CN108424770B - Near-infrared fluorescent powder with broadband emission characteristic and preparation method and application thereof - Google Patents
Near-infrared fluorescent powder with broadband emission characteristic and preparation method and application thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
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- 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
- C09K11/7706—Aluminates
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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- 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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Abstract
A near-infrared fluorescent powder with broadband emission characteristic and a preparation method and application thereof belong to the technical field of luminescent materials. The problem of how to provide the near-infrared fluorescent powder which is suitable for being excited by near ultraviolet and blue light chips and has the broadband emission characteristic, the preparation method and the application thereof is solved. The near-infrared fluorescent powder has a chemical general formula as follows: ca2+xLn1‑x‑yZr2‑xAl3O12:xCr3+,yCe3+And with Cr3+Is a luminous center; in the formula, Ln is Y3+、Lu3+And Gd3+X and y are mole fractions, and the value ranges are respectively as follows: 0<x is less than or equal to 0.15, and y is less than or equal to 0.1 and more than or equal to 0. The fluorescent powder can be used as a light conversion material of a near ultraviolet LED chip or a blue light LED chip, a broadband near infrared light source is realized, and the requirements of applications such as blood oxygen detection or coherence tomography on an infrared light source with broadband emission characteristics are met.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to near-infrared fluorescent powder with broadband emission characteristics, and a preparation method and application thereof.
Background
Near-infrared light sources have gained great attention from people under the background of rapid development of various emerging demands. 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, the characteristic that human tissues have different absorption capacities to infrared light with different wavelengths is utilized, so that the heartbeat, the blood oxygen concentration and the like can be detected by utilizing the infrared light. The infrared light source is also applied to the aspects of safety monitoring, structured light technology, automatic driving assistance system, optical fiber communication, information processing, biosensor, fluorescence immunoassay and the like.
The current near-infrared light source mainly comprises a tungsten lamp, an infrared LED and an infrared laser. Tungsten lamps are traditional infrared light sources, have the advantages of wide emission spectrum and high brightness, but have low efficiency, large volume and short service life, and the spectrum contains a large amount of visible light. The infrared LED and the infrared laser have the advantages of high efficiency and small volume, and are rapidly popularized in application in recent years. However, the bandwidth of infrared light emitted by infrared LEDs and infrared lasers is very narrow, which limits their application in some fields. For example, an infrared light source with a broadband emission characteristic is required in the optical coherence tomography technology, and two beams of coherent infrared light with different wave bands can be provided simultaneously.
In view of the foregoing, there is a need for an infrared light source with broadband emission characteristics.
Disclosure of Invention
The invention aims to provide a near-infrared fluorescent powder which is suitable for being excited by a near-ultraviolet chip and a blue-light chip and has a broadband emission characteristic, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the near-infrared fluorescent powder with broadband emission characteristics has a chemical general formula as follows: ca2+xLn1-x-yZr2- xAl3O12:xCr3+,yCe3+And with Cr3+Is a luminous center;
in the formula, Ln is Y3+、Lu3+And Gd3+X and y are mole fractions, and the value ranges are respectively as follows: 0<x≤0.15，0≤y≤0.1。
The preparation method of the near-infrared fluorescent powder with the broadband emission characteristic comprises the following steps:
step one, respectively weighing Ca according to stoichiometric ratio2+Compound of (1), containing Ln3+Compound of (1), containing Zr2+Compound of (2) and containing Al3+Compound of (1), containing Cr3+And containing Ce2+Grinding and uniformly mixing the compound (1) to obtain a mixture;
step two, calcining the mixture for 3-8 hours at 1400-1650 ℃ in a reducing atmosphere to obtain a sintered body;
and step three, grinding the sintered body, washing, filtering and drying to obtain the near-infrared fluorescent powder with the broadband emission characteristic.
Preferably, CO or H is used2And N2The mixed gas of (2) is used as a reducing atmosphere.
Preferably, the sintering temperature is 1550-1600 ℃ and the time is 4-6 h.
The application of the near-infrared fluorescent powder with the broadband emission characteristic comprises the steps of mixing the near-infrared fluorescent powder with the broadband emission characteristic with glue to obtain glue containing the fluorescent powder, coating the glue containing the fluorescent powder on an LED chip, and curing to obtain a near-infrared LED light source;
the LED chip is a near ultraviolet LED chip or a blue light LED chip.
Preferably, the glue is epoxy resin or silica gel.
Preferably, in the fluorescent powder-containing glue, the mass fraction of the fluorescent powder is 10-40%.
Preferably, the LED chip is of a forward mounting structure or a flip chip structure, and the wavelength of the LED chip is 400nm-470 nm.
Preferably, the near-infrared LED light source further comprises an LED support, and the LED chip is adhered to the LED support and is connected with the positive electrode and the negative electrode of the LED support through metal wires or conductive adhesive.
Preferably, the LED holder is an SMD holder or a COB holder.
Compared with the prior art, the invention has the beneficial effects that:
the near infrared fluorescent powder with wide band emitting characteristic features that transition metal Cr is used3+The ions are used as a luminescence center, and the ions are placed in an octahedral coordination matrix material with a weak field environment by utilizing the characteristic that the 3d orbit of the ions is regulated and controlled by the size of a crystal field, so that broadband near-infrared emission can be realized. For strengthening Cr3+Further introducing a sensitizer Ce3+Using Ce3+Has the characteristic of strong 4f-5d transition absorption, and transfers the absorbed energy to the luminescence center Cr3+And the absorption of the fluorescent powder can be effectively enhanced. With Ca2+Substituted Ln3+Ions, compensating for Cr3+Substituted for Zr4+Temporal charge mismatch, stabilization of Cr3+The valence state of (2) plays a role in charge compensation and radius compensation.
The near-infrared fluorescent powder with the broadband emission characteristic can emit the broadband near-infrared light of 700nm-850nm under the excitation of the wavelength light of 400nm-470 nm.
The near-infrared fluorescent powder with the broadband emission characteristic can be used as a light conversion material of a near-ultraviolet LED chip and a blue-light LED chip, a broadband near-infrared light source is realized, the problem of narrow bandwidth of an infrared LED and an infrared laser at present is solved, and the requirement of the broadband infrared light source in applications such as blood oxygen detection or coherence tomography can be met.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows Ca in example 12.02Lu0.98Zr1.98Al3O12:0.02Cr3+XRD diffractogram of.
FIG. 2 shows Ca in example 12.02Lu0.98Zr1.98Al3O12:0.02Cr3+Emission spectrum (450nm excitation).
FIG. 3 shows Ca in example 12.02Lu0.98Zr1.98Al3O12:0.02Cr3+Excitation spectrum of (monitoring 760 nm).
FIG. 4 shows Ca in example 12.02Lu0.98Zr1.98Al3O12:0.02Cr3+And (3) an electroluminescence spectrogram of the packaged white light LED.
FIG. 5 shows Ca in example 22.02Lu0.96Zr1.98Al3O12:0.02Cr3+,0.02Ce3+And (3) an electroluminescence spectrogram of the packaged white light LED.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the detailed description, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention and not to limit the claims to the invention.
The near-infrared fluorescent powder with the broadband emission characteristic has the chemical general formula as follows: ca2+xLn1-x-yZr2-xAl3O12:xCr3+,yCe3+And with Cr3+Is a luminous center; in the formula, Ln is Y3+、Lu3+And Gd3+X and y are mole fractions, and the value ranges are respectively as follows: 0<x is 0.15 or less, y is 0 or less 0.1 or less, preferably 0.04<x is less than or equal to 0.1, and y is less than or equal to 0 and less than or equal to 0.05. The fluorescent powder emits 700nm-850nm broadband near infrared light under the excitation of light with the wavelength within the range of 400nm-470 nm.
The preparation method of the near-infrared fluorescent powder with the broadband emission characteristic comprises the following steps:
step one, respectively weighing Ca according to stoichiometric ratio2+Compound of (1), containing Ln3+Compound of (1), containing Zr2+Compound of (1), containing Al3+Compound of (2) containing Cr3+And containing Ce2+Is ground andmixing uniformly to obtain a mixture;
wherein, usually, Ca is contained2+The compound (B) is Ca-containing2+One or any combination of the oxides, carbonates, nitrates, halides of (a); containing Lu3+The compound of (A) is Lu-containing3+One or any combination of the oxides, carbonates, nitrates, halides of (a); containing Zr2+The compound of (A) is a compound containing Zr2+One or any combination of the oxides, carbonates, nitrates, halides of (a); containing Al3+The compound of (A) is a compound containing Al3+One or any combination of the oxides, carbonates, nitrates, halides of (a); containing Cr3+The compound of (A) is a compound containing Cr3+One or any combination of the oxides, carbonates, nitrates, halides of (a); containing Ce2+The compound of (A) is Ce-containing2+One of an oxide, a carbonate, a nitrate, a halide, or any combination thereof.
Step two, calcining the mixture for 3-8 hours at 1400-1650 ℃ in a reducing atmosphere to obtain a sintered body;
wherein CO or H is used2And N2The mixed gas is used as reducing atmosphere, the sintering temperature is preferably 1550-1600 ℃, and the time is preferably 4-6 h.
And step three, grinding the sintered body, washing, filtering and drying to obtain the near-infrared fluorescent powder with the broadband emission characteristic.
The invention also provides the application of the near-infrared fluorescent powder with the broadband emission characteristic, the near-infrared fluorescent powder with the broadband emission characteristic is mixed with glue to obtain glue containing the fluorescent powder, then the glue containing the fluorescent powder is coated on an LED chip, and a near-infrared LED light source is obtained after curing;
the LED chip is a near ultraviolet LED chip or a blue LED chip, and can be of a forward mounting structure or an inverted mounting structure, and the wavelength is 400nm-470 nm; the glue is a common glue which can be obtained commercially, and is preferably epoxy resin or silica gel; in the fluorescent powder-containing glue, the content of the fluorescent powder is not particularly limited, the fluorescent powder can play a role as long as the fluorescent powder is added, and the mass fraction of the fluorescent powder is preferably 10-40%. The near-infrared LED light source also comprises an LED support, the LED chip is bonded on the LED support and is connected with the anode and the cathode of the LED support through metal wires or conductive adhesive, and the LED support can be an SMD support, a COB support and the like.
The invention is further illustrated below with reference to examples and figures.
Example 1
Ca2.02Lu0.98Zr1.98Al3O12:0.02Cr3+The preparation method comprises the following steps: weighing CaCO according to stoichiometric ratio3、Lu2O3、ZrO2、Al2O3And Cr2O3Fully grinding, uniformly mixing, placing into a high-purity corundum crucible, and placing in a furnace H2And N2Keeping the temperature of 1400 ℃ for 5h under the mixed gas, cooling and discharging, slightly grinding, washing, filtering and drying to obtain the near-infrared fluorescent powder with broadband emission characteristics.
XRD analysis is carried out on the near-infrared fluorescent powder obtained in the example 1, and an XRD diffraction pattern is shown in figure 1; as can be seen from FIG. 1, the phosphor is pure phase Ca2LuZr2Al3O12And (5) structure.
The emission spectrum and the excitation spectrum of the near-infrared phosphor obtained in example 1 are analyzed, and the results are shown in fig. 2 and fig. 3, and it can be seen from fig. 2 that the phosphor comprises three effective excitation bands of 200-250nm, 400-500nm and 570-700 nm; from FIG. 3, it can be seen that the emission spectrum of the phosphor covers 700-850 nm.
The glue containing the fluorescent powder is obtained by mixing the near-infrared fluorescent powder in the embodiment 1 with epoxy resin glue, the glue containing the fluorescent powder is coated on a 460nm blue light LED chip, then the blue light LED chip is bonded and fixed in a 5730SMD LED support, and the blue light LED chip is connected with the anode and the cathode of the support through gold threads, so that the near-infrared LED light source is obtained. The emission characteristics of the near-infrared LED light source were analyzed, as shown in fig. 4, and it can be seen from fig. 4 that the near-infrared light emitting source had a broadband emission characteristic.
Example 2
Ca2.02Lu0.96Zr1.98Al3O12:0.02Cr3+,0.02Ce3+The preparation method comprises the following steps: weighing CaCO according to stoichiometric ratio3、Lu2O3、ZrO2、Al2O3、CeO2And Cr2O3Fully grinding and uniformly mixing the weighed raw materials, placing the mixture into a high-purity corundum crucible, preserving the heat for 4 hours at 1600 ℃ under the CO reduction condition, slightly grinding the mixture after cooling and discharging, and washing, filtering and drying the mixture to obtain the near-infrared fluorescent powder with the broadband emission characteristic.
The glue containing the fluorescent powder is obtained after the near-infrared fluorescent powder in the embodiment 2 is mixed with the epoxy resin glue, the glue containing the fluorescent powder is coated on a 410nm blue light LED chip, then the LED chip is bonded and fixed in a 19 x 19mm mirror aluminum COB support and is connected with the positive electrode and the negative electrode of the support through gold threads, and a near-infrared LED light source is obtained. The emission characteristics of the near-infrared LED light source were analyzed, as shown in fig. 5, and it can be seen from fig. 5 that the near-infrared light emitting source had a broadband emission characteristic.
Example 3 to example 15: the preparation steps are the same as those of example 1, the chemical formulas, the synthesis temperature and the roasting time are shown in the attached table 1, and the raw materials used in examples 3 to 15 are oxides or salt compounds of each metal element, which has no influence on the results.
TABLE 1 chemical formulas, synthesis temperatures and calcination times for examples 1-15
The embodiment shows that the fluorescent powder has simple preparation method, no pollution, low cost and stable chemical performance, and can become a near-infrared fluorescent powder luminescent material with broadband emission characteristic and very practical value.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The near-infrared fluorescent powder with broadband emission characteristic is characterized in that the chemical general formula of the fluorescent powder is as follows: ca2+ xLn1-x-yZr2-xAl3O12:xCr3+,yCe3+And with Cr3+Is a luminous center;
in the formula, Ln is Y3+、Lu3+And Gd3+X and y are mole fractions, and the value ranges are respectively as follows: 0<x≤0.15，0≤y≤0.1。
2. The method for preparing a near-infrared phosphor having a broadband emission characteristic as claimed in claim 1, comprising the steps of:
step one, respectively weighing Ca according to stoichiometric ratio2+Compound of (1), containing Ln3+Compound of (1), containing Zr2+Compound of (2) and containing Al3+Compound of (1), containing Cr3+And containing Ce2+Grinding and uniformly mixing the compound (1) to obtain a mixture;
step two, calcining the mixture for 3-8 hours at 1400-1650 ℃ in a reducing atmosphere to obtain a sintered body;
and step three, grinding the sintered body, washing, filtering and drying to obtain the near-infrared fluorescent powder with the broadband emission characteristic.
3. The method of claim 2, wherein CO or H is used2And N2The mixed gas of (2) is used as a reducing atmosphere.
4. The method of claim 2, wherein the sintering temperature is 1550-1600 ℃ and the sintering time is 4-6 h.
5. The application of the near-infrared fluorescent powder with the broadband emission characteristic as claimed in claim 1, wherein the near-infrared fluorescent powder with the broadband emission characteristic is mixed with glue to obtain glue containing the fluorescent powder, then the glue containing the fluorescent powder is coated on an LED chip, and a near-infrared LED light source is obtained after curing;
the LED chip is a near ultraviolet LED chip or a blue light LED chip.
6. The use of the near-infrared phosphor with broadband emission characteristics as claimed in claim 5, wherein the glue is epoxy or silica gel.
7. The application of the near-infrared phosphor with broadband emission characteristic as claimed in claim 5, wherein the mass fraction of the phosphor in the phosphor-containing glue is 10-40%.
8. The use of the near-infrared phosphor with broadband emission characteristics according to claim 5, wherein the LED chip is of a face-up structure or a flip-chip structure, and the wavelength is 400nm to 470 nm.
9. The application of the near-infrared fluorescent powder with broadband emission characteristics as claimed in claim 5, wherein the near-infrared LED light source further comprises an LED support, and the LED chip is adhered to the LED support and connected with the positive electrode and the negative electrode of the LED support through metal wires or conductive adhesive.
10. The use of a near-infrared phosphor with broadband emission characteristics according to claim 5, wherein the LED support is an SMD support or a COB support.
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| PCT/CN2019/073183 WO2019144933A1 (en) | 2018-01-29 | 2019-01-25 | Near-infrared fluorescent powder, preparation method for near-infrared fluorescent powder and use of same |
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| WO2019144933A1 (en) * | 2018-01-29 | 2019-08-01 | 中国科学院长春光学精密机械与物理研究所 | Near-infrared fluorescent powder, preparation method for near-infrared fluorescent powder and use of same |
| WO2020037874A1 (en) * | 2018-08-23 | 2020-02-27 | 有研稀土新材料股份有限公司 | Near-infrared light-emitting material and light-emitting device containing said light-emitting material |
| CN109192844A (en) * | 2018-08-30 | 2019-01-11 | 合肥工业大学智能制造技术研究院 | One kind is repaired and regenerated LED light emitting device and application for retina cell |
| CN110970541B (en) * | 2018-09-29 | 2023-04-21 | 有研稀土新材料股份有限公司 | Semiconductor light source and optical device prepared by same |
| CN109874803B (en) * | 2019-04-15 | 2020-05-05 | 兰州大学 | Fluorescent powder capable of promoting plant growth and preparation method thereof |
| CN111073644B (en) * | 2019-12-28 | 2021-08-20 | 中国科学院长春光学精密机械与物理研究所 | Near-infrared fluorescent powder, preparation and application methods, near-infrared light source and preparation method of near-infrared white light source |
| TWI761979B (en) | 2020-09-30 | 2022-04-21 | 隆達電子股份有限公司 | Phosphate phosphor, light emitting device, and detecting device |
| CN112322283B (en) * | 2020-11-06 | 2021-07-20 | 旭宇光电（深圳）股份有限公司 | Near-infrared fluorescent powder, preparation method thereof and light-emitting device |
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| CN105567236A (en) * | 2014-10-15 | 2016-05-11 | 有研稀土新材料股份有限公司 | Garnet type fluorescent powder, method for preparing same and device comprising same |
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