopants and luminescent sensitizers in various materials, and have become the focus of many optical spectroscopy and luminescent material research. However, Cr3+The inevitable existence of Cr in the ion-doped phosphor6+Ion, to Cr3+The luminescence of the ions causes severe quenching, resulting in low luminescence efficiency; although some minority Cr3+Doped phosphors such as: ca3Sc2Si3O12:Cr3+Literature (Jia, Z.et al.light: Science)&Applications,2020,9,86) and Na3ScF6:Cr3+(He, F.et al. advanced Functional Materials,2021,31,2103743) achieves an internal quantum efficiency of greater than 90%, but due to Cr3+The forbidden transition of ions 3d-3d results in phosphors with low absorption coefficients and low external quantum efficiencies, hindering their commercialization process.
Eu2+As a well-known activator ion, the phosphor prepared by doping the ion has been widely used in the fields of illumination and display, such as: BaMgAl10O17:Eu2+Blue powder, beta-SiAlON: Eu2+Green powder of Sr [ LiAl ]3N4]:Eu2+Red pink, and the like. But due to Eu2+The 5d-4f transition of the ion depends largely on the crystal field environment of the host, and it is difficult to achieve a large Stokes shift, so Eu is observed in only a few hosts2+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 the commercial application of the near infrared light source is limited (Qiao, J.et. effective incident-near-concerned-emitting-near-phosphor for light-emitting diodes. Nat. Commun.2019,10,5267; Yang, Z.etGiant Red-Shifted emulsion in (Sr, Ba) Y2O4 Eu2+ phosphorous Toward broad Near-isolated luminescence, Adv. Funct. Mater.,2021,2103927). Based on this, to the existing Eu2+The performance of the doped near-infrared fluorescent powder is optimized to obtain the novel near-infrared fluorescent powder with excellent luminous efficiency and thermal stability and a device thereof, and the novel near-infrared fluorescent powder has important guiding significance for the production of related system products.
At present, the methods of matrix regulation (cation doping/anion substitution and the like) and preparation process improvement (step synthesis method, coprecipitation method and the like) are used for improving the comprehensive performance of the fluorescent material, and the like, but the problem that the luminous performance of the existing near-infrared fluorescent material is difficult to improve is not solved. By adding specific additives such as GeO to the fluorescent material2、SnO2Or PbO2Methods for reducing oxygen vacancies to improve luminescence properties and thermal stability properties have not been similarly reported.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide low-quality CaO Eu2+The optimization scheme of the fluorescent powder aims to solve the problem that the luminous efficiency and the thermal stability of the near-infrared fluorescent powder in the prior art are not ideal. And further packaging the optimized fluorescent powder and an InGaN or GaN blue light chip to obtain the high-performance near-infrared LED device.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
lifting CaO Eu2+The method for the luminous intensity and the thermal stability of the near-infrared fluorescent powder comprises the following steps: with CaO Eu as2+Based on near infrared fluorescent powder, by adding special additive GeO2、SnO2Or PbO2To reduce oxygen vacancy in CaO crystal lattice, thereby increasing CaO to Eu2+The luminous intensity of the near-infrared fluorescent powder and the thermal 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: xEu2+,yMO2Weighing the raw materials according to the stoichiometric ratio, 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 performance2+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. The raw materials of the additive are oxides, carbonates, sulfates, phosphates, nitrates and other salts which can be converted into oxides of germanium, tin and lead.
Further, the reducing atmosphere in the step (2) is CO or H2And N2Mixed gas (80% N)2/20％H2)。
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: xEu2 +,yMO2Wherein 0 is<x≤1％,0<y is less than or equal to 8 percent, M is one of Ge, Sn and Pb, and Eu is used2+Is a luminescent center.
The invention 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 method2+Near-infrared fluorescent powder.
Further, the LED chip is an InGaN or GaN semiconductor chip.
The preparation process of the near-infrared LED light-emitting device comprises the following steps: the method comprises the steps of 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 invention has the following beneficial effects:
(1) in the invention, GeO is used2、SnO2、PbO2As an additive and near-infrared fluorescent powder CaO, Eu2+And the excellent performances of high luminous intensity and high thermal stability of the near-infrared fluorescent powder are realized by mixed sintering. When GeO2When the added mass percentage is 2%, the luminous intensity is improved to 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 method2+The near-infrared LED device manufactured by packaging the near-infrared fluorescent powder and the blue light chip realizes 319.52mW luminous power output under 100mA driving current, can be applied to the fields of night vision monitoring, medical treatment and the like, and 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, low cost, obvious effect and easy popularization and application, and encourages more people to focus on Eu2+And (5) exploring the performance optimization of the doped fluorescent powder.
Drawings
FIG. 1 shows CaO of a near-infrared fluorescent material prepared in comparative example 1 at 0.2% Eu2+And the performance optimized near-infrared fluorescent material CaO prepared in the embodiment 1 is 0.2 percent Eu2+,2％GeO2An X-ray diffraction pattern of the powder;
FIG. 2 shows CaO of the near-infrared fluorescent material prepared in comparative example 1 at 0.2% Eu2+And the performance optimized near-infrared fluorescent material CaO prepared in the embodiment 1 is 0.2 percent Eu2+,2％GeO2Excitation and emission spectra of the powder;
FIG. 3 shows CaO of the near-infrared fluorescent material prepared in comparative example 1 at 0.2% Eu2+And the performance-optimized near-infrared fluorescent material CaO prepared in the example 1 is 0.2 percent of Eu2+,2％GeO2A graph of integrated luminescence intensity of the powder as a function of temperature;
FIG. 4 shows CaO of the near-infrared fluorescent material prepared in comparative example 1 at 0.2% Eu2+And the performance-optimized near-infrared fluorescent material CaO prepared in the embodiment 2 is 0.2 percent Eu2+,1％SnO2Powder X-ray diffraction pattern of (a);
FIG. 5 shows CaO of the near-infrared fluorescent material prepared in comparative example 1 at 0.2% Eu2+And the performance-optimized near-infrared fluorescent material CaO prepared in the embodiment 2 is 0.2 percent Eu2+,1％SnO2Excitation and emission spectra of (a);
FIG. 6 shows CaO of the near-infrared fluorescent material prepared in comparative example 1 at 0.2% Eu2+And the performance-optimized near-infrared fluorescent material CaO prepared in the embodiment 2 is 0.2 percent Eu2+,1％SnO2A plot of integrated intensity of luminescence as a function of temperature;
fig. 7 is a spectrum diagram of the near-infrared LED light-emitting device manufactured in example 4.
Detailed Description
The present invention is further illustrated by the following description in conjunction with the accompanying drawings and specific examples, it is to be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention, which is defined in the appended claims as a matter of modification by those skilled in the art after reading this disclosure.
Comparative example 1
In this example, the chemical composition formula of the prepared near-infrared phosphor for comparison is CaO: 0.2% Eu2+. Accurately weighing 2g of CaCO according to the stoichiometric ratio of each element in the chemical formula3(purity 99.9%), 0.006g Eu2O3(purity 99.99%) the raw materials were ground in an agate mortar for 30 minutes to mix the raw materials thoroughly and uniformly. The mixed raw materials were transferred to an alumina crucible, covered and placed in a reducing atmosphere (80% N)2/20％H2) Sintering at 1400 deg.C for 4 hr in high temperature reaction furnace, naturally cooling, taking out, grinding for 20 min to obtain CaO of 0.2% Eu2+And (3) fluorescent powder.
Example 1
This exampleThe chemical composition formula of the near-infrared fluorescent powder is CaO, 0.2 percent Eu2+,2％GeO2. Accurately weighing 2g of CaCO according to the stoichiometric ratio of each element in the chemical formula3(purity 99.9%), 0.02g GeO2(purity 99.99%) 0.006g Eu2O3(purity 99.99%) the raw materials were ground in an agate mortar for 30 minutes to mix the raw materials thoroughly and uniformly. The mixed raw materials were transferred to an alumina crucible, covered and placed in a reducing atmosphere (80% N)2/20％H2) Sintering at 1400 deg.C for 4 hr in high temperature reaction furnace, naturally cooling, taking out, and grinding for 20 min to obtain CaO 0.2% Eu2+,2％GeO2And (3) fluorescent powder.
XRD diffraction spectra of the phosphors obtained in comparative example 1 and example 1 are shown in FIG. 1, CaO being 0.2% Eu2+,2％GeO2And CaO 0.2% Eu2+The diffraction spectrum of the product has no difference, the diffraction peak is consistent with that of standard card JCPDS-48-1467 of CaO, which indicates that 2 percent GeO is introduced2The additive of (3) does 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% Eu2+,2％GeO2The luminous intensity ratio of CaO to 0.2% Eu2+The improvement is about 2.7 times. And 0.2% Eu compared with CaO2+Fluorescent powder, CaO 0.2% Eu at 150 ℃2+,2％GeO2The thermal stability of (A) was improved from 47% to 85%, as shown in FIG. 3. Shows that the preparation method of the invention can improve CaO to Eu2+The near infrared fluorescent powder has high luminous intensity and thermal stability.
Example 2
The chemical composition formula of the near-infrared phosphor of the embodiment is CaO and 0.2% Eu2+,1％SnO2. Accurately weighing 2g of CaCO according to the stoichiometric ratio of each element in the chemical formula3(purity 99.9%) 0.015g SnO2(purity 99.99%) 0.006g Eu2O3(purity 99.99%) the raw materials were ground in an agate mortar for 30 minutes to mix the raw materials thoroughly and uniformly. The mixed raw materials were transferred to an alumina crucible, covered and placed in a reducing atmosphere (80% N)2/20％H2) In a high-temperature reaction furnaceSintering at 1400 deg.C for 4 hr, naturally cooling, taking out, and grinding for 20 min to obtain CaO 0.2% Eu2+,1％SnO2And (3) fluorescent powder.
The XRD diffraction spectrum of the phosphor is shown in FIG. 4, CaO is 0.2% Eu2+,1％SnO2And CaO 0.2% Eu2+The diffraction spectrum of the composite has no difference, the diffraction peak of the composite is consistent with that of standard card JCPDS-48-1467 of CaO, and the 1 percent SnO is illustrated2The additive of (2) does not introduce a hetero phase; the two phosphors have excitation and emission spectra of the same shape, as shown in FIG. 5, except that CaO is 0.2% Eu2+,1％SnO2Luminous intensity ratio of CaO to 0.2% Eu2+Improved by about 1.6 times; and 0.2% Eu compared with CaO2+Fluorescent powder, CaO 0.2% Eu at 150 ℃2+,1％SnO2The thermal stability of (A) was improved from 47% to 73%, as shown in FIG. 6.
Example 3
The chemical composition formula of the near-infrared phosphor of this embodiment is CaO 0.2% Eu2+,1％PbO2. Accurately weighing 2g of CaCO according to the stoichiometric ratio of each element in the chemical formula3(purity 99.9%) 0.022g PbO2(purity 99.99%) 0.006g Eu2O3(purity 99.99%) the raw materials were ground in an agate mortar for 30 minutes to mix the raw materials thoroughly and uniformly. The mixed raw materials were transferred to an alumina crucible, covered and placed in a reducing atmosphere (80% N)2/20％H2) Sintering at 1400 deg.C for 4 hr in high temperature reaction furnace, naturally cooling, taking out, grinding for 20 min to obtain CaO of 0.2% Eu2+,1％PbO2And (3) fluorescent powder.
Likewise, PbO2The additive does not introduce a hetero-phase. CaO 0.2% Eu2+,1％PbO2Fluorescent powder and CaO 0.2% Eu2+The phosphor has excitation and emission spectra of the same shape, with the difference that CaO is 0.2% Eu2+,1％PbO2The luminous intensity ratio of CaO to 0.2% Eu2+Improved by about 1.3 times; and 0.2% Eu compared with CaO2+Fluorescent powder, CaO 0.2% Eu at 150 ℃2+,1％PbO2The thermal stability of (A) 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% Eu2+,2％GeO2As shown in fig. 2, the near-infrared phosphor has a broad excitation spectrum and a broad 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 method for preparing the near-infrared LED light-emitting device comprises the following specific steps: and uniformly dispersing the near-infrared fluorescent powder in the 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-emitting spectrum of the near-infrared LED device is shown in FIG. 7, and the output power of the prepared near-infrared LED device is 319.52mW under the drive of 100mA current and 13.6V voltage.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. Lifting CaO Eu2+The method for the luminous intensity and the thermal stability of the near-infrared fluorescent powder is characterized in that the luminous intensity and the thermal stability of the near-infrared fluorescent powder are obtained by adding CaO, Eu2+GeO is introduced into near-infrared fluorescent powder2、SnO2Or PbO2The material additive makes up oxygen vacancy formed by a CaO lattice structure in the high-temperature reduction sintering process, so that the luminous intensity and the thermal stability of the fluorescent powder are improved.
2. Eu as a lifting agent for CaO according to claim 12+The method for the luminous intensity and the thermal stability of the near-infrared fluorescent powder is characterized by comprising the following steps of:
(1) according to the chemical general formula CaO: xEu2+,yMO2Weighing the raw materials according to the stoichiometric ratio, 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) and (3) grinding the sintered body obtained in the step (2) into powder to obtain the near-infrared fluorescent powder with optimized performance.
3. Eu as a lifting agent for CaO according to claim 12+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 and other salts which can be converted into oxides of germanium, tin and lead.
4. Eu as a lifting agent for CaO according to claim 22+The method for improving 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 H2And N2The mixed gas of (1).
5. Eu as a lifting agent for CaO according to claim 22+The method for improving 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 hours.
6. Eu as a lifting agent for CaO according to claim 22+The method for improving 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.
7. The near-infrared fluorescent powder with optimized performance prepared by the preparation method of claims 1-6, which is characterized in that the chemical general formula is CaO: xEu2+,yMO2Wherein 0 is<x≤1％,0<y is less than or equal to 8 percent, and M is Ge or SnPb and with Eu2+Is a luminescent center.
8. The use of the performance optimized near-infrared phosphor of claim 7 in a near-infrared LED lighting device.
9. The application of the performance-optimized near-infrared fluorescent powder in a near-infrared LED light-emitting device according to claim 8, wherein the near-infrared LED light-emitting device comprises a packaging substrate, an LED chip and prepared performance-optimized CaO, Eu2+Near-infrared fluorescent powder.
10. The use of the performance optimized near-infrared phosphor in a near-infrared LED light emitting device according to claim 9, wherein the LED chip is an InGaN or GaN semiconductor chip.
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| CN115873595A (en) * | 2022-12-12 | 2023-03-31 | 华南理工大学 | Adjustable red light and near-infrared rare earth luminescent material, preparation method thereof and infrared LED device |
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| US20090085009A1 (en) * | 2005-06-09 | 2009-04-02 | Niigata University | Fluorescent substance for light-emitting diode |
| CN110093154A (en) * | 2019-05-23 | 2019-08-06 | 东北大学 | Mg2+/Si4+Replace Ga3+Mix Cr3+Gallic acid zinc-base near-infrared long-afterglow material and preparation method |
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| US20090085009A1 (en) * | 2005-06-09 | 2009-04-02 | Niigata University | Fluorescent substance for light-emitting diode |
| CN110093154A (en) * | 2019-05-23 | 2019-08-06 | 东北大学 | Mg2+/Si4+Replace Ga3+Mix Cr3+Gallic acid zinc-base near-infrared long-afterglow material and preparation method |
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| CN115873595A (en) * | 2022-12-12 | 2023-03-31 | 华南理工大学 | Adjustable red light and near-infrared rare earth luminescent material, preparation method thereof and infrared LED device |
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