CN108865139B - Broad-band near-infrared emission substance and light-emitting device containing same - Google Patents
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- 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
- C09K11/7708—Vanadates; Chromates; Molybdates; Tungstates
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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
- C09K11/7776—Vanadates; Chromates; Molybdates; Tungstates
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- 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
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- H01L33/502—Wavelength conversion materials
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Abstract
The invention belongs to the technical field of luminescent materials, in particular to a broadband near-infrared emitting luminescent material, and particularly relates to a material which can generate red light and near-infrared emission in the range of 650nm-1600nm under the excitation of ultraviolet light, purple light, blue light and red light, and further discloses a preparation method thereof and a luminescent device containing the luminescent material. The invention relates to a broad-band near-infrared emission luminescent material, which comprises a molecular formula AaDbMcOeAn inorganic compound of xCr, the luminescent material having a strictly occupied ordered structure, the luminescent material having a relatively broad excitation wavelength (250-700 nm); the material is a single substance, takes Cr as an optical active center, can well absorb ultraviolet light, blue light and red light, and can realize broadband red light and near infrared emission in the range of 650nm-1600nm under the excitation of ultraviolet light, purple light or blue light.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, in particular to a broadband near-infrared emitting luminescent material, and particularly relates to a material which can generate red light and near-infrared emission in the range of 650nm-1600nm under the excitation of ultraviolet light, purple light, blue light and red light, and further discloses a preparation method thereof and a luminescent device containing the luminescent material.
Background
In the chemical detection field, because the red light and near infrared region in the range of 650nm-1600nm cover the characteristic information of the frequency combination of the vibration of the hydrogen-containing group (O-H, N-H, C-H) and the absorption region of each level of frequency multiplication, the characteristic information of the hydrogen-containing group of the organic molecule in the sample can be analyzed and obtained by scanning the near infrared spectrum of the sample, and the method has positive significance for the structural identification and analysis of chemical substances. And the near infrared spectrum technology is utilized to analyze the sample, so that the method has the advantages of convenience, rapidness, high efficiency, accuracy and lower cost, has the advantages of no need of not damaging the sample, no consumption of chemical reagents, no pollution to the environment and the like, can be widely applied to the fields of petrochemical industry, macromolecules, pharmacy, clinical medicine, environmental science, textile industry, food detection and the like, and is favored by more and more people.
In the prior art, there are several ways to obtain red and near infrared spectra, such as:
1. wide spectrum for obtaining red and near infrared spectra using LED chips
Because the full width at half maximum of the light-emitting peak of the LED chip is limited (typical width is 20nm), in order to obtain a spectrum with a width in the range of 650nm to 1600nm (red light and near infrared), tens of chips are required to obtain the spectrum, for example, chinese patent CN103156620A discloses a multi-channel parallel near infrared spectrum imaging system, but because the packaging form, the driving voltage and the driving current of each chip are different, the multi-chip is used to realize the ultra-wide range of red light and near infrared spectrum (650nm to 1600nm), and the technical difficulty is usually very high.
2. Obtaining broad spectra using phosphor conversion materials
For example, chinese patent CN202268389U discloses a near-infrared diode using a blue-light chip to excite a down-conversion phosphor, which discloses a method for obtaining emission of near-infrared light with a wavelength range of 900nm to 1100nm based on the blue-light chip to excite the down-conversion phosphor. The range of the emission spectrum is not broad, mainly because very broad red and near infrared emissions (e.g., 650nm-1600nm) cannot be obtained with a single phosphor. Therefore, in order to obtain a wider spectrum, a technical scheme of exciting a plurality of phosphors with a plurality of light sources has appeared.
For example, the chinese patent CN105932140A discloses a near-infrared wavelength led light source, which comprises an excitation light source and a wavelength conversion componentAnd the wavelength optimizing component, the excitation light source is a visible light or near infrared light source, which comprises a single LED (or LD), or a plurality of groups of LED (or LD) visible light or near infrared light chips, or an LED visible light or near infrared light integrated light source, or a visible light or near infrared light laser, or a group of visible light or near infrared light laser arrays, and provides a visible light or near infrared light luminous light source; the wavelength conversion component is prepared by mixing fluorescent powder and a transparent material, comprises a fluorescent glass coating wavelength conversion component, a fluorescent resin wavelength conversion component and a fluorescent powder lens wavelength conversion component, and can also be a phosphor thick film; the wavelength conversion component contains uniformly distributed fluorescent bodies C, the fluorescent bodies C adopt fluorescent powder which can generate near infrared wavelength by excitation, and the fluorescent bodies C can emit light rays with specific central wavelength by excitation of visible light or near infrared light; the wavelength range of the excited light of the phosphor C covers the wavelength range of near infrared, namely the wavelength range is 650nm to 2500 nm; under the excitation of visible light or near infrared light source, the central wavelength of the light emitted by the fluorescent powder should be at or near the center of the light emitting wavelength of the light source finally needed. The excitation light source is not limited to visible light or near infrared light source, but also can be near ultraviolet light source, correspondingly, the phosphor C must be near ultraviolet light to emit near infrared light; using near-infrared phosphor (Y)1-xLax)2O3:Er3+The wavelength conversion component mainly used for wavelength conversion emits 1.5 mu m near infrared light under the irradiation of 980nmLD near infrared light; using near infrared phosphor Ba9.99Bi0.01(PO4)6Cl2(ii) a The wavelength conversion component mainly used for wavelength conversion can emit near-infrared light of 1.25 mu m under the irradiation of 690nm red light; and near-infrared fluorescent powder 26.6B is adopted2O3-52.33PbO-16GeO2-4Bi2O3-lSm2O3The wavelength conversion component mainly used for wavelength conversion emits 978nm and 1.18 mu m near infrared rays under the irradiation of 488nm blue light; adopts near-infrared phosphor Cr3+:GdAl3(BO3)4(ii) a Mainly taking the same asThe wavelength conversion component for wavelength conversion can emit 720nm near-infrared light under the irradiation of 420nm blue light; adopts near-infrared fluorescent powder CaMoO4:(Tb3+，Yb3+) (ii) a The wavelength conversion component mainly used for wavelength conversion emits 1.05 mu m near infrared light under the irradiation of 306nm ultraviolet light. Obviously, in the scheme, after a plurality of kinds of fluorescent powder are mixed, light sources with different wavelengths are adopted for excitation, and then wider red light and near infrared emission can be obtained. However, after a plurality of phosphors are mixed, the phenomenon of mutual absorption of light emission exists between different phosphors, which often results in low light emitting efficiency, and because a plurality of (at least 5 in the scheme) light sources are required for excitation, the packaging form and the driving mode of each light source are different, which inevitably results in the complexity of the manufacturing process of the red light and near infrared emitting device, and is difficult to have better red light and near infrared emitting performance.
In addition, regarding the red light and infrared emission material alone, for example, chinese patent CN103194232A discloses a broadband ultraviolet-visible light excited near-infrared fluorescence emission material, and its preparation method and application, in the luminescent material, the chemical formula is Y1-x-zMzAl3-y(BO3)4:Crx 3+,Yby 3+Wherein M is Bi3+And La3+One or two of them, 0<x≤0.2，0<y is less than or equal to 0.2, z is less than or equal to 0.2 and less than or equal to 0.2, the excitation wavelength of the fluorescent material is between 350nm and 650nm, the emission spectrum range is between 900nm and 1100nm, and the emission spectrum range is narrow.
For another example, German patent DE102014107321A1 discloses an Infraot LED which provides a near-infrared phosphor having the general formula MAL12O19xTi, wherein M is Ca or Sr, the phosphor can generate red light and near infrared emission between 650nm and 1000nm under the excitation of light within the range of 400-600nm, and the emission spectrum range is narrow and the intensity is low.
Also as in non-patent document LaAlO3:Mn4+As Near-involved superconducting Phosphor for Medical Imaging A Charge compression Study (Materials 2017, 10, 1422, 1) discloses a chemical composition LaAlO3:Mn4+The fluorescent powder can generate red light emission from 600nm to 800nm under the excitation of ultraviolet light, has narrow emission spectrum range and can not be excited by blue light, and still has certain application defects.
For another example, European patent EP2480626A2 discloses a composition of LiGaO2:0.001Cr3+,0.001Ni2+The fluorescent powder can generate near-infrared emission between 1000nm and 1500nm under the excitation of ultraviolet light, has the problem of narrow emission spectrum range, has long afterglow effect, lasts for several minutes, and is not suitable for being used as a light-emitting device.
Non-patent literature rare earth ion doped CaWO4Near-infrared quantum cutting research of phosphor (Master thesis of Tai principals university, Liyunqing, 2015) discloses a chemical component CaWO4:1％Yb3+The fluorescent powder can generate near infrared emission of 900nm-1100nm under the excitation of ultraviolet light, has narrow emission spectrum range, cannot be excited by blue light, and has low luminous intensity.
Non-patent document Ca3Sc2Si3O12:Ce3+，Nd3+In the preparation and luminescent properties of near-infrared phosphor (silicate science, vol. 38, No. 10, 2010), it is believed that the phosphor Ca is excited by blue light3Sc2Si3O12:Ce3+，Nd3+Can generate near infrared emission between 800nm and 1100nm, but has narrow emission spectrum range and low luminous intensity.
In addition, since the ions of the Cr element have abundant variable valence states, which include +2, +3, +4, +5, and +6, etc., the luminescence properties of the valence states are different in different crystal environments. Non-patent literature "The photophysicsof Chromium (III) complexes, Chemical Reviews" (Volume 90, Number 2, March/April1990) clearly indicates that +3 valent Cr ions cannot exist in a tetrahedral coordination environment, but can emit light in a 6-coordination/octahedral crystallographic environment; also, for example, non-patent document "Spectroscopy of lantanum lutetium gallium garnet crystals with chromium" (J.Opt.Soc.Am.B., Vol.20, No.3, March2003) And non-patent literature "Electronic and vironic transitions of the Cr4+doped garnetsLu3Al5O12，Y3Al5O12，Y3Ga5O12and Gd3Al5O12It is clearly shown in J.Lumin.68, 1-14, 1996 that the +4 Cr ion has luminescence property only in the tetrahedral coordination environment.
In summary, in the prior art, a material capable of generating ultra-wide red light and near-infrared emission, especially a material capable of generating high-intensity ultra-wide red light and near-infrared emission, is not available yet; on the other hand, materials which can be excited by a blue light source with mature technology to generate ultra-wide red light and near-infrared emission are lacked, and particularly materials which have short fluorescence life and can generate high-intensity ultra-wide red light and near-infrared emission are lacked; moreover, a device which is based on a single excitation light source and has a simple packaging form and can generate ultra-wide red light and near infrared emission is lacked, and Cr ions based on different valence states emit light completely differently in different crystal environments, and no luminescent material with mixed valence state Cr is found. Therefore, it is very necessary to develop a material which has a single component, can be excited by various light sources/wave bands, has high luminous intensity, has short fluorescence lifetime (no more than second level) and can generate ultra-wide red light and near infrared emission, and has positive significance for the fields of petrochemical industry, high molecules, pharmacy, clinical medicine, environmental science, textile industry, food detection and the like.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to provide a broadband near-infrared emitting luminescent material, which has the emission performance that the luminescent material can be excited by the spectrum with rich wavelength range (ultraviolet or purple light or blue light) to generate extremely wide red light and near infrared spectrum (650nm-1600nm), and solves the problems of weak light emission intensity, long fluorescence lifetime and narrow emission spectrum range of a single group of light-emitting materials in the prior art;
the second technical problem to be solved by the present invention is to provide a light emitting device containing the above luminescent material, which can generate red light and near infrared light in the range of 650nm to 1600nm by using a single excitation light source and the luminescent material of the present invention
In order to solve the technical problem, the invention provides a broadband near-infrared emission luminescent material, which comprises a molecular formula AaDbMcOeAn inorganic compound of xCr, wherein,
the element A includes La and/or Y;
the D element comprises Hf element, and Zr element or Sn element can be selectively added;
the M element comprises one or two of Ga, Al or Sc elements;
and the parameters a, b, c, e and x satisfy the following conditions: a is more than or equal to 2.8 and less than or equal to 3.2; b is more than or equal to 0.9 and less than or equal to 1.1; c is more than or equal to 4.5 and less than or equal to 5.5; e is more than or equal to 13.5 and less than or equal to 14.5; x is more than or equal to 0.002 and less than or equal to 0.2.
Preferably, the broad-band near-infrared-emitting luminescent material has a crystal structure in which the D element occupies a crystallographic octahedral site of the material, the M element occupies a crystallographic tetrahedral site of the material, and the tetrahedral/octahedral site occupation is strictly ordered.
Specifically, in the red and near infrared emission material, in the crystal structure of the material, the element represented by D strictly occupies a crystallographic octahedral position, and the element represented by M strictly occupies a crystallographic tetrahedral position, that is, the material is a crystal structure with a strictly ordered tetrahedral/octahedral occupancy; wherein D element (one or two of Hf, Zr and Sn, wherein Hf must be contained) strictly occupies octahedral crystallographic positions, i.e. the D element coordinates with 6O ions and forms octahedrons; the M element (one or two of Ga, Al and Sc) strictly occupies tetrahedral crystallographic positions, i.e. the M element coordinates with 4O ions and forms a tetrahedron.
In the broadband near-infrared emission luminescent material, the Cr element comprises Cr3+Ions and Cr4+Ions.
More preferably, the Cr is3+The ions occupy the crystallographic positions where the D elements are located, namely octahedral crystallographic positions; the Cr is4+The ions occupy the crystallographic positions of the M element, i.e. tetrahedral crystallographic positions。
On the other hand, if not occupied according to the above coordination, i.e., if Cr4+The ions occupy the crystallographic positions in which the D element is located, i.e. the octahedral crystallographic positions, while Cr3+The ions occupy the crystallographic positions in which the M element is located, i.e., tetrahedral crystallographic positions. Then, the ionic radius (octahedral crystallographic position, 6 coordinates) of the element D is
Left and right, Cr4+The ionic radius (octahedral crystallographic position, 6 coordinates) of an ion is only
When Cr is generated4+When D element is substituted by ion, because the difference between the two ionic radii is over 40%, the mutual substitution is possible only when the ionic radii are different by less than 15% according to the general principle of crystal chemistry. Obviously, if it is Cr4+The ion occupies the crystallographic position (octahedral crystallographic position, 6 coordination) of the element D, and does not accord with the general crystallographic law; if it occurs, it inevitably results in Cr occupying the crystallographic position (octahedral crystallographic position, 6-coordinate) of the D element4+The octahedron formed by the ions and the surrounding coordinated O ions is strongly contracted and distorted, so that the coordination environment of the adjacent ions in the unit cell is damaged, and finally the crystal structure of the material is damaged, namely the crystal symmetry of the material is changed. At this time AaDbMcOexCr will no longer be a crystal structure with strictly ordered tetrahedral/octahedral occupation and will not be related to the present invention with the formula AaDbMcOexCr and a crystal structure with strictly ordered tetrahedral/octahedral occupation does not produce corresponding technical effects.
Preferably, in the element D, the mole percentage of the element Hf in the element D is 80-100%.
Most preferably, in the broadband near-infrared emission luminescent material, the element A is La, the element D is Hf, and the element M is Ga.
The invention also discloses a method for preparing the broadband near-infrared emission luminescent material, which comprises the following steps:
(1) uniformly mixing compounds corresponding to selected A, D, M, Cr elements (O element is from compounds corresponding to A or D or M or Cr) according to a selected stoichiometric ratio (molar ratio) to obtain a mixture;
(2) the obtained mixture is sintered for 4 to 24 hours at the temperature of 800-1100 ℃ in the air atmosphere to obtain a roasted product;
(3) the obtained calcined product is crushed again, and the obtained powder is sintered for 4 to 24 hours in an atmosphere of hydrogen, nitrogen/hydrogen mixture, carbon monoxide or ammonia (preferably in a nitrogen/hydrogen mixture), and the required luminescent material is obtained through conventional treatment.
The chemical molecular formulas of the luminescent materials are obtained by the mixture ratio of the raw materials, and the difference caused by different valence of Cr element can be finely adjusted by the content of O element.
The red and near infrared emitting materials described in the present invention can be prepared using methods of the prior art or new methods discovered in the future.
The near-infrared emitting material can be used for manufacturing luminescent devices, and the luminescent devices manufactured by the near-infrared emitting material can be used in the fields of petrochemical industry, high molecules, pharmacy, clinical medicine, environmental science, textile industry, food detection and the like.
The invention also discloses a luminescent device, which at least comprises a luminescent light source and a phosphor, wherein the phosphor at least comprises the broadband near-infrared-emitting luminescent material.
Preferably, the phosphor further contains a phosphor having a structure such as Y3-yGa5-xO12:xCr,yYb、Y3-xAl5O12:x(Ce,Nd)、La3GeGa5-xO14:xCr、La3-xSi6N11X (Ce, Er) or CaxSr1-x-yAlSiN3Y (Er, Ce, Eu) is shown in the chemical formula.
More preferably, the light-emitting light source includes a light-emitting diode, a laser diode, or an organic EL light-emitting device. Preferably, the light-emitting source is a light-emitting diode having an emission peak wavelength in the range of 250nm to 500nm, preferably 440nm to 470 nm.
Further, the light-emitting device can generate red light-near infrared emission in the range including but not limited to 650nm-1600 nm.
The invention relates to a broad-band near-infrared emission luminescent material, which comprises a molecular formula AaDbMcOeAn inorganic compound of xCr, the luminescent material having a strictly occupied ordered structure, the luminescent material having a relatively broad excitation wavelength (250-700 nm); the material is a single substance, takes Cr as an optical active center, can well absorb ultraviolet light, blue light and red light, and can realize broadband red light and near infrared emission in the range of 650nm-1600nm under the excitation of the ultraviolet light, the purple light or the blue light; compared with the luminescent material with the disordered space occupying structure, the luminescent material has stronger and wider near infrared luminescence and shorter fluorescence lifetime.
The phosphor of the luminescent device comprises the broad band near infrared emission luminescent material, and the luminescent device can obtain a device capable of generating 650nm-1600nm ultra-wide red light and near infrared emission by using a single excitation light source, has a better application effect, and can meet the application requirements of various fields such as petrochemical industry, high molecules, pharmacy, clinical medicine, environmental science, textile industry, food detection and the like.
Drawings
In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
FIG. 1 is an X-ray diffraction pattern of the phosphor obtained in example 1 of the present invention;
FIG. 2 is a graph of the emission spectrum of the phosphor obtained in example 1 of the present invention under 450nm excitation;
FIG. 3 is a diagram showing an excitation spectrum of the phosphor obtained in example 1 of the present invention at a monitoring wavelength of 958 nm;
FIG. 4 is an excitation spectrum of the phosphor obtained in example 1 of the present invention at a monitoring wavelength of 1200 nm;
FIG. 5 is a graph of the emission spectrum of the phosphor obtained in example 2 of the present invention under 450nm excitation;
FIG. 6 is an X-ray diffraction pattern of the phosphor obtained in comparative example 1 of the present invention;
FIG. 7 is a graph showing an emission spectrum of the phosphor obtained in comparative example 1 of the present invention under excitation at 450 nm;
FIG. 8 is a graph showing an emission spectrum of the phosphor obtained in comparative example 2 of the present invention under excitation at 450 nm;
fig. 9 is a schematic view of a light emitting device according to the present invention;
the reference numbers in the figures denote: 1-a first lead, 2-a heat sink, 3-a light-emitting diode, 4-a fluorescent powder coating, 5-a pouring sealant, 6-a reflector, 7-a second lead and 8-a gold wire.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The devices and reagents used in the following examples are all commercially available.
Example 1
The broadband near-infrared emission luminescent material described in this embodiment contains a compound with a composition formula of La3Hf0.998Ga5O14:0.002Cr。
According to the formula La3Hf0.998Ga5O140.002Cr, accurately weighing the raw material La2O3、HfO2、Ga2O3And Cr2O3Grinding the raw materials, uniformly mixing, putting into a crucible, and sintering at 950 ℃ for 10 hours in a high-temperature furnace in an air atmosphere; cooling to the room along with the furnaceAnd (3) crushing the sample, sintering the sample in a nitrogen/hydrogen mixed gas atmosphere at 1400 ℃ for 10 hours, and performing ball milling, water washing and screening on the sample to obtain the required broadband near-infrared emission luminescent material.
The fluorescent material obtained in example 1 was analyzed by X-ray diffraction to obtain an X-ray diffraction pattern thereof, as shown in fig. 1.
The fluorescent material obtained in example 1 was analyzed by a fluorescence spectrometer and excited at 450nm of blue light to obtain an excitation spectrum thereof, as shown in fig. 2. Therefore, the red light and near infrared spectrum of the material under the excitation of blue light are very wide and reach 650nm-1600nm, and the intensity is higher. The fluorescent material obtained in example 1 was analyzed by a fluorescence spectrometer, and the excitation spectra thereof were measured at 958nm and 1200nm, respectively, as shown in FIGS. 3 and 4, respectively. It can be seen that the phosphor can be effectively excited by ultraviolet, violet and blue light. The fluorescence lifetime of the material was measured and ranged from microseconds to milliseconds.
Example 2
The broadband near-infrared emission luminescent material described in this embodiment contains a compound with a composition formula of La2.8Hf0.9Al5.2O13.95:0.1Cr。
According to the formula La2.8Hf0.9Al5.2O13.950.1Cr, accurately weighing the raw material La2O3、HfO2、Al2O3And Cr2O3Grinding and uniformly mixing the raw materials, putting the raw materials into a crucible, sintering the raw materials at 950 ℃ for 10 hours in a high-temperature furnace under the air, cooling the raw materials to room temperature along with the furnace, crushing a sample, sintering the sample in a nitrogen/hydrogen mixed gas at 1400 ℃ for 10 hours, and performing ball milling, water washing and screening on the sample to obtain the required broadband near-infrared emission luminescent material.
The fluorescent material obtained in example 2 was analyzed by a fluorescence spectrometer and excited at 450nm of blue light to obtain an excitation spectrum thereof, as shown in fig. 5. Therefore, the red light and near infrared spectrum of the material under the excitation of blue light are very wide and reach 650nm-1600 nm.
Examples 3 to 14
The materials in each example are prepared in the same way as in example 1, and only by selecting compounds with proper amount according to the chemical formula composition of the target compounds in each example, mixing, grinding and roasting the selected compounds, the required broadband near-infrared-emitting luminescent material is obtained. The properties of the luminescent materials obtained in the respective examples were examined, and the results of the examination are shown in Table 1 below.
Comparative example 1
According to the formula La3GeGa4.998O140.002Cr, accurately weighing the raw material La2O3、Ga2O3、GeO2And Cr2O3The raw materials are ground, uniformly mixed and put into a crucible, the mixture is sintered for 10 hours at 980 ℃ in a high-temperature furnace under the air atmosphere, the mixture is cooled to room temperature along with the furnace, then a sample is crushed and sintered under the nitrogen/hydrogen atmosphere, the sintering temperature is 1400 ℃, the sintering time is 8 hours, and the sample is subjected to ball milling, water washing and screening to obtain the required luminescent material. The fluorescent material obtained in comparative example 1 was analyzed by X-ray diffraction to obtain an X-ray diffraction pattern thereof, as shown in fig. 6.
The fluorescent material obtained in comparative example 1 was analyzed by a fluorescence spectrometer and excited at 450nm of blue light to obtain an emission spectrum thereof, as shown in fig. 7. Therefore, the red light and near infrared spectrum of the material under the excitation of blue light are narrow, the intensity is low, the fluorescence life of the material is measured, and the service life range is about tens of seconds.
The luminescent materials prepared in comparative example 1 and examples 1 to 14 were tested for their performance under the excitation of 450nm blue light, and the test results are reported in table 1 below.
TABLE 1 test results of luminescent Material Properties
Comparative example 2
According to the formula La3Hf0.998Ga5O140.002Cr, accurately weighing the raw material La2O3、HfO2、Ga2O3And Cr2O3The raw materials are ground, uniformly mixed and put into a crucible, the mixture is sintered for 10 hours at 950 ℃ in a high-temperature furnace in the air atmosphere, the mixture is cooled to room temperature along with the furnace, then a sample is crushed and sintered in the air, the sintering temperature is 1400 ℃, the sintering time is 10 hours, and the sample is subjected to ball milling, water washing and screening to obtain the required luminescent material.
The luminescent material obtained in comparative example 2 was analyzed by a fluorescence spectrometer and excited at 450nm of blue light to obtain an emission spectrum thereof, as shown in fig. 8. It can be seen that the positions of the red light and near infrared spectrum peaks of the material under the excitation of blue light are completely different from those of the embodiment 1, the shapes of the red light and near infrared spectrum peaks are completely different from those of the embodiment 1, the intensities of the red light and near infrared spectrum peaks are far lower than those of the embodiment 1, the fluorescence lifetime of the material is measured, and the lifetime range is about several seconds.
Example 15
As shown in fig. 9, a 460nm blue light emitting diode 3 is fixed on a reflector 6, a heat sink 2 is disposed under the reflector 6, an anode of the blue light emitting diode 3 is connected to a first wire 1, and a cathode of the light emitting diode 3 is connected to a second wire 7 through a gold wire 8.
The chemical composition of example 1 was La3Hf0.998Ga5O14The fluorescent powder coating 4 is obtained by mixing and coating 0.002Cr fluorescent powder and epoxy resin on a blue light emitting diode 3, and finally the fluorescent powder coating 4, the blue light emitting diode 3 and a gold wire 8 are protected by using a pouring sealant 5. The device is detected to finally obtain a red light-near infrared emission device capable of generating light in the range including but not limited to 650nm-1600 nm.
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 (9)
1. A broad-band near-infrared emitting substance is characterized by that it contains AaDbMcOeAn inorganic compound of xCr, wherein,
the element A includes La and/or Y;
the D element comprises Hf element, and Zr element or Sn element can be selectively added; in the D element, the mole percentage of the Hf element in the D element is 80-100%;
the M element comprises one or two of Ga, Al or Sc elements;
and the parameters a, b, c, e and x satisfy the following conditions: a is more than or equal to 2.8 and less than or equal to 3.2; b is more than or equal to 0.9 and less than or equal to 1.1; c is more than or equal to 4.5 and less than or equal to 5.5; e is more than or equal to 13.5 and less than or equal to 14.5; x is more than or equal to 0.002 and less than or equal to 0.2.
2. The broadband emitting near-infrared emitting substance of claim 1, wherein the D element occupies crystallographic octahedral sites of the material, the M element occupies crystallographic tetrahedral sites of the material, and the emitting substance is a tetrahedrally/octahedrally space-occupying strictly ordered crystal structure.
3. A broadband near infrared emitting phosphor according to claim 2, wherein the Cr element comprises Cr3 +Ions and Cr4+Ions.
4. A broadband near infrared emitting phosphor according to claim 3, wherein said Cr is3+Ions occupy the crystallographic positions of the D element, the Cr4+The ions occupy the crystallographic positions of the M element.
5. The broadband-emitting near-infrared-emitting substance according to any one of claims 1 to 4, wherein the element A is an element La, the element D is an element Hf, and the element M is an element Ga.
6. A method for the preparation of a broadband near infrared-emitting luminescent substance according to any one of claims 1 to 5, comprising the steps of:
(1) uniformly mixing compounds corresponding to selected A, D, M, Cr elements according to a selected stoichiometric ratio to obtain a mixture;
(2) the obtained mixture is sintered for 4 to 24 hours at the temperature of 800-1100 ℃ in the air atmosphere to obtain a roasted product;
(3) and re-crushing the obtained roasted product, sintering the obtained powder for 4-24 hours in the atmosphere of hydrogen, nitrogen/hydrogen mixed gas, carbon monoxide or ammonia gas, and performing conventional treatment to obtain the required luminescent material.
7. A light-emitting device comprising at least a light-emitting source and a phosphor, characterized in that the phosphor comprises at least a broadband near-infrared-emitting luminescent substance as claimed in any one of claims 1 to 5.
8. The light-emitting device according to claim 7, wherein the phosphor further comprises a phosphor having a structure as Y3-yGa5-xO12:xCr,yYb、Y3-xAl5O12:x(Ce,Nd)、La3GeGa5-xO14:xCr、La3-xSi6N11X (Ce, Er) or CaxSr1-x-yAlSiN3Y (Er, Ce, Eu) is shown in the chemical formula.
9. The light-emitting device according to claim 7 or 8, wherein the light-emitting light source comprises a light-emitting diode, a laser diode, or an organic EL light-emitting device.
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| CN110079319B (en) * | 2019-05-24 | 2020-12-25 | 厦门大学 | Mixed-state infrared fluorescent material and preparation method thereof |
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| CN111676015B (en) * | 2020-06-23 | 2023-03-28 | 厦门大学附属心血管病医院 | Near-infrared long-afterglow luminescent material excited by biological window and preparation method thereof |
| CN113845911B (en) * | 2020-12-04 | 2023-02-03 | 有研稀土新材料股份有限公司 | Luminescent material and luminescent device comprising same |
| CN115125002A (en) * | 2021-03-25 | 2022-09-30 | 中国科学院宁波材料技术与工程研究所 | Silicon-based garnet near-infrared fluorescent material and preparation method and application thereof |
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