CN113403073B - Broadband short-wave infrared luminescent material and preparation method and application thereof - Google Patents

Broadband short-wave infrared luminescent material and preparation method and application thereof Download PDF

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CN113403073B
CN113403073B CN202110819657.0A CN202110819657A CN113403073B CN 113403073 B CN113403073 B CN 113403073B CN 202110819657 A CN202110819657 A CN 202110819657A CN 113403073 B CN113403073 B CN 113403073B
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luminescent material
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wave infrared
infrared luminescent
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CN113403073A (en
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梁延杰
苗世海
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Shandong University
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
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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
    • C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
    • C09K11/71—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus also containing alkaline earth metals
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    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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

Abstract

The invention belongs to the technical field of short-wave infrared luminescent materials, and relates to a broadband short-wave infrared luminescent material, and a preparation method and application thereof. The broadband short-wave infrared luminescent material comprises: li1‑zAzMg1‑x‑y‑ cBcPO4:xCr3+,yNi2+Wherein x is more than or equal to 0 and less than or equal to 10 percent, y is more than 0 and less than or equal to 0.1 percent, and x and y are respectively Cr and Ni in (LiA) (MgB) PO4Mole percent of (c); z is more than or equal to 0<1，A+Is Na+And K+One or more of (a); c is not less than 0<1，B2+Is Ca2+，Sr2+And Ba2+One or more of (a). The luminescent material can effectively absorb visible light and near infrared light of 350-800 nm, generates short-wave infrared light emission with the main peak wavelength near 1350nm, and can be packaged with a blue light chip into a short-wave infrared LED device. In addition, the preparation method has the characteristics of simple process, low manufacturing cost, no environmental pollution, high product purity, good uniformity and the like, and can be widely applied to the technical field of short-wave infrared light. The blue light excited broadband short wave infrared luminescent material is used in night vision, optical anti-counterfeiting, biomedicine and short waveThe infrared spectroscopy technology and other fields have good application prospects.

Description

Broadband short-wave infrared luminescent material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of short-wave infrared luminescent materials, and relates to a broadband short-wave infrared luminescent material, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Short-wave infrared (SWIR, wavelength range 900-. Presently, the SWIR light sources used for spectral analysis are mainly incandescent halogen lamps, lasers and Light Emitting Diodes (LEDs), but at the same time they each have advantages and disadvantages: halogen lamps can produce continuous emission from visible light to infrared light, but are large in size, short in life, low in efficiency and high in bulb temperature; laser diodes or fiber lasers have very high radiance, but the coherence and narrow-band emission spectrum of laser beams hinder their application in industrial vision; supercontinuum lasers also cannot meet wide applications due to their small divergence angle, high power consumption, and relatively high cost. The SWIR-LED chip has the advantages of small size and suitability for intelligent SWIR devices, and is an attractive solid-state light source, but the application of the SWIR-LED chip in the SWIR spectrum technology field is limited due to the characteristics of narrow spectral coverage (<50nm), low output power, high cost and the like. Compared with the SWIR light source, the fluorescent powder conversion LED based on the combination of the commercial high-power blue LED chip and the SWIR fluorescent powder is gradually becoming an ideal choice of a novel solid SWIR light source, and by means of a mature fluorescent powder conversion white light LED technology, the obtained SWIR device has high output power, low price and long service life. Despite these advantages, the development of SWIR phosphors with desirable absorption bands in the visible region (especially blue), broad-band emission in the SWIR region, and high luminous efficiency remains a challenging task.
Doping lanthanides in general can achieve SWIR emission, including Yb3+、Nd3+、Pr3+、Sm3+、Tm3+And Er3+Ions. These lanthanide-doped emitters are typically located in inorganic matrices (e.g., optical glasses and ceramics). However, the SWIR phosphor conversion LED obtained by combining the visible light LED and the glass phosphor doped with lanthanide ions has a narrow spectral bandwidth and low efficiency due to the 4f-4f forbidden band transition, which limits its wide application. In recent years, trivalent chromium (Cr)3+) Is becoming a good Near Infrared (NIR) luminescence center because of Cr3+The activated inorganic material can produce a broad band emission from-700 nm to-1000 nm, with the position of the main peak of the emission depending on the crystal field strength of the host lattice. In recent years, with the continuous research of researchers, a series of Cr having high luminous efficiency and suitable wavelength have been prepared and reported3+The doped broadband near-infrared luminescent material has certain application potential in economic and efficient portable and miniaturized near-infrared light-emitting diodes. However, the optimum emission peak position of these phosphors has to date only reached around 1100nm at the maximum, which is far from sufficient for SWIR spectroscopy applications. At the same time, by divalent nickel (Ni)2+) The doping of ions can realize the short-wave infrared luminescence of the material, Ni2+The activated inorganic material can produce tunable emissions with wavelengths greater than 1000 nm. However, with respect to Cr3+/Ni2+The research of the co-doped broadband near-infrared luminescent material and the development and application of the co-doped broadband near-infrared luminescent material in the SWIR LED device are relatively slow, and the research cannot meet the requirements of advanced applications such as night vision monitoring, short-wave infrared spectroscopy technology and biomedical imaging.
Disclosure of Invention
In order to solve the problems of short emission wavelength (emission peak value less than 1100nm), small emission half-peak width and the like of a chromium-doped near-infrared luminescent material in the prior art, the invention provides a broadband short-wave infrared luminescent material, a preparation method and application thereof, the short-wave infrared (SWIR) luminescent material can be efficiently excited by blue light, a main emission area is positioned in a 700-1600nm broadband infrared area, the luminescence peak value is positioned at 1350nm, and the optimal excitation peak is positioned at 450 nm.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the present invention, the present invention provides a broadband short-wave infrared luminescent material, comprising:
Li1-zAzMg1-x-y-cBcPO4:xCr3+,yNi2+wherein x is more than or equal to 0 and less than or equal to 10 percent, y is more than 0 and less than or equal to 1 percent, and x and y are respectively Cr and Ni in (LiA) (MgB) PO4Mole percent of (c); z is more than or equal to 0<1，A+Is Na+And K+One or more of (a); c is not less than 0<1，B2+Is Ca2+，Sr2+And Ba2+One or more of (a).
In a second aspect of the present invention, the present invention provides a method for preparing a broadband short-wave infrared luminescent material, comprising: mixing the materials, pre-sintering at low temperature, and sintering at high temperature to obtain the broadband short-wave infrared luminescent material.
In a third aspect of the invention, the invention provides a broadband short-wave infrared LED device, which at least comprises a light emitting source and a phosphor, wherein the phosphor at least comprises the broadband short-wave infrared light emitting material.
One or more embodiments of the present invention have the following advantageous effects:
(1) the material prepared by the invention can generate light emission in a short wave infrared region (700-.
(2) The broadband short-wave infrared luminescent material prepared by the invention has the advantages of high phase purity, good crystallization property, high short-wave infrared luminescent intensity, simple and easy preparation method, low requirement on equipment, no need of atmosphere protection, no by-product, suitability for large-scale industrial production and good application prospect.
(3) The short-wave infrared LED device prepared by the invention has simple preparation method, can emit short-wave infrared light with different intensities under different currents, and can be used in the fields of night vision, optical anti-counterfeiting, biomedicine, short-wave infrared spectroscopy technology and the like.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is an X-ray diffraction pattern of a broadband short-wave infrared luminescent material prepared in example 1 of the present invention;
FIG. 2 shows the excitation spectrum and emission spectrum of a broadband short-wave infrared luminescent material prepared in example 1 of the present invention;
FIG. 3 is a broadband short-wave infrared LED device prepared in example 1 of the present invention;
fig. 4 is a schematic diagram of a broadband short-wave infrared LED device prepared in embodiment 1 of the present invention in the fields of night vision and optical anti-counterfeiting application.
FIG. 5 shows the excitation spectrum and the emission spectrum of a broadband short-wave infrared luminescent material prepared in example 2 of the present invention;
FIG. 6 shows the excitation spectrum and the emission spectrum of a broadband short-wave infrared luminescent material prepared in example 3 of the present invention;
FIG. 7 shows the excitation spectrum and the emission spectrum of a broadband short-wave infrared luminescent material prepared in example 4 of the present invention;
FIG. 8 shows the excitation spectrum and the emission spectrum of a broadband short-wave infrared luminescent material prepared in example 5 of the present invention;
FIG. 9 shows the excitation spectrum and the emission spectrum of a broadband short-wave infrared luminescent material prepared in example 6 of the present invention;
FIG. 10 shows the excitation spectrum and the emission spectrum of a broadband short-wave infrared luminescent material prepared in example 7 of the present invention;
FIG. 11 shows the excitation spectrum and the emission spectrum of a broadband short-wave infrared luminescent material prepared in example 8 of the present invention;
FIG. 12 shows the excitation spectrum and the emission spectrum of the broadband short-wave infrared luminescent material prepared in example 9 of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the defects of few types, narrow half-peak width, need of special light source excitation and the like of the existing broadband shortwave infrared luminescent material, the invention provides a broadband shortwave infrared luminescent material, a preparation method and application thereof, in order to solve the problem of the broadband shortwave infrared luminescent material in the prior art, the broadband shortwave infrared luminescent material can be efficiently excited by blue light, a main emission area is positioned in a 700-1600nm broadband shortwave infrared light area, and a luminescent peak value is positioned about 1350 nm.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the present invention, the present invention provides a broadband short-wave infrared luminescent material, comprising:
Li1-zAzMg1-x-y-cBcPO4:xCr3+,yNi2+wherein x is more than or equal to 0 and less than or equal to 10 percent, y is more than 0 and less than or equal to 1 percent, and x and y are respectively Cr and Ni(LiA)(MgB)PO4Mole percent of (c); z is more than or equal to 0<1，A+Is Na+And K+One or more of (a); c is not less than 0<1，B2+Is Ca2+，Sr2+And Ba2+One or more of (a).
In one or more embodiments of the invention, x is 0.5% to 5%, y is 0.001% to 0.1%, z is 0 to 0.2, and c is 0 to 0.2;
preferably, x is 0.5% or more and 1% or less, and more preferably 0.5% or less.
Preferably, 0.001% ≦ y ≦ 0.03%, and more preferably 0.01%.
In one or more embodiments of the invention, the broadband short wave infrared luminescent material is selected from LiMgPO4:0.5％Cr3+,0.001％Ni2+、Li0.8Na0.2MgPO4:0.5％Cr3+,0.001％Ni2+、Li0.8K0.2MgPO4:0.5％Cr3+,0.001％Ni2+、LiMg0.8Ca0.2PO4:0.5％Cr3+,0.001％Ni2+、LiMg0.8Sr0.2PO4:0.5％Cr3+,0.001％Ni2+、LiMg0.8Ba0.2PO4:0.5％Cr3+,0.001％Ni2+、LiMgPO4:0.5％Cr3+,0.01％Ni2+、LiMgPO4:0.5％Cr3+,0.1％Ni2+And LiMgPO4:0.1％Ni2+。
When the variety or content of Li, Mg, P, O, Cr, Ni, Na, K, Ca, Sr and Ba elements is changed or exceeds the specified range or proportion of the invention, the prepared material has no broadband shortwave infrared luminescence property, poor stability, low strength and no use value.
In a second aspect of the present invention, the present invention provides a method for preparing a broadband short-wave infrared luminescent material, comprising: mixing the materials, evaporating to dryness at low temperature, and sintering at high temperature to obtain the broadband short-wave infrared luminescent material. Further, the material includes a Li-containing compound, a Mg-containing compound, a P-containing compound, a Cr-containing compound, a Ni-containing compound, a Na-containing compound, a K-containing compound, a Ca-containing compound, a Sr-containing compound, and a Ba-containing compound.
In one or more embodiments of the present invention, the preparation method specifically includes: and mixing the materials, dissolving the materials in distilled water, fully stirring, placing in an oven at 80-100 ℃ for evaporation, grinding the product obtained at low temperature again, heating to not less than 900 ℃, and sintering at high temperature to obtain the broadband short-wave infrared luminescent material.
In one or more embodiments of the invention, the materials are mixed by grinding in a mortar to obtain a mixture.
In one or more embodiments of the present invention, the Li-containing compound refers to a compound containing Li element, such as lithium hydroxide, lithium oxide, lithium carbonate, lithium nitrate. Preferably, in one or more embodiments of this embodiment, to provide the luminescent properties of the material, the Li-containing compound is lithium nitrate.
Preferably, the Mg-containing compound refers to a compound containing Mg element, preferably magnesium hydroxide, magnesium oxide, magnesium carbonate, magnesium nitrate. In one or more embodiments of this embodiment, the Mg-containing compound is magnesium nitrate in order to provide luminescent properties of the material.
Preferably, the compound containing P refers to a compound containing P element, preferably ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate. In one or more embodiments of this embodiment, to provide the luminescent properties of the material, the P-containing compound is ammonium dihydrogen phosphate.
Preferably, the Cr-containing compound refers to a compound containing a Cr element, preferably chromium oxide, chromium chloride, chromium nitrate. In one or more embodiments of this embodiment, the Cr-containing compound is chromium nitrate in order to provide luminescent properties of the material.
Preferably, the Ni-containing compound refers to a compound containing a Ni element, and is preferably nickel oxide, nickel chloride, or nickel nitrate. In one or more embodiments of this embodiment, the Ni-containing compound is nickel nitrate in order to provide the luminescent properties of the material.
Preferably, the Na-containing compound refers to a compound containing Na element, preferably sodium carbonate, sodium hydroxide, sodium nitrate. In one or more embodiments of this embodiment, to provide the luminescent properties of the material, the Na-containing compound is sodium nitrate.
Preferably, the K-containing compound is a compound containing K element, preferably potassium carbonate, potassium hydroxide, potassium nitrate. In one or more embodiments of this embodiment, the K-containing compound is potassium nitrate in order to provide the luminescent properties of the material.
Preferably, the Ca-containing compound refers to a compound containing a Ca element, preferably calcium carbonate, calcium oxide, calcium nitrate. In one or more embodiments of this embodiment, the Ca-containing compound is calcium nitrate in order to provide the luminescent properties of the material.
Preferably, the Sr-containing compound refers to a compound containing Sr element, preferably strontium carbonate, strontium oxide, strontium nitrate. In one or more embodiments of this embodiment, to provide the luminescent properties of the material, the Sr-containing compound is strontium nitrate.
Preferably, the Ba-containing compound refers to a compound containing Ba element, preferably barium carbonate, barium oxide, barium nitrate. In one or more embodiments of this embodiment, the Ba-containing compound is barium nitrate in order to provide the luminescent properties of the material.
In one or more embodiments of the invention, the temperature of the oven is 80-100 ℃, and the drying time is 5-8 h.
Preferably, the temperature of the oven is 90-100 ℃, the drying time is 6-8 h, and the short-wave infrared luminescent material has better performance.
More preferably 100 ℃ for 8 hours.
In one or more embodiments of the invention, the high-temperature sintering temperature is 900-1100 ℃, and the sintering time is 6-12 h;
preferably, the high-temperature sintering temperature is 950-1050 ℃, the sintering time is 9-11 h, and the short-wave infrared luminescent material has the best performance.
More preferably 1000 ℃ for 10 hours.
In one or more embodiments of the invention, the high temperature sintering is performed in an air atmosphere. No protection by a reducing atmosphere is required.
In one or more embodiments of the invention, the materials are mixed and ground, and the grinding time is 0.5-2h, preferably 1 h;
in a third aspect of the invention, the invention also discloses a short-wave infrared LED device, which at least comprises a light emitting source and fluorescent powder, wherein the fluorescent powder at least comprises the broadband short-wave infrared luminescent material.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
The formula comprises the following components: broadband short-wave infrared luminescent material LiMgPO4:0.5％Cr3+,0.001％Ni2+In LiMgPO4As a matrix, the doping ions are Cr ions and Ni ions, wherein the doping amount of Cr is 0.5mol percent, and the doping amount of Ni is 0.001mol percent. Lithium nitrate (LiNO) was accurately weighed3)0.2108g of magnesium nitrate (Mg (NO)3)2·6H2O)0.7766g, ammonium dihydrogen phosphate (NH)4H2PO4)0.3287g, chromium nitrate (Cr (NO)3)3·9H20.0057g of nickel nitrate (Ni (NO) at a concentration of 0.01 mol/L)3)2) 2.86 μ L of aqueous solution. Dissolving the raw materials in a beaker, stirring for about 1 hour, fully mixing the raw materials, transferring the mixture to an evaporating dish, and drying the mixture in an oven at 100 ℃ for 8 hours. The dried powder is reground and sintered at the high temperature of 1000 ℃ for 10 hours to obtain blue light excited LiMgPO4:0.5％Cr3+,0.001％Ni2+Broadband short-wave infrared luminescent material.
The samples prepared in this example were tested:
x-ray diffraction pattern of the sample is shown in FIG. 1, with LiMgPO4The standard diffraction spectra of (A) were consistent. FIG. 1 illustrates that the synthesized sample is pure phase and no other impure phase is formed.
Excitation and emission spectra of the samples referring to fig. 2, the samples have a broad emission band in the short wavelength infrared region under excitation of blue light at 450nm, covering the short wavelength infrared region from 600nm to 1650nm, with an emission peak around 1350 nm. The wavelength range of the excitation spectrum is between 350nm and 800nm, and the peak values of the excitation peaks are respectively 450nm and 614 nm.
A broadband short-wave infrared LED device prepared by packaging a sample and a blue light chip participates in the figure 3, after current is switched on, the device can generate short-wave infrared light emission, and the short-wave infrared light emitting brightness of the device is gradually enhanced along with the current increasing.
The night vision and optical anti-counterfeiting application schematic diagram of the broadband short-wave infrared LED device is shown in figure 4. The short wave infrared light has different penetrability to different materials, can see through non-carbon material, and then the formation of image is different under the short wave camera, can be used for applications such as night vision and optics anti-fake.
Example 2
The formula comprises the following components: broadband short-wave infrared luminescent material Li0.8Na0.2MgPO4:0.5％Cr3+,0.001％Ni2+With Li0.8Na0.2MgPO4As a matrix, the doping ions are Cr ions and Ni ions, wherein the doping amount of Cr is 0.5mol percent, and the doping amount of Ni is 0.001mol percent. Lithium nitrate (LiNO) was accurately weighed3)0.1686g, sodium nitrate (NaNO)3)0.0520g of magnesium nitrate (Mg (NO)3)2·6H2O)0.7766g, ammonium dihydrogen phosphate (NH)4H2PO4)0.3287g, chromium nitrate (Cr (NO)3)3·9H20.0057g of nickel nitrate (Ni (NO) at a concentration of 0.01 mol/L)3)2) 2.86 μ L of aqueous solution. Dissolving the raw materials in a beaker, stirring for about 1 hour, fully mixing the raw materials, transferring the mixture to an evaporating dish, and drying the mixture in an oven at 100 ℃ for 8 hours. The dried powder is reground and sintered at the high temperature of 1000 ℃ for 10 hours to obtain the Li excited by blue light0.8Na0.2MgPO4:0.5％Cr3+,0.001％Ni2+Broadband short-wave infrared luminescent material.
The samples prepared in this example were tested:
excitation and emission spectra of the sample referring to fig. 5, the sample has a broad emission band in the short wavelength infrared region under excitation of blue light at 450nm, covering the short wavelength infrared region from 600nm to 1650nm, with an emission peak around 1340 nm. The wavelength range of the excitation spectrum is between 350nm and 700nm, and the peak values of the excitation peaks are respectively 450nm and 613 nm.
Example 3
The formula comprises the following components: broadband short-wave infrared luminescent material Li0.8K0.2MgPO4:0.5％Cr3+,0.001％Ni2+With Li0.8K0.2MgPO4As a matrix, the doping ions are Cr ions and Ni ions, wherein the doping amount of Cr is 0.5mol percent, and the doping amount of Ni is 0.001mol percent. Lithium nitrate (LiNO) was accurately weighed3)0.1686g, potassium nitrate (KNO)3)0.0619g, magnesium nitrate (Mg (NO)3)2·6H2O)0.7766g, ammonium dihydrogen phosphate (NH)4H2PO4)0.3287g, chromium nitrate (Cr (NO)3)3·9H20.0057g of nickel nitrate (Ni (NO) at a concentration of 0.01 mol/L)3)2) 2.86 μ L of aqueous solution. Dissolving the raw materials in a beaker, stirring for about 1 hour, fully mixing the raw materials, transferring the mixture to an evaporating dish, and drying the mixture in an oven at 100 ℃ for 8 hours. The dried powder is reground and sintered at the high temperature of 1000 ℃ for 10 hours to obtain the Li excited by blue light0.8K0.2MgPO4:0.5％Cr3+,0.001％Ni2+Broadband short-wave infrared luminescent material.
The samples prepared in this example were tested:
excitation and emission spectra of the samples referring to fig. 6, the samples have a broad emission band in the short wavelength infrared region under excitation of blue light at 457nm, covering the short wavelength infrared region from 600nm to 1650nm, with an emission peak around 1335 nm. The wavelength range of the excitation spectrum is between 350nm and 700nm, and the peak values of the excitation peaks are respectively 457nm and 612 nm.
Example 4
The formula comprises the following components: broadband short-wave infrared luminescent material LiMg0.8Ca0.2PO4:0.5％Cr3+,0.001％Ni2+With LiMg0.8Ca0.2PO4As a matrix, the doping ions are Cr ions and Ni ions, wherein the doping amount of Cr is 0.5mol percent, and the doping amount of Ni is 0.001mol percent. Lithium nitrate (LiNO) was accurately weighed3)0.2108g of magnesium nitrate (Mg (NO)3)2·6H2O)0.6212g, calcium nitrate (Ca (NO)3)2·4H2O)0.1349g, ammonium dihydrogen phosphate (NH)4H2PO4)0.3287g, chromium nitrate (Cr (NO)3)3·9H20.0057g of nickel nitrate (Ni (NO) at a concentration of 0.01 mol/L)3)2) 2.86 μ L of aqueous solution. Dissolving the raw materials in a beaker, stirring for about 1 hour, fully mixing the raw materials, transferring the mixture to an evaporating dish, and drying the mixture in an oven at 100 ℃ for 8 hours. The dried powder is reground and sintered at the high temperature of 1000 ℃ for 10 hours to obtain blue light excited LiMg0.79499Ca0.2PO4:0.5％Cr3+,0.001％Ni2+Broadband short-wave infrared luminescent material.
The samples prepared in this example were tested:
excitation and emission spectra of the samples referring to fig. 7, the samples have a broad emission band in the short wavelength infrared region under excitation of blue light at 456nm, covering the short wavelength infrared region from 600nm to 1650nm, with an emission peak around 1350 nm. The wavelength range of the excitation spectrum is between 350nm and 800nm, and the peak values of the excitation peaks are respectively 456nm and 618 nm.
Example 5
The formula comprises the following components: broadband short-wave infrared luminescent material LiMg0.8Sr0.2PO4:0.5％Cr3+,0.001％Ni2+With LiMg0.8Sr0.2PO4As a matrix, the doping ions are Cr ions and Ni ions, wherein the doping amount of Cr is 0.5mol percent, and the doping amount of Ni is 0.001mol percent. Lithium nitrate (LiNO) was accurately weighed3)0.2108g of magnesium nitrate (Mg (NO)3)2·6H2O)0.6212g, strontium nitrate (Sr (NO)3)2)0.1209g ammonium dihydrogen phosphate (NH)4H2PO4)0.3287g, chromium nitrate (Cr (NO)3)3·9H20.0057g of nickel nitrate (Ni (NO) at a concentration of 0.01 mol/L)3)2) 2.86 μ L of aqueous solution. Dissolving the raw materials in a beaker, stirring for about 1 hour, fully mixing the raw materials, transferring the mixture to an evaporating dish, and drying the mixture in an oven at 100 ℃ for 8 hours. The dried powder is reground and sintered at the high temperature of 1000 ℃ for 10 hours to obtain blue light excited LiMg0.8Sr0.2PO4:0.5％Cr3+,0.001％Ni2+Broadband short-wave infrared luminescent material.
The samples prepared in this example were tested:
excitation and emission spectra of the samples referring to fig. 8, the samples have a broad emission band in the short wavelength infrared region under excitation of 460nm blue light, covering the short wavelength infrared region from 600nm to 1650nm, with an emission peak around 1333 nm. The wavelength range of the excitation spectrum is between 350nm and 800nm, and the peak values of the excitation peaks are respectively 460nm and 629 nm.
Example 6
The formula comprises the following components: broadband short-wave infrared luminescent material LiMg0.8Ba0.2PO4:0.5％Cr3+,0.001％Ni2+With LiMg0.8Ba0.2PO4As a matrix, the doping ions are Cr ions and Ni ions, wherein the doping amount of Cr is 0.5mol percent, and the doping amount of Ni is 0.001mol percent. Lithium nitrate (LiNO) was accurately weighed3)0.2108g of magnesium nitrate (Mg (NO)3)2·6H2O)0.6212g, barium nitrate (Ba (NO)3)2)0.1493g ammonium dihydrogen phosphate (NH)4H2PO4)0.3287g, chromium nitrate (Cr (NO)3)3·9H20.0057g of nickel nitrate (Ni (NO) at a concentration of 0.01 mol/L)3)2) 2.86 μ L of aqueous solution. Dissolving the raw materials in a beaker, stirring for about 1 hour, fully mixing the raw materials, transferring the mixture to an evaporating dish, and drying the mixture in an oven at 100 ℃ for 8 hours. The dried powder is reground and sintered at the high temperature of 1000 ℃ for 10 hours to obtain blue light excited LiMg0.8Ba0.2PO4:0.5％Cr3+,0.001％Ni2+Broadband short-wave infrared luminescent material.
The samples prepared in this example were tested:
excitation and emission spectra of the sample referring to fig. 9, the sample has a broad emission band in the short wavelength infrared region under excitation of blue light at 459nm, covering the short wavelength infrared region from 600nm to 1650nm, with an emission peak at about 1330 nm. The wavelength range of the excitation spectrum is between 350nm and 800nm, and the peak values of the excitation peaks are respectively 459nm and 610 nm.
Example 7
The formula comprises the following components: broadband short-wave infrared luminescent material LiMgPO4:0.5％Cr3+,0.01％Ni2+In LiMgPO4As a matrix, the doping ions are Cr ions and Ni ions, wherein the doping amount of Cr is 0.5mol percent, and the doping amount of Ni is 0.01mol percent. Lithium nitrate (LiNO) was accurately weighed3)0.2108g of magnesium nitrate (Mg (NO)3)2·6H2O)0.7766g, ammonium dihydrogen phosphate (NH)4H2PO4)0.3287g, chromium nitrate (Cr (NO)3)3·9H20.0057g of nickel nitrate (Ni (NO) at a concentration of 0.01 mol/L)3)2) Aqueous solution 28.60. mu.L. Dissolving the raw materials in a beaker, stirring for about 1 hour, fully mixing the raw materials, transferring the mixture to an evaporating dish, and drying the mixture in an oven at 100 ℃ for 8 hours. The dried powder is reground and sintered at the high temperature of 1000 ℃ for 10 hours to obtain blue light excited LiMgPO4:0.5％Cr3+,0.01％Ni2+Broadband short-wave infrared luminescent material.
The samples prepared in this example were tested:
excitation and emission spectra of the samples referring to fig. 10, the samples have a broad emission band in the short wavelength infrared region under excitation of blue light at 450nm, covering the short wavelength infrared region from 1000nm to 1650nm, with an emission peak at about 1380 nm. The wavelength range of the excitation spectrum is between 350nm and 800nm, and the peak values of the excitation peaks are respectively 450nm and 614 nm.
Example 8
The formula comprises the following components:broadband short-wave infrared luminescent material LiMgPO4:0.5％Cr3+,0.1％Ni2+In LiMgPO4As a matrix, the doping ions are Cr ions and Ni ions, wherein the doping amount of Cr is 0.5mol percent, and the doping amount of Ni is 0.1mol percent. Lithium nitrate (LiNO) was accurately weighed3)0.2108g of magnesium nitrate (Mg (NO)3)2·6H2O)0.7766g, ammonium dihydrogen phosphate (NH)4H2PO4)0.3287g, chromium nitrate (Cr (NO)3)3·9H20.0057g of nickel nitrate (Ni (NO) at a concentration of 0.01 mol/L)3)2) 0.29mL of aqueous solution. Dissolving the raw materials in a beaker, stirring for about 1 hour, fully mixing the raw materials, transferring the mixture to an evaporating dish, and drying the mixture in an oven at 100 ℃ for 8 hours. The dried powder is reground and sintered at the high temperature of 1000 ℃ for 10 hours to obtain blue light excited LiMgPO4:0.5％Cr3+,0.1％Ni2+Broadband short-wave infrared luminescent material.
The samples prepared in this example were tested:
excitation and emission spectra of the samples referring to fig. 11, the samples have a broad emission band in the short wavelength infrared region under excitation of blue light at 450nm, covering the short wavelength infrared region from 1000nm to 1650nm, with an emission peak around 1440 nm. The wavelength range of the excitation spectrum is between 350nm and 800nm, and the peak values of the excitation peaks are respectively 450nm and 611 nm.
Example 9
The formula comprises the following components: broadband short-wave infrared luminescent material LiMgPO4:0.1％Ni2+In LiMgPO4As a matrix, the doping ions are Ni ions, wherein the doping amount of Ni is 0.1 mol%. Lithium nitrate (LiNO) was accurately weighed3)0.2108g of magnesium nitrate (Mg (NO)3)2·6H2O)0.7766g, ammonium dihydrogen phosphate (NH)4H2PO4)0.3287g of nickel nitrate (Ni (NO) at a concentration of 0.01mol/L3)2) 0.29mL of aqueous solution. Dissolving the raw materials in a beaker, stirring for about 1 hour, fully mixing the raw materials, transferring the mixture to an evaporating dish, and drying the mixture in an oven at 100 ℃ for 8 hours. The dried powder is reground and then driedSintering at 1000 ℃ for 10 hours to obtain blue light excited LiMgPO4:0.1％Ni2+Broadband short-wave infrared luminescent material.
The samples prepared in this example were tested:
excitation and emission spectra of the samples referring to fig. 12, the samples have a broad emission band in the short wavelength infrared region under excitation of 405nm blue light, covering the short wavelength infrared region from 1000nm to 1650nm, with an emission peak around 1320 nm. The wavelength range of the excitation spectrum is between 350nm and 800nm, and the peak values of the excitation peaks are respectively 459nm, 462nm, 664nm and 681 nm.
Short wave infrared LED illuminator application example:
the short-wave infrared LED light emitting device of the present invention was prepared as follows. The short-wave infrared LED light-emitting device comprises a packaging substrate, a blue LED chip and fluorescent powder capable of effectively absorbing the light emitted by the LED chip and releasing short-wave infrared light; wherein the fluorescent powder of the short-wave infrared light is the fluorescent powder, and the chemical composition formula of the fluorescent powder is LiMgPO4:0.5％Cr3+,0.001％Ni2+. Wherein, the blue LED chip is an InGaN semiconductor chip, and the light-emitting peak wavelength thereof is 450-455 nm. The short-wave infrared fluorescent powder is uniformly dispersed in transparent high polymer materials such as silica gel or transparent inorganic materials such as glass, a chip and a light conversion film are combined together, and a circuit is welded, so that the short-wave infrared LED light-emitting device is obtained.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (25)

1. A broadband short-wave infrared luminescent material, comprising:
Li1-zAzMg1-x-y-cBcPO4:xCr3+,yNi2+x and y are Cr and Ni in (LiA) (MgB) PO respectively4Mole percent of (c); a. the+Is Na+And K+One or more of (a); b is2+Is Ca2+，Sr2+And Ba2+One or more of (a);
wherein x is more than or equal to 0.5 percent and less than or equal to 5 percent, y is more than 0.001 percent and less than or equal to 0.05 percent, z is more than or equal to 0 and less than or equal to 0.2 percent, and c is more than or equal to 0 and less than or equal to 0.2 percent.
2. The broadband shortwave infrared luminescent material as claimed in claim 1, wherein x is 0.5% to 1%, and y is 0.001% to 0.03%.
3. A broadband shortwave infrared luminescent material according to claim 1, wherein x is 0.5% and y is 0.01%.
4. The broadband shortwave infrared luminescent material of claim 1, selected from the group consisting of LiMgPO4:0.5％Cr3+,0.001％Ni2+、Li0.8Na0.2MgPO4:0.5％Cr3+,0.001％Ni2+、Li0.8K0.2MgPO4:0.5％Cr3+,0.001％Ni2+、LiMg0.8Ca0.2PO4:0.5％Cr3+,0.001％Ni2+、LiMg0.8Sr0.2PO4:0.5％Cr3+,0.001％Ni2+、LiMg0.8Ba0.2PO4:0.5％Cr3+,0.001％Ni2+、LiMgPO4:0.5％Cr3+,0.01％Ni2+And LiMgPO4:0.5％Cr3+,0.1％Ni2+。
5. A method for preparing the broadband short-wave infrared luminescent material as claimed in any one of claims 1 to 4, which comprises:
mixing the materials, pre-burning, and sintering to obtain a broadband short-wave infrared luminescent material;
wherein the material includes a Li-containing compound, a Mg-containing compound, a P-containing compound, a Cr-containing compound, a Ni-containing compound, a Na-containing compound, a K-containing compound, a Ca-containing compound, a Sr-containing compound, and a Ba-containing compound;
the preparation method comprises the following steps: and mixing the materials, dissolving the materials in distilled water, fully stirring, placing in an oven at 80-100 ℃ for evaporation to dryness for 5-8 h, grinding the product obtained at low temperature again, heating to not lower than 900 ℃ for high-temperature sintering, and obtaining the broadband short-wave infrared luminescent material.
6. The preparation method of the broadband shortwave infrared luminescent material as claimed in claim 5, wherein the Li-containing compound is a compound containing Li element, and comprises lithium hydroxide, lithium oxide, lithium carbonate and lithium nitrate.
7. The preparation method of the broadband short-wave infrared luminescent material as claimed in claim 5, wherein the Mg-containing compound is a compound containing Mg element, and comprises magnesium hydroxide, magnesium oxide, magnesium carbonate and magnesium nitrate.
8. The preparation method of the broadband shortwave infrared luminescent material as claimed in claim 5, wherein the P-containing compound is a compound containing P element, and comprises ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
9. The method for preparing broadband shortwave infrared luminescent material according to claim 5, wherein the Cr-containing compound is a compound containing Cr element, and comprises chromium oxide, chromium chloride and chromium nitrate.
10. The preparation method of the broadband short-wave infrared luminescent material as claimed in claim 5, wherein the Ni-containing compound is a compound containing Ni element, and comprises nickel oxide, nickel chloride and nickel nitrate.
11. The preparation method of broadband shortwave infrared luminescent material as claimed in claim 5, wherein the Na-containing compound is a compound containing Na element, and comprises sodium carbonate, sodium hydroxide and sodium nitrate.
12. The preparation method of the broadband short-wave infrared luminescent material as claimed in claim 5, wherein the K-containing compound is a compound containing K element, and comprises potassium carbonate, potassium hydroxide and potassium nitrate.
13. The method for preparing broadband shortwave infrared luminescent material according to claim 5, wherein the Ca-containing compound is a compound containing Ca element, and comprises calcium carbonate, calcium oxide and calcium nitrate.
14. The preparation method of the broadband short-wave infrared luminescent material as claimed in claim 5, wherein the Sr-containing compound is a Sr-containing compound comprising strontium carbonate, strontium oxide and strontium nitrate.
15. The method for preparing broadband shortwave infrared luminescent material according to claim 5, wherein the Ba-containing compound is a compound containing Ba element, and comprises barium carbonate, barium oxide and barium nitrate.
16. The preparation method of the broadband shortwave infrared luminescent material as claimed in claim 5, wherein the temperature of the oven is 90-100 ℃ and the drying time is 6-8 h.
17. The preparation method of the broadband shortwave infrared luminescent material as claimed in claim 5, wherein the oven temperature is 100 ℃ and the evaporation time is 8 h.
18. The preparation method of the broadband short-wave infrared luminescent material as claimed in claim 5, wherein the high-temperature sintering temperature is 900-1100 ℃ and the sintering time is 6-12 h.
19. The preparation method of the broadband short-wave infrared luminescent material as claimed in claim 5, wherein the high-temperature sintering temperature is 950-1050 ℃ and the sintering time is 9-11 h.
20. The preparation method of the broadband short-wave infrared luminescent material as claimed in claim 5, wherein the high-temperature sintering temperature is 1000 ℃ and the sintering time is 10 h.
21. The preparation method of the broadband shortwave infrared luminescent material as claimed in claim 5, wherein the material and the fluxing agent are mixed and ground, and the grinding time is 0.5-2 h.
22. The method for preparing a broadband shortwave infrared luminescent material as claimed in claim 21, wherein the milling time is 1 hour.
23. A broadband short-wave infrared LED device, characterized in that the device at least comprises a light emitting source and a phosphor, wherein the phosphor at least comprises the broadband short-wave infrared luminescent material according to any one of claims 1 to 4.
24. The broadband short wave infrared LED device of claim 23, wherein the light emitting source is a blue chip.
25. Use of the broadband short-wave infrared luminescent material according to any one of claims 1 to 4 and/or the broadband short-wave infrared luminescent material prepared by the method for preparing the broadband short-wave infrared luminescent material according to any one of claims 5 to 22 in the technical fields of night vision, optical anti-counterfeiting, biomedicine and short-wave infrared spectroscopy.
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