CN117736729A - Near infrared luminescent material, preparation method thereof and LED light source containing luminescent material - Google Patents
Near infrared luminescent material, preparation method thereof and LED light source containing luminescent material Download PDFInfo
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Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention discloses a near infrared luminescent material, a preparation method thereof and an LED light source comprising the luminescent material, wherein the chemical composition of the luminescent material is represented by a chemical formula A a B b P c O x M y ：zCr 3+ Wherein the A element is selected from one or more of Li, na, K, rb, cs, mg, ca, sr and Ba; the B element is selected from one or more of Al, ga, sc, in, fe, nd, ta, ti, zr, V, ni and rare earth elements, and the M element is selected from one of F, cl and N; cr (Cr) 3+ For the luminescent center ion, z is more than or equal to 0.01% and less than or equal to 100%, and a, b, x and y are the simplest stoichiometric numbers of elements, namely, a is more than or equal to 0<10，0≤b<10，0≤c<20，0<x<30，0<y<30. The near infrared luminescent material has higher luminescenceStability, luminescence quantum yield.
Description
Technical Field
The invention belongs to the field of luminescent materials, and particularly relates to a near infrared luminescent material, a preparation method thereof and an LED light source containing the luminescent material.
Background
Near infrared light has a higher penetration capacity than visible light intensity in biological tissues, and natural substances have different characteristic absorption to the near infrared light, so that the near infrared light is focused on the fields of security monitoring, biological identification, sensing, food/medical detection, plant illumination and the like based on the unique characteristics of the near infrared light.
The near infrared light source is a precondition of near infrared spectrum technology application, and early near infrared light sources are mainly halogen tungsten lamps, which have the advantages of wide emission spectrum and high brightness, but have low efficiency, large volume and short service life, so that the near infrared light source is gradually disfavored by new markets. As a fourth generation novel solid-state lighting source, the light-emitting diode (LED) has the advantages of high efficiency, energy conservation, small volume, no pollution, long service life and the like, thereby becoming the first choice of energy-saving and environment-friendly light sources. The near infrared LED light source prepared by exciting the near infrared fluorescent powder by adopting the near ultraviolet or blue InGaN chip has the advantages of rich wavelength types, half-width of the spectrum wave width, and the like, so that the near infrared LED light source can be freely combined into the required pure monochromatic light or composite spectrum according to the requirements. Meanwhile, the LED lighting system has less heat and small occupied space, and the high durability of the LED lighting system also reduces the running cost. Therefore, in order to obtain a high-performance LED light source, development of a high-efficiency stable near-infrared luminescent material has great significance.
However, the near infrared materials disclosed in the prior art are mainly Cr 3+ Doped oxide and fluoride materials, wherein Cr 3+ Doped oxide near infrared luminescent materials are of a large variety, such as borates, phosphates, gallates, aluminates, silicates and the like, and in such materials, the luminescent efficiency and stability of the materials are required to be improved because the oxide has relatively high phonon energy and relatively weak covalent property. And at Cr 3+ In the doped fluoride near infrared luminescent materials, most materials are synthesized by adopting a wet chemical method, and an HF solution is inevitably used, so that the safety of material preparation is tested.
Therefore, how to develop a near-infrared luminescent material which can be excited by blue light or red light, has simple preparation process, high luminous efficiency and good stability, and uses the material to prepare a fluorescence conversion type near-infrared LED device, so as to be applied to various fields such as biological identification, sensing, food/medical detection, plant illumination and the like, and become a technical problem to be solved in the field.
Disclosure of Invention
In order to improve the technical problems, the invention provides a luminescent material with near infrared broadband emission, a preparation method thereof and an LED light source comprising the luminescent material.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a near infrared luminescent material, the chemical composition of the luminescent material is represented by a chemical formula A a B b P c O x M y ：zCr 3+ The representation, wherein,
the A element is one or more selected from Li, na, K, rb, cs, mg, ca, sr and Ba;
the B element is one or more selected from Al, ga, in, fe, nd, ta, ti, zr, V, ni and rare earth elements;
the M element is at least one selected from F, cl and N;
Cr 3+ z is more than or equal to 0.01% and less than or equal to 100%, preferably more than or equal to 1% and less than or equal to 10% for luminescent center ions;
a. b, x and y are the simplest stoichiometric numbers of elements, 0.ltoreq.a <10, 0.ltoreq.b <10, 0.ltoreq.c <20,0< x <30,0< y <30.
According to an embodiment of the invention, the rare earth element is La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sc or Y.
According to an embodiment of the invention, the luminescent material A a B b P c O x M y ：zCr 3+ The material is prepared from raw materials including an A source, a B source, a P source, an M source and a Cr source through high-temperature calcination.
According to an embodiment of the invention, the a source is provided by a compound comprising an element a. Preferably, the a source is selected from at least one of a carbonate, an oxide, a nitride, a nitrate, and a halide containing an a element; illustratively, the A source is Na 2 CO 3 、NaF、KF、NaPO 4 、Li 2 CO 3 、LiF、K 2 CO 3 、SrF 2 、CaF 2 、Rb 2 CO 3 And Cs 2 CO 3 At least one of them.
According to an embodiment of the invention, the B source is provided by a compound comprising an element B; for example, at least one selected from the group consisting of a carbonate, an oxide, a nitride, a nitrate, and a halide containing a B element; illustratively, the B source compound is Al 2 O 3 、AlN、AlF 3 、TiO 2 、V 2 O 5 、ZrO 2 、Sc 2 O 3 、ScF 3 、In 2 O 3 、Ga 2 O 3 And GeO 2 At least one of them.
According to an embodiment of the invention, the Cr source is provided by a compound comprising Cr element; for example, at least one selected from the group consisting of a carbonate, an oxide, a nitride, a nitrate, and a halide of a Cr-containing element; illustratively, the Cr source is Cr 2 O 3 、CrF 3 At least one of CrN.
According to an embodiment of the invention, the P source is provided by a compound comprising an element P; for example, at least one selected from the group consisting of phosphate containing P element and oxide containing P element, preferably NaPO 4 Ammonium dihydrogen phosphate, and sodium dihydrogen phosphate.
According to an embodiment of the invention, the M source is provided by an M element-containing compound; for example, by at least one of a fluorine source, a chlorine source, and a nitrogen source.
For example, the fluorine source is KF, naF, caF 2 Ammonium fluoride, aluminum fluoride and SrF 2 At least one of them.
For example, the chlorine source is at least one of potassium chloride, sodium chloride, ammonium chloride and aluminum chloride.
For example, the nitrogen source is at least one of AlN and urea.
According to one embodiment of the invention, the B source and the M source may be identical. For example, all NaF, alN, srF 2 。
According to an embodiment of the present invention, the luminescent material may be Na 3 AlP 3 O 9 N：4％Cr 3+ 、Na 3 TiP 3 O 9 N：2％Cr 3+ 、NaAlPO 4 F：4％Cr 3+ 、KAlPO 4 F：2％Cr 3+ 、NaVPO 4 F：2％Cr 3+ 、Na 5 AlP 2 O 8 F 2 ：3％Cr 3+ 、Na 3 Al 2 P 2 O 8 F 3 :2％Cr 3+ 、SrAl 2 P 2 O 8 F 2 :4％Cr 3+ 、CaAl 2 P 2 O 8 F 2 :4％Cr 3+ 。
According to an embodiment of the invention, the luminescent material is capable of being excited by violet, blue or red light. Preferably, the luminescent material has near infrared broadband emission properties, for example, is capable of emitting near infrared light having a wavelength in the range of 650-1300nm, with a peak in the range of 700-1000 nm.
The luminescent material provided by the invention has a higher thermal quenching temperature and shows excellent luminescent thermal stability.
< preparation method of luminescent Material >
The invention also provides a preparation method of the near infrared luminescent material, which comprises the following steps:
(1) According to chemical formula A a B b P c O x M y ：zCr 3+ The stoichiometric ratio of each element in the (a), B, P, M and Cr sources are mixed to obtain a mixture;
(2) And calcining the mixture to obtain the near infrared luminescent material.
According to an embodiment of the present invention, in step (1), the compound of formula A a B b P c O x M y ：zCr 3+ The stoichiometric ratios of the elements of a source, B source, P source, M source and Cr source are weighed, wherein the P source may be used in a suitable excess, for example in an excess of 5wt.% to 200wt.%.
According to an embodiment of the present invention, in step (1), grinding may be performed after mixing the a source, the B source, the P source, the M source, and the Cr source. The method of grinding is not particularly limited, and grinding equipment such as a mortar, a ball mill, and a mixer can be used.
According to the inventionIn an embodiment, in step (2), the calcination may be performed in air, an inert atmosphere, or a reducing atmosphere. The inert atmosphere is, for example, nitrogen, argon or the like; the reducing atmosphere is, for example, (5-15% by volume) H 2 And (95 v% -85 v%) N 2 A mixed gas, or a calcination environment containing carbon powder.
According to an embodiment of the present invention, in step (2), the calcination temperature is 150-1500 ℃, preferably 500-1200 ℃, more preferably 700-1100 ℃, and exemplarily 150 ℃,300 ℃,500 ℃, 700 ℃, 1000 ℃, 1200 ℃, 1500 ℃; the calcination time is 1 to 30 hours, preferably 5 to 20 hours, more preferably 8 to 15 hours, and exemplified by 1 hour, 3 hours, 5 hours, 8 hours, 12 hours, 15 hours, 20 hours, 30 hours.
According to an embodiment of the present invention, in step (2), the number of times of calcination is at least one, and may be, for example, two times, three times or more. Preferably, the temperatures of each calcination are different from each other. More preferably, the temperature of each calcination is in an ascending trend. Preferably, the last calcination product may be milled before the next calcination.
In an exemplary embodiment of the present invention, in step (2), two calcination steps are performed, the first calcination step being performed at a temperature of 150-700 ℃, exemplary 150 ℃,300 ℃,500 ℃, 700 ℃; the time of the first calcination is 1-12h, and is exemplified by 1h, 3h, 5h, 8h and 12h; the temperature of the second calcination is 700-1500deg.C, and is exemplified by 800 deg.C, 1000 deg.C, 1200 deg.C, and 1500 deg.C; the second calcination time is 1-20h, and is exemplified by 1h, 3h, 5h, 8h, 12h, 15h, and 20h.
According to an embodiment of the present invention, the preparation method further comprises step (3): and carrying out post-treatment on the calcined product to obtain the near infrared luminescent material. Preferably, in step (3), the post-treatment may include grinding, washing, filtering, drying, and the like.
Illustratively, the temperature of the drying is 60-100deg.C.
Illustratively, the post-treatment may be grinding the calcined product, washing with deionized water 1-3 times, washing with absolute ethanol 1-2 times, filtering, and oven drying at 80deg.C.
The invention also provides application of the luminescent material in a luminescent device. Wherein, the light emitting device is used in the fields of petrochemical industry, high polymer, pharmacy, clinical medicine, environmental science, textile industry or food detection, etc.
Preferably, the light emitting device is a fluorescence conversion type near infrared LED device. Further, the fluorescence conversion type near infrared LED device is used in the fields of biological identification, 3D sensing, food/medical detection, agricultural production or biological imaging and the like.
The invention also provides an LED light source, which comprises the near infrared luminescent material A a B b P c O x M y ：zCr 3+ . Preferably, the fluorescent conversion layer of the LED light source comprises the near infrared luminescent material A a B b P c O x M y ：zCr 3+ 。
According to an embodiment of the present invention, the LED light source further comprises an LED semiconductor chip, the fluorescent conversion layer is disposed on the LED semiconductor chip, and the fluorescent conversion layer comprises the near infrared luminescent material a described above a B b P c O x M y ：zCr 3+ 。
According to an embodiment of the present invention, the LED light source further comprises a glue layer disposed on the LED semiconductor chip, wherein the glue layer contains the luminescent material a uniformly dispersed therein a B b P c O x M y ：zCr 3+ . Wherein, the glue in the glue layer can be epoxy resin, polycarbonate or silica gel; preferably silica gel. The amount of the paste is not particularly limited as long as it can be uniformly applied on the LED semiconductor chip according to the known operation in the art.
According to an embodiment of the present invention, the fluorescent conversion layer is coated on an LED semiconductor chip for carrying the above-mentioned fluorescent conversion layer.
According to an embodiment of the present invention, the LED semiconductor chip is at least one of a violet LED chip, a blue LED chip, and a red LED chip.
According to the embodiment of the invention, the peak value of the purple light LED chip is in the range of 280-400 nm.
According to the embodiment of the invention, the peak value of the blue LED chip is in the range of 420-490 nm.
According to an embodiment of the present invention, the peak value of the red LED chip is in the range of 590-680 nm.
According to an embodiment of the invention, the LED light source is a fluorescence conversion type near infrared LED device. Further, the fluorescence conversion type near infrared LED device is used in the fields of biological identification, sensing, food detection, medical detection, temperature measurement, agricultural production or biological imaging and the like.
The invention also provides a preparation method of the LED light source, which comprises the following steps: the above luminescent material is mixed with glue and then coated on an LED semiconductor chip.
The invention also provides the application of the LED light source containing the luminescent material in the fields of petrochemical industry, high polymer, pharmacy, clinical medicine, environmental science, textile industry, food detection and the like.
The invention has the beneficial effects that:
(1) The near infrared luminescent material with broadband emission characteristic provided by the invention can be used as a light conversion material of a near ultraviolet LED chip, a blue light LED chip and a red light LED chip to be used as a high-efficiency stable broadband near infrared luminescent light source, so that the problem of narrow bandwidth of the existing infrared LEDs and infrared lasers is solved, and the requirements of the broadband infrared light source in the applications of food detection, medical detection, agricultural production or biological imaging and the like can be met. Compared with the existing materials, the broadband near infrared luminescent material has higher luminescence stability and luminescence quantum yield.
(2) The near infrared luminescent material provided by the invention has excellent moisture resistance and high temperature resistance stability, and the light output power of the prepared LED light source is still more than 98% of that of the LED light source at room temperature after the LED light source is aged for 480 hours in an environment with 85 ℃ and 85% of humidity.
(3) The luminescent material provided by the invention has the advantages of simple preparation process, no pollution and low cost.
Drawings
Fig. 1 is an XRD pattern of a luminescent material prepared in example 1 of the present invention.
Fig. 2 is an excitation spectrum of the luminescent material prepared in example 1 of the present invention.
Fig. 3 is an emission spectrum of the luminescent material prepared in example 1 of the present invention.
Fig. 4 is a graph showing the change of the integrated luminous intensity with temperature of the luminescent material prepared in example 1 of the present invention.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1: na (Na) 3 AlP 3 O 9 N：4％Cr 3+ Preparation of luminescent materials
The embodiment adopts a solid phase reaction method to synthesize, firstly, the chemical formula Na is adopted 3 AlP 3 O 9 N：4％Cr 3+ The stoichiometric ratio of each element is weighed, alN is 0.1131g, naPO 4 2.4617g, cr 2 O 3 0.0187g (due to NaPO therein) 4 And volatilize during firing, and the raw materials are added in excess). The raw materials are uniformly mixed in a mortar, then are put into a corundum crucible, are put into a box-type furnace, are calcined for 5 hours at 300 ℃ in air atmosphere, and are ground again after being cooled to room temperature. And then placing the mixture into an atmosphere furnace, carrying out secondary calcination for 8 hours at 780 ℃ in a nitrogen atmosphere, grinding the obtained sample after the calcination is finished, washing the sample with deionized water for 1-3 times, washing the sample with absolute ethyl alcohol for 1-2 times, and drying the sample in an oven at 80 ℃ after filtering to obtain the final near infrared luminescent material.
Example 2: na (Na) 3 TiP 3 O 9 N：2％Cr 3+ Preparation of luminescent materials
In this example, the synthesis was carried out by solid phase reaction, and raw materials (NH) 4 )H 2 PO 4 1.1356g, na 2 CO 3 0.7355, 1.7624g of urea, mixing the above three materials, placing into a muffle furnace, maintaining at 300deg.C for 2 hr, taking out, and weighing TiO 2 0.0834g and Cr 2 O 3 0.0086g of the above calcined raw materials are added and ground together, and are put into a corundum crucible after being uniformly mixed, and are put into an atmosphere furnace, and the mixture is put into a furnace with 5v percent of H 2 -95v％N 2 And (3) calcining for the second time at 750 ℃ for 8 hours under the mixed gas, grinding the obtained sample after the calcining is finished, washing for 1-3 times with deionized water, washing for 1-2 times with absolute ethyl alcohol, filtering, and drying in an oven at 80 ℃ to obtain the final near infrared luminescent material.
Example 3: naAlPO 4 F：4％Cr 3+ Preparation of luminescent materials
This example is synthesized by solid phase reaction, first according to the chemical formula NaAlPO 4 F：4％Cr 3+ The stoichiometric ratio of each element is used for weighting, naF is 0.2546g, al 2 O 3 0.2968g, (NH) 4 )H 2 PO 4 0.6973g, cr 2 O 3 0.0184g. The raw materials are uniformly mixed in a mortar, then the mixture is put into a small-sized corundum crucible, the small-sized corundum crucible is put into a large-sized crucible filled with carbon powder (the dosage of the small-sized corundum crucible is one third of the height of the small-sized crucible, the small-sized crucible is usually covered by the carbon powder), the large-sized crucible is put into a box-type furnace, the small-sized corundum crucible is calcined for 4 hours at the temperature of 500 ℃ in an air atmosphere, and the small-sized corundum crucible is ground again after being cooled to the room temperature. Then placing the mixture into a box-type furnace, calcining for the second time for 12 hours at 1050 ℃, grinding the obtained sample after the calcining is finished, washing the sample with deionized water for 1-3 times, washing the sample with absolute ethyl alcohol for 1-2 times, filtering the sample, and drying the sample in an oven at 80 ℃ to obtain the final near infrared luminescent material.
Example 4: KAlPO 4 F：2％Cr 3+ Preparation of luminescent materials
The present example uses a solid phase reaction methodSynthesis of the first KAlPO according to the chemical formula 4 F：2％Cr 3+ The stoichiometric ratio of each element is used for weighing, KF is 0.3214g, al 2 O 3 0.2769g, (NH) 4 )H 2 PO 4 0.6374g, cr 2 O 3 0.0084g. The raw materials are uniformly mixed in a mortar, then the mixture is put into a small-sized corundum crucible, the small-sized corundum crucible is put into a large-sized crucible filled with carbon powder (the dosage of the small-sized corundum crucible is one third of the height of the small-sized crucible, the small-sized crucible is usually covered by the carbon powder), the large-sized crucible is put into a box-type furnace, the small-sized corundum crucible is calcined for 4 hours at the temperature of 500 ℃ in an air atmosphere, and the small-sized corundum crucible is ground again after being cooled to the room temperature. Then placing the mixture into a box-type furnace, calcining for the second time for 10 hours at 1050 ℃, grinding the obtained sample after the calcining is finished, washing the sample with deionized water for 1-3 times, washing the sample with absolute ethyl alcohol for 1-2 times, filtering the sample, and drying the sample in an oven at 80 ℃ to obtain the final near infrared luminescent material.
Example 5: naVPO 4 F：2％Cr 3+ Preparation of luminescent materials
The embodiment adopts a solid phase reaction method for synthesis, firstly, raw material NaF is weighed to be 0.2373g, V 2 O 5 0.5138g, (NH) 4 )H 2 PO 4 0.6850g, cr 2 O 3 0.0062g, carbon powder 0.0678g (used as reducing agent, V 5+ Reduction to V 3+ ). Mixing the above materials in a mortar, loading into a small-size corundum crucible, placing the small-size crucible into a large-size crucible containing carbon powder, placing into a box furnace, calcining at 500 ℃ for 4 hours in air atmosphere, cooling to room temperature, and grinding again. Then placing the mixture into a box-type furnace, calcining for the second time for 10 hours at 1050 ℃, grinding the obtained sample after the calcining is finished, washing the sample with deionized water for 1-3 times, washing the sample with absolute ethyl alcohol for 1-2 times, filtering the sample, and drying the sample in an oven at 80 ℃ to obtain the final near infrared luminescent material.
Example 6: na (Na) 5 AlP 2 O 8 F 2 ：3％Cr 3+ Preparation of luminescent materials
The embodiment adopts a solid phase reaction method to synthesize, firstly, the chemical formula Na is adopted 5 AlP 2 O 8 F 2 ：3％Cr 3+ The stoichiometric ratio of each element is used for weighting, naF is 0.5665g, al 2 O 3 0.1334g, (NH) 4 )H 2 PO 4 0.6206g, cr 2 O 3 0.0062g. The raw materials are uniformly mixed in a mortar, then are put into a corundum crucible, are put into a box-type furnace, are calcined for 5 hours at 300 ℃ in air atmosphere, and are ground again after being cooled to room temperature. Then placing the mixture into a box-type furnace, calcining for the second time for 10 hours at 800 ℃, grinding the obtained sample after the calcining is finished, washing the sample with deionized water for 1-3 times, washing the sample with absolute ethyl alcohol for 1-2 times, filtering the sample, and drying the sample in an oven at 80 ℃ to obtain the final near infrared luminescent material.
Example 7: na (Na) 3 Al 2 P 2 O 8 F 3 :2％Cr 3+ Preparation of luminescent materials
The embodiment adopts a solid phase reaction method to synthesize, firstly, the chemical formula Na is adopted 3 Al 2 P 2 O 8 F 3 :2％Cr 3+ The stoichiometric ratio of each element is used for weighting, naF is 0.2582g, al 2 O 3 0.2048g, (NH) 4 )H 2 PO 4 0.4714g, cr 2 O 3 0.0062g. The raw materials are uniformly mixed in a mortar, then are put into a corundum crucible, then are put into an atmosphere furnace, are calcined for 5 hours at 300 ℃ under the nitrogen atmosphere, and are ground again after being cooled to room temperature. And then placing the mixture into an atmosphere furnace, calcining for the second time at 850 ℃ for 10 hours under nitrogen atmosphere, grinding the obtained sample after the calcining is finished, washing the sample with deionized water for 1-3 times, washing the sample with absolute ethyl alcohol for 1-2 times, filtering the sample, and drying the sample in an oven at 80 ℃ to obtain the final near infrared luminescent material.
Example 8: srAl 2 P 2 O 8 F 2 :4％Cr 3+ Preparation of luminescent materials
The embodiment adopts a solid phase reaction method for synthesis, and is firstly synthesized according to the chemical formula SrAl 2 P 2 O 8 F 2 :4％Cr 3+ The stoichiometric ratio of each element is used for weighting the materials, srF 2 0.3381g, (NH) 4 )H 2 PO 4 0.6192g of Al 2 O 3 0.2636g, cr 2 O 3 0.0164g. The raw materials are uniformly mixed in a mortar, then are put into a corundum crucible, are put into a box-type furnace, are calcined for 5 hours at 300 ℃ in air atmosphere, and are ground again after being cooled to room temperature. And then placing the mixture into an atmosphere furnace, calcining for the second time at 750 ℃ for 8 hours under nitrogen atmosphere, grinding the obtained sample after the calcining is finished, washing the sample with deionized water for 1-3 times, washing the sample with absolute ethyl alcohol for 1-2 times, filtering the sample, and drying the sample in an oven at 80 ℃ to obtain the final near infrared luminescent material.
Example 9: caAl (CaAl) 2 P 2 O 8 F 2 :4％Cr 3+ Preparation of luminescent materials
The embodiment adopts a solid phase reaction method for synthesis, and firstly CaAl is prepared according to the chemical formula 2 P 2 O 8 F 2 :4％Cr 3+ The stoichiometric ratio of each element is used for weighting, caF 2 0.2408g, (NH) 4 )H 2 PO 4 0.7102g, al 2 O 3 0.3023g of Cr 2 O 3 0.0188g. The raw materials are uniformly mixed in a mortar, then are put into a corundum crucible, are put into a box-type furnace, are calcined for 5 hours at 300 ℃ in air atmosphere, and are ground again after being cooled to room temperature. And then placing the mixture into an atmosphere furnace, calcining for the second time for 8 hours at 780 ℃ in a nitrogen atmosphere, grinding the obtained sample after the calcining is finished, washing the sample with deionized water for 1-3 times, washing the sample with absolute ethyl alcohol for 1-2 times, filtering the sample, and drying the sample in an oven at 80 ℃ to obtain the final near infrared luminescent material.
The phases of the near infrared luminescent material samples of the present invention were analyzed using an X-ray powder diffractometer (Minflex 600, japan physics).
The excitation and emission spectra of the samples were measured with a FLS980 (Edinburgh instruments) fluorescence spectrometer, and the thermal stability of the materials was evaluated by testing the temperature-varying emission spectra of the materials in combination with a 77-600K temperature-varying stage.
The luminescent quantum yield of the materials was tested by fiber optic coupling using a fiber optic spectrometer (ideaotics, PG 2000).
The materials were evaluated for their moisture and high temperature stability at 85 ℃ and 85% humidity using a constant temperature and humidity test box.
XRD analysis of the samples synthesized in examples 1-9 using the solid phase reaction method showed pure phases. The XRD diffractogram of the near infrared luminescent material prepared in example 1 is shown in fig. 1; as can be seen from FIG. 1, the luminescent material is Na in pure phase 3 AlP 3 O 9 N。
The excitation and emission spectra of the samples were measured with an FLS980 (Edinburgh instruments) fluorescence spectrometer. The excitation spectrum of the luminescent material obtained in example 1 is shown in fig. 2, from which it can be seen that: the excitation spectrum of the luminescent material comprises three effective excitation bands, namely 250-320nm, 380-500nm and 520-730nm; the emission spectrum of the luminescent material obtained in example 1 is shown in fig. 3, from which it can be seen that: the emission spectrum of the luminescent material covers 640-1000nm, so that the luminescent material has near infrared broadband emission performance.
Regarding the thermal stability of the luminescent material, the ratio of the integrated luminescence intensity of the luminescent material at 150 ℃ to the integrated luminescence intensity at room temperature was used for evaluation. The testing method comprises the following steps: the luminescent material is placed on a heating table, excitation light is introduced through an optical fiber, the emission spectrum of the luminescent material is tested after the heating table is heated to a target temperature, and the emission spectra of samples at different temperatures are tested. As shown in FIG. 4, na obtained in example 1 of the present invention 3 AlP 3 O 9 N：4％Cr 3+ The ratio of the integrated luminous intensity at 150 ℃ to the integrated luminous intensity at room temperature can reach 82%, as shown in fig. 4.
The luminescence quantum yield eta of the material is calculated by adopting the following formula:
wherein N is em To emit photon number, N ex To absorb the number of photons. The quantum yield of the luminescent material provided by the invention is in the range of 70-85% through test calculation.
Moisture and high temperature resistance stability test of luminescent materials: the near infrared luminescent materials prepared in examples 1 to 9 were aged in a constant temperature and humidity test chamber at 85℃and 85% relative humidity, and after 480 hours, the samples were subjected to luminescence intensity test to evaluate the moisture resistance and high temperature resistance stability of the luminescent materials. The test results are shown in Table 1, and it can be seen from Table 1 that the luminescent material of the present invention can maintain the maximum luminous intensity of 98% or more at room temperature under the high-temperature and high-humidity environment. Therefore, the near infrared luminescent material prepared by the invention has higher moisture resistance and high temperature resistance stability.
TABLE 1
Example 10: LED light source
The present example provides an LED light source comprising an LED semiconductor chip and the luminescent material prepared in example 1, wherein the LED semiconductor chip is a commercially available blue LED chip having a wavelength of 450 nm.
The preparation method of the LED light source comprises the following steps: near-infrared luminescent material Na prepared in example 1 of the present invention 3 AlP 3 O 9 N：4％Cr 3+ Uniformly mixing the materials in silica gel according to the mass ratio of 1:1, coating the mixture on an LED semiconductor chip, and curing the mixture to obtain the LED light source.
The performance of the LED light source prepared in example 1 was tested using HASS-2000 (photovoltaics, inc. In hangzhou) single LED/module photo-electric test system with a test current of 60mA and a voltage of 3V. The light output power of the light source in the near infrared range can reach 21mW (at 350mA current and 3V, the light output power of the light source in the near infrared range can reach 92 mW.
The embodiments of the present invention have been described above by way of example. However, the scope of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art, which fall within the spirit and principles of the present invention, are intended to be included within the scope of the present invention.
Claims (10)
1. A near infrared luminescent material is characterized in that the chemical composition of the luminescent material is represented by a chemical formula A a B b P c O x M y ：zCr 3+ The representation, wherein,
the A element is one or more selected from Li, na, K, rb, cs, mg, ca, sr and Ba;
the B element is one or more selected from Al, ga, in, fe, nd, ta, ti, zr, V, ni and rare earth elements;
the M element is at least one selected from F, cl and N;
Cr 3+ z is more than or equal to 0.01% and less than or equal to 100%, preferably more than or equal to 1% and less than or equal to 10% for luminescent center ions;
a. b, x and y are the simplest stoichiometric numbers of elements, 0.ltoreq.a <10, 0.ltoreq.b <10, 0.ltoreq.c <20,0< x <30,0< y <30;
preferably, the rare earth element is La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sc or Y.
2. The near infrared light emitting material of claim 1, wherein the light emitting material a a B b P c O x M y ：zCr 3+ The material is prepared from raw materials including an A source, a B source, a P source, an M source and a Cr source through high-temperature calcination.
Preferably, the a source is provided by a compound comprising element a. Preferably, the a source is selected from at least one of a carbonate, an oxide, a nitride, a nitrate, and a halide containing an a element.
Preferably, the B source is provided by a compound comprising element B; for example, at least one selected from the group consisting of a carbonate, an oxide, a nitride, a nitrate, and a halide containing a B element.
Preferably, the Cr source is provided by a compound comprising Cr element; for example, at least one selected from the group consisting of carbonates, oxides, nitrides, nitrates and halides of Cr-containing elements.
Preferably, the P source is provided by a compound comprising an element P; for example, at least one selected from the group consisting of a phosphate containing a P element and an oxide containing a P element.
Preferably, the M source is provided by an M element-containing compound; for example, by at least one of a fluorine source, a chlorine source, and a nitrogen source.
Preferably, the fluorine source is KF, naF, caF 2 Ammonium fluoride, aluminum fluoride and SrF 2 At least one of them.
Preferably, the chlorine source is at least one of potassium chloride, sodium chloride, ammonium chloride and aluminum chloride.
Preferably, the nitrogen source is at least one of AlN and urea.
3. The near infrared light emitting material according to any one of claims 1 to 2, wherein the light emitting material may be Na 3 AlP 3 O 9 N：4％Cr 3+ 、Na 3 TiP 3 O 9 N：2％Cr 3+ 、NaAlPO 4 F：4％Cr 3+ 、KAlPO 4 F：2％Cr 3+ 、NaVPO 4 F：2％Cr 3+ 、Na 5 AlP 2 O 8 F 2 ：3％Cr 3+ 、Na 3 Al 2 P 2 O 8 F 3 :2％Cr 3+ 、SrAl 2 P 2 O 8 F 2 :4％Cr 3+ 、CaAl 2 P 2 O 8 F 2 :4％Cr 3+ 。
Preferably, the luminescent material is capable of being excited by violet, blue or red light.
Preferably, the luminescent material has near infrared broadband emission performance, and can emit near infrared light with a wavelength range of 650-1300nm, and a peak value in a range of 700-1000 nm.
4. A method for producing a near infrared light emitting material according to any one of claims 1 to 3, characterized in that the method comprises the steps of:
(1) According to chemical formula A a B b P c O x M y ：zCr 3+ The stoichiometric ratio of each element in the (a), B, P, M and Cr sources are mixed to obtain a mixture;
(2) And calcining the mixture to obtain the near infrared luminescent material.
5. The process according to claim 4, wherein in step (1), the compound of formula A is represented by formula A a B b P c O x M y ：zCr 3+ The stoichiometric ratio of each element of the group A source, the group B source, the group P source, the group M source and the group Cr source are weighed, wherein the use amount of the group P source can be 5wt.% to 200wt.% in excess.
6. The method according to claim 4 or 5, wherein in step (2), the calcination is performed in air, an inert atmosphere, or a reducing atmosphere.
Preferably, the inert atmosphere is nitrogen or argon.
Preferably, the reducing atmosphere is (5-15% by volume) H 2 And (95 v% -85 v%) N 2 A mixed gas, or a calcination environment containing carbon powder.
Preferably, in step (2), the calcination temperature is 150-1500 ℃, preferably 500-1200 ℃, more preferably 700-1100 ℃; the calcination time is 1 to 30 hours, preferably 5 to 20 hours, more preferably 8 to 15 hours.
Preferably, in step (2), the number of times of calcination is at least one, and may be, for example, two, three or more times.
Preferably, in the step (2), two times of calcination are performed, wherein the temperature of the first time of calcination is 150-700 ℃, and the time of the first time of calcination is 1-12 hours; the temperature of the second calcination is 700-1500 ℃, and the time of the second calcination is 1-20h.
7. Use of the near infrared light emitting material according to any one of claims 1 to 3 and/or the light emitting material produced by the production method according to any one of claims 4 to 6 in a light emitting device. Wherein, the light emitting device is used in the fields of petrochemical industry, high polymer, pharmacy, clinical medicine, environmental science, textile industry or food detection, etc.
Preferably, the light emitting device is a fluorescence conversion type near infrared LED device. Further, the fluorescence conversion type near infrared LED device is used in the fields of biological identification, 3D sensing, food/medical detection, agricultural production or biological imaging and the like.
8. An LED light source, characterized in that the LED light source comprises the near infrared luminescent material as claimed in any one of claims 1 to 3 and/or the near infrared luminescent material a produced by the production method as claimed in any one of claims 4 to 6 a B b P c O x M y ：zCr 3+ 。
Preferably, the fluorescent conversion layer of the LED light source comprises the near infrared luminescent material of any one of claims 1 to 3 and/or the near infrared luminescent material a produced by the production method of any one of claims 4 to 6 a B b P c O x M y ：zCr 3+ 。
9. The LED light source of claim 8, further comprising an LED semiconductor chip, wherein the phosphor conversion layer is disposed on the LED semiconductor chip, and wherein the phosphor conversion layer comprises the near infrared luminescent material a a B b P c O x M y ：zCr 3+ 。
Preferably, the LED light source further comprises a glue layer disposed on the LED semiconductor chip, wherein the glue layer contains the luminescent material a uniformly dispersed therein a B b P c O x M y ：zCr 3+ 。
Preferably, the fluorescent conversion layer is coated on an LED semiconductor chip, and the LED semiconductor chip is used for carrying the fluorescent conversion layer.
Preferably, the LED semiconductor chip is at least one of a violet LED chip, a blue LED chip, and a red LED chip.
Preferably, the LED light source is a fluorescence conversion type near infrared LED device and is used in the fields of biological identification, sensing, food detection, medical detection, temperature measurement, agricultural production or biological imaging.
10. The method for manufacturing the LED light source according to claim 8 or 9, characterized in that the method for manufacturing comprises the steps of: the near infrared light emitting material according to any one of claims 1 to 3 and/or the near infrared light emitting material prepared by the preparation method according to any one of claims 4 to 6 is mixed with glue and then coated on an LED semiconductor chip.
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