CN112266788B - Wide-spectrum near-infrared fluorescent material, near-infrared fluorescent glass, preparation method and device - Google Patents

Wide-spectrum near-infrared fluorescent material, near-infrared fluorescent glass, preparation method and device Download PDF

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CN112266788B
CN112266788B CN202011260230.3A CN202011260230A CN112266788B CN 112266788 B CN112266788 B CN 112266788B CN 202011260230 A CN202011260230 A CN 202011260230A CN 112266788 B CN112266788 B CN 112266788B
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CN112266788A (en
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解荣军
游莉
周天亮
毛敏倩
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Xiamen University
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    • H01S5/0608—Arrangements for controlling the laser output parameters, e.g. by operating on the active medium by varying physical parameters other than the potential of the electrodes, e.g. by an electric or magnetic field, mechanical deformation, pressure, light, temperature controlled by light, e.g. optical switch
    • H01S5/0609—Arrangements for controlling the laser output parameters, e.g. by operating on the active medium by varying physical parameters other than the potential of the electrodes, e.g. by an electric or magnetic field, mechanical deformation, pressure, light, temperature controlled by light, e.g. optical switch acting on an absorbing region, e.g. wavelength convertors
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Abstract

The invention relates to a wide-spectrum near-infrared fluorescent material, near-infrared fluorescent glass, a preparation method and a device, wherein the general chemical formula of the wide-spectrum near-infrared fluorescent material is BaO, aMgO and bAl2O3·cCr2O3Wherein a is more than or equal to 0.5 and less than or equal to 0.9, b is more than or equal to 4 and less than or equal to 4.9, and c is more than or equal to 0.1 and less than or equal to 0.8; under the excitation of blue light, the wide-spectrum near-infrared fluorescent material can generate an emission wavelength range of 600-1100 nm, a main peak of an emission spectrum is more than or equal to 700nm, and the full width at half maximum of the emission spectrum is more than 90 nm. The wide-spectrum near-infrared fluorescent material prepared by the invention has the advantages of good thermal quenching property, low raw material cost and relatively low synthesis temperature, can be excited by blue light to emit near-infrared light, and has the characteristic of large half-height width of an emission spectrum, so that the luminescent material has good prospect when being applied to manufacturing a near-infrared light source and a luminescent device.

Description

Wide-spectrum near-infrared fluorescent material, near-infrared fluorescent glass, preparation method and device
Technical Field
The invention relates to the technical field of luminescent material preparation, in particular to a wide-spectrum near-infrared fluorescent material, near-infrared fluorescent glass, a preparation method and a device.
Background
The near infrared spectrum analysis technology has the advantages of convenience, rapidness, no damage, no pollution and the like, and in recent years, near infrared spectrum analysis is gradually applied to the fields of food detection, petrochemical industry, macromolecules, pharmacy, facial recognition, security monitoring, machine vision and the like based on different wave bands (particularly 700-1700 nm) and different effects between substances.
The near infrared light source is the precondition of the application of the near infrared spectrum analysis technology. It is generally desirable that the near infrared spectrum output by the near infrared light source be sufficiently broad to cover a sufficient range. Conventional near-infrared light sources include xenon lamps or near-infrared lasers. The xenon lamp has large volume, high power consumption and short service life; the near-infrared laser has a narrow spectral range and poor applicability, and cannot meet technical requirements for various technical applications requiring a wide spectrum, such as food detection and the like.
The near-infrared LED chip mainly used in the application fields of remote controllers, optical communication, security monitoring and the like can also generate near-infrared spectrums. Although the multiband near-infrared chips are spliced, the near-infrared spectrum in the range of 700-1700 nm can be obtained, but a single chip of the near-infrared LED has the defects of small emission power, poor thermal attenuation characteristic, narrow emission spectrum (the typical half-height width of the emission spectrum is 20nm), high cost and the like, for example, a spectrum-adjustable LED near-infrared light source is disclosed in patent document 1 (chinese utility model patent CN203167371U, lugcun, vermilion, and crystal, and civilization, a spectrum-adjustable LED near-infrared light source), wherein the spectrum-adjustable LED near-infrared light source comprises 8 paths of independent controllable PWM wave generation modules, a key control module, an LED driving circuit, an LED array, and an installed light scattering sheet and an optical filter for spectrum adjustment. And each path of PWM wave controls the brightness of 8 LED lamps with one peak wavelength through an LED driving circuit. The LEDs with different peak wavelengths are selected, 8 LEDs with each peak wavelength are selected and are in annular arrangement, and the group of keys indirectly control the brightness of the LED lamp by controlling the pulse width of the PWM wave. The pulse width of each path of PWM wave is adjusted through a key, so that the brightness of the LED with each wavelength is adjusted, and the purpose of adjusting the spectrum is achieved through light scattering and light filtering. Obviously, the design of the near-infrared light source with continuous spectrum obtained by splicing the multiband near-infrared chips is very complicated, and because the packaging form, the driving voltage and the current of each chip are different, the manufacturing technology difficulty is very high, the cost is high, and the stability, the reliability and the practicability of the device are poor.
In recent years, in a white light LED technology, a technology for obtaining near infrared light by exciting a near infrared fluorescent material with a blue light LED chip has attracted attention. The near-infrared light source obtained by the technology has the advantages of all solid state, small volume, long service life, high efficiency, energy conservation, wide spectrum and the like. Because the blue light LED chip technology is mature, the wide-spectrum emission near-infrared fluorescent material with stable chemical property, high quantum efficiency and high thermal quenching characteristic becomes the key for the practicability of the near-infrared light source based on the blue light LED excitation fluorescent powder type. Therefore, it is of great importance to develop a near-infrared luminescent material with a broad spectrum.
Recently, near-infrared materials have been disclosed, for example, patent document 2 (chinese invention patent application CN110857388A, banyuanhong, liuronghui, xianxiao, maxiaole, Liyanfeng, chengmue, a near-infrared luminescent material containing a near-infrared luminescent material of the chemical formula M) discloses a near-infrared luminescent materialaAb(QO3)czZ, wherein, the M element is one or two of Sc, Y, La, Lu, Gd, Ca, Sr, Ba or Mg element; the element A is one or two of Sc, Y, La, Lu or Gd elements; q element is selected from one or two of Ga, Al, B or In elements; the Z element includes a Cr element; the M element and the A element are different; a. b, c and z satisfy the following conditions: a is more than or equal to 0.8 and less than or equal to 3.2, b is more than or equal to 1.8 and less than or equal to 3.2, c is more than or equal to 3.5 and less than or equal to 4.5, and z is more than or equal to 0.0001 and less than or equal to 0.5. In essence, the matrix structure protected by this patent is borate LaSc3(BO3)4. Doping Cr, LaSc with proper concentration3(BO3)4The main peak of the emission spectrum can reach about 850nm, but the heat quenching characteristic of the fluorescent powder is poor due to the low structural rigidity of borate.
Patent document 3 (chinese invention patent CN108795424B, zhangliang, zhangyeye, hushoudong, zhangxia, pannational emblem, wuhuajun, near-infrared phosphor with broadband emission and preparation method and application thereof) discloses a near-infrared fluorescent material, which has the chemical formula: (R)aLnbCecCrd)(LeCrg)(MkBmCrn)O12(ii) a Wherein R is Ca2+、Sr2+、Ba2+One or more of them, Ln is Lu3+、Y3+、La3+、Gd3+L is Hf4+And/or Zr4+M is Al3+And/or Ga3+B is Si4+And/or Ge4+；a、b、c、d、eG, k, m and n are the mole fractions of the elements. The near-infrared fluorescent material obtains wide-spectrum near-infrared emission by means of energy transfer, and the efficiency of the obtained near-infrared light source is low due to the low efficiency of the energy transfer.
Patent document 4 (chinese invention patent application CN110003909A, jiao qian bar, linqiting, king cuiping, qinlingshui, huding fang, xieiding, changjiawei, chentaoyang, wangxing, xulinging, Cr3+Activated broadband emission near-infrared fluorescent powder and preparation method) discloses a chemical formula of MN0.83Ga10.95-xO19:xCr3+The near-infrared fluorescent material of (1), wherein M is one or a combination of Mg, Ca, Sr and Ba; n is one or the combination of lanthanide elements; x is more than or equal to 0.01 and less than or equal to 0.20. The fluorescent material provided by the invention has an emission wavelength of 650-1200 nm, can be excited by light with a wavelength of 350-550 nm, and has poor thermal quenching characteristics.
Patent document 5 (chinese patent application CN111171811A, zhhao 2815678, wealth from huang, a near-infrared luminescent material and a preparation method thereof and an LED device thereof) discloses a near-infrared luminescent material and a preparation method thereof and an LED device thereof. The chemical formula of the luminescent material is as follows: AMAlF6:xCr3+Wherein A is alkali metal, M is alkaline earth metal, and x is more than or equal to 0.0001 and less than or equal to 30 at.%; it can be effectively excited in the range of 360-500 nm and can emit near infrared light of 700-1000 nm. The LED device is obtained by packaging the luminescent material and the purple light or blue light chip, and can be used as a near-infrared light source for the fields of analysis and detection, iris recognition, automobile sensing, security and the like. This patent dissolves the various compounds in a solvent and must rely on highly toxic HF to achieve the combination of the various compounds. The composite salt obtained by coprecipitation is fluoride, which has unstable chemical property and is easy to decompose when meeting water, and the excitation light source of the device is an LED, the power density of the excitation source is low, and the output power of the device is low.
In summary, it can be seen from the prior publications that the near infrared fluorescent material with wide spectrum and good thermal quenching property is very lacking, and the thermal quenching property of the fluorescent material is a key index for its practical application. Therefore, it is very necessary to develop a near-infrared fluorescent material with high thermal quenching property, and a device manufactured by using the material is applied to a near-infrared detection technology and serves the fields of security monitoring, biological identification, 3D sensing and food/medical detection.
Disclosure of Invention
The first purpose of the invention is to obtain a wide-spectrum near-infrared fluorescent material. The chemical general formula of the wide-spectrum near-infrared fluorescent material is as follows: BaO, aMgO, bAl2O3·cCr2O3Wherein a is more than or equal to 0.5 and less than or equal to 0.9, b is more than or equal to 4 and less than or equal to 4.9, and c is more than or equal to 0.1 and less than or equal to 0.8; under the excitation of blue light, the near-infrared fluorescent material can generate near-infrared emission with the emission wavelength range of 600-1100 nm, the main peak of an emission spectrum of more than 700nm and the full width at half maximum of the emission spectrum of more than 90 nm. Preferably, in the chemical general formula of the wide-spectrum near-infrared fluorescent material, a is more than or equal to 0.6 and less than or equal to 0.8, b is more than or equal to 4.5 and less than or equal to 4.8, and c is more than or equal to 0.12 and less than or equal to 0.15.
The second purpose of the invention is to provide a preparation method of the wide-spectrum near-infrared fluorescent material. The preparation method comprises the following steps: and mixing the Ba precursor, the Mg precursor, the Al precursor and the Cr precursor, and carrying out high-temperature solid-phase reaction in a reducing atmosphere to obtain the wide-spectrum near-infrared fluorescent material. Specifically, the molar ratio of the Ba precursor to the Mg precursor to the Al precursor to the Cr precursor is 1: a: b: c, and the obtained material has a chemical general formula: BaO, aMgO, bAl2O3·cCr2O3Wherein a is more than or equal to 0.5 and less than or equal to 0.9, b is more than or equal to 4 and less than or equal to 4.9, and c is more than or equal to 0.1 and less than or equal to 0.8.
The invention also provides near-infrared fluorescent glass and a preparation method thereof, wherein the near-infrared fluorescent glass is obtained by mixing the wide-spectrum near-infrared fluorescent material and glass powder and then carrying out high-temperature solid-phase reaction, and specifically, the high-temperature solid-phase reaction is carried out in the air atmosphere, wherein the temperature of the high-temperature solid-phase reaction is 500-800 ℃, and the time of the high-temperature solid-phase reaction is 0.1-1 h.
The invention also provides a laser near-infrared device, which comprises a blue laser diode and a light-emitting layer, wherein the light-emitting layer comprises the near-infrared fluorescent glass.
The specific scheme is as follows:
a wide-spectrum near-infrared fluorescent material has a chemical general formula as follows: BaO, aMgO, bAl2O3·cCr2O3Wherein a is more than or equal to 0.5 and less than or equal to 0.9, b is more than or equal to 4 and less than or equal to 4.9, and c is more than or equal to 0.1 and less than or equal to 0.8.
Furthermore, in the chemical general formula of the wide-spectrum near-infrared fluorescent material, a is more than or equal to 0.6 and less than or equal to 0.8, b is more than or equal to 4.5 and less than or equal to 4.8, and c is more than or equal to 0.12 and less than or equal to 0.15;
optionally, the preparation method of the wide-spectrum near-infrared fluorescent material comprises the steps of mixing a Ba precursor, a Mg precursor, an Al precursor and a Cr precursor, and carrying out high-temperature solid-phase reaction under a reducing atmosphere to obtain the wide-spectrum near-infrared fluorescent material, wherein the preferable temperature of the high-temperature solid-phase reaction is 1500-1700 ℃, and the time of the high-temperature solid-phase reaction is 4-10 hours.
Further, under the excitation of blue light, the wide-spectrum near-infrared fluorescent material generates near-infrared light with the emission wavelength range of 600-1100 nm, the main peak of the emission spectrum more than or equal to 700nm, and the full width at half maximum of the emission spectrum more than or equal to 90 nm;
optionally, the luminous intensity of the wide-spectrum near-infrared fluorescent material at 200-250 ℃ is not lower than 50% of the luminous intensity at room temperature.
The invention also provides a preparation method of the wide-spectrum near-infrared fluorescent material, which is to mix a Ba precursor, a Mg precursor, an Al precursor and a Cr precursor, and carry out high-temperature solid-phase reaction in a reducing atmosphere to obtain the wide-spectrum near-infrared fluorescent material.
Further, the Ba precursor is selected from one or more of a carbonate of Ba, an oxide of Ba or a nitrate of Ba;
optionally, the Mg precursor is selected from one or more of a carbonate of Mg, an oxide of Mg or a nitrate of Mg;
optionally, the Al precursor is Al2O3；
Optionally, the Cr precursor is Cr2O3；
Optionally, the purity of the Ba precursor, the Mg precursor, the Al precursor and the Cr precursor is not lower than 99.5 wt%.
Further, the temperature of the high-temperature solid-phase reaction is 1500-1700 ℃, and the time of the high-temperature solid-phase reaction is 4-10 hours;
optionally, the reducing atmosphere is ammonia gas or a nitrogen-hydrogen gas mixture, and preferably, the volume content of hydrogen in the nitrogen-hydrogen gas mixture is 10-25%.
The invention also provides near-infrared fluorescent glass, which is obtained by mixing the wide-spectrum near-infrared fluorescent material with glass powder and then carrying out high-temperature solid phase reaction, preferably, the mass ratio of the wide-spectrum near-infrared fluorescent material to the glass powder is 1: 1-1: 4; the melting point of the glass powder is 500-800 ℃.
The invention also provides a preparation method of the near-infrared fluorescent glass, which is to mix the wide-spectrum near-infrared fluorescent material with glass powder and carry out high-temperature solid-phase reaction in the air atmosphere to obtain the near-infrared fluorescent glass.
Further, the temperature of the high-temperature solid-phase reaction is 500-800 ℃, and the time of the high-temperature solid-phase reaction is 0.1-1 h;
optionally, the mass ratio of the wide-spectrum near-infrared fluorescent material to the glass powder is 1: 1-1: 4; the melting point of the glass powder is 500-800 ℃.
The invention also discloses a laser near-infrared device, which comprises a blue laser diode and a light-emitting layer, wherein the light-emitting layer comprises the near-infrared fluorescent glass.
Has the advantages that:
the invention provides a wide-spectrum near-infrared fluorescent material and a preparation method thereof, and the chemical of the fluorescent material is BaO, aMgO and bAl2O3·cCr2O3Wherein a is more than or equal to 0.5 and less than or equal to 0.9, b is more than or equal to 4 and less than or equal to 4.9, and c is more than or equal to 0.1 and less than or equal to 0.8; under the excitation of blue light, the near-infrared fluorescent material can generate an emission wavelength range of 600-1100 nm, a main peak of an emission spectrum of more than 700nm, and a full width at half maximum of the emission spectrum of more than 90 nm. Compared with the prior art, the wide-spectrum near-infrared fluorescent material prepared by the invention has brand-new chemical composition and chemical propertyThe material has the advantages of stable quality, no decomposition in water, good heat quenching property, low raw material cost and relatively low synthesis temperature, and can be excited by blue light to emit near infrared light, so that the luminescent material is applied to a near infrared light source.
Drawings
FIG. 1 is a graph showing an emission spectrum of a luminescent material obtained in comparative example 1 of the present invention;
FIG. 2 is a thermal quenching characteristic spectrum of the luminescent material obtained in comparative example 7 of the present invention;
FIG. 3 is a thermal quenching characteristic spectrum of the luminescent material obtained in comparative example 8 of the present invention;
FIG. 4 is a thermal quenching characteristic spectrum of the luminescent material obtained in comparative example 11 of the present invention;
FIG. 5 is a thermal quenching characteristic spectrum of the luminescent material obtained in comparative example 12 of the present invention;
FIG. 6 is a graph showing an emission spectrum of a luminescent material obtained in example 1 of the present invention;
FIG. 7 is a thermal quenching characteristic spectrum of the luminescent material obtained in example 1 of the present invention;
FIG. 8 is a graph showing an emission spectrum of a luminescent material obtained in example 21 of the present invention;
FIG. 9 is a thermal quenching characteristic spectrum of a luminescent material obtained in example 21 of the present invention;
FIG. 10 is a graph showing an emission spectrum of a near-infrared device obtained in example 22 of the present invention.
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.
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
The chemical general formula of the wide-spectrum near-infrared fluorescent material is as follows:
BaO·aMgO·bAl2O3·cCr2O3
wherein a is more than or equal to 0.5 and less than or equal to 0.9, b is more than or equal to 4 and less than or equal to 4.9, and c is more than or equal to 0.1 and less than or equal to 0.8. In some embodiments provided herein, a is preferably 0.5, b is preferably 4, and c is preferably 0.1; in some embodiments provided herein, a is preferably 0.6, b is preferably 4.5, and c is preferably 0.1; in some embodiments provided herein, a is preferably 0.6, b is preferably 4.5, and c is preferably 0.12; in some embodiments provided herein, a is preferably 0.6, b is preferably 4.5, and c is preferably 0.15; in some embodiments provided herein, a is preferably 0.6, b is preferably 4.5, and c is preferably 0.18; in some embodiments provided herein, a is preferably 0.6, b is preferably 4.5, and c is preferably 0.25; in some embodiments provided herein, a is preferably 0.6, b is preferably 4.5, and c is preferably 0.3; in some embodiments provided herein, a is preferably 0.6, b is preferably 4.5, and c is preferably 0.4; in some embodiments provided herein, a is preferably 0.6, b is preferably 4.5, and c is preferably 0.5; in some embodiments provided herein, a is preferably 0.6, b is preferably 4.5, and c is preferably 0.6; in some embodiments provided herein, a is preferably 0.6, b is preferably 4.5, and c is preferably 0.7; in some embodiments provided herein, a is preferably 0.6, b is preferably 4.5, and c is preferably 0.8; in some embodiments provided herein, a is preferably 0.7, b is preferably 4.5, and c is preferably 0.15; in some embodiments provided herein, a is preferably 0.8, b is preferably 4.5, and c is preferably 0.15; in some embodiments provided herein, a is preferably 0.9, b is preferably 4.5, and c is preferably 0.15; in some embodiments provided herein, a is preferably 0.8, b is preferably 4.6, and c is preferably 0.15; in some embodiments provided herein, a is preferably 0.8, b is preferably 4.7, and c is preferably 0.15; in some embodiments provided herein, a is preferably 0.8, b is preferably 4.8, and c is preferably 0.15; in some embodiments provided herein, a is preferably 0.8, b is preferably 4.9, and c is preferably 0.15; in some embodiments provided herein, a is preferably 0.9, b is preferably 4.9, and c is preferably 0.15; in other embodiments provided herein, a is preferably 0.9, b is preferably 4.9, and c is preferably 0.8.
The preparation method of the wide-spectrum near-infrared fluorescent material comprises the following specific steps:
and mixing the Ba precursor, the Mg precursor, the Al precursor and the Cr precursor, and carrying out high-temperature solid-phase reaction in a reducing atmosphere to obtain the wide-spectrum near-infrared fluorescent material.
In the step, the molar ratio of the Ba precursor to the Mg precursor to the Al precursor to the Cr precursor is 1: a: b: c, and the obtained material has a chemical general formula: BaO, aMgO, bAl2O3·cCr2O3Wherein a is more than or equal to 0.5 and less than or equal to 0.9, b is more than or equal to 4 and less than or equal to 4.9, and c is more than or equal to 0.1 and less than or equal to 0.8.
In the step, the Ba precursor is a compound containing Ba well known in the art, and is not particularly limited, and in the present invention, the Ba precursor is preferably one or more selected from the group consisting of a carbonate of Ba, an oxide of Ba, and a nitrate of Ba, and more preferably a carbonate of Ba (i.e., barium carbonate); the Mg precursor is selected from one or more of Mg carbonate, Mg oxide and Mg nitrate, and is more preferably Mg oxide, namely magnesium oxide; the Al precursor is derived from Al2O3(ii) a The Cr precursor is from Cr2O3。
The purity of the Ba precursor, the purity of the Mg precursor, the purity of the Al precursor and the purity of the Cr precursor are all not lower than 99.5%, and the higher the purity is, the fewer impurities in the obtained luminescent material are.
The reducing atmosphere in the step is not particularly limited as long as it is a dry atmosphere known to those skilled in the art, and a nitrogen-hydrogen mixed gas is preferred in the present invention.
The temperature of the high-temperature solid phase in the step is preferably 1500-1700 ℃, the atmosphere is nitrogen-hydrogen mixed gas, and in some embodiments provided by the invention, the temperature of the high-temperature solid phase is preferably 1600 ℃.
The time of high-temperature solid phase in the step is preferably 4-10 h, and more preferably 5-8 h; in some embodiments provided herein, the time period for the high temperature solid phase is preferably 6 hours.
The high temperature solid reaction phase is preferably carried out in a high temperature furnace. After the reaction is carried out, the reaction product is cooled to room temperature along with the furnace, and the wide-spectrum near-infrared fluorescent material can be obtained.
The invention adopts high-temperature solid-phase reaction to successfully prepare the wide-spectrum near-infrared fluorescent material.
The near-infrared device made of the wide-spectrum near-infrared fluorescent material at least comprises a blue laser diode and a light emitting layer. The luminescent layer is near-infrared fluorescent glass.
The near-infrared fluorescent glass uses the chemical general formula as follows: BaO, aMgO, bAl2O3·cCr2O3(wherein a is more than or equal to 0.5 and less than or equal to 0.9, b is more than or equal to 4 and less than or equal to 4.9, and c is more than or equal to 0.1 and less than or equal to 0.8) is mixed with the low-melting-point glass powder, and then the mixture is subjected to high-temperature solid-phase reaction to finally prepare the fluorescent material.
The preparation of the near-infrared fluorescent glass is carried out in an air atmosphere, the temperature of the high-temperature solid-phase reaction is preferably 500-800 ℃, and in some embodiments provided by the invention, the temperature of the high-temperature solid-phase reaction is preferably 700 ℃; the time of the high-temperature solid-phase reaction is preferably 0.1-1 h, and in some embodiments provided by the invention, the time of the high-temperature solid-phase reaction is preferably 0.5h, so that the near-infrared fluorescent glass is finally obtained.
In order to further illustrate the present invention, the following describes a broad spectrum near infrared fluorescent material and a preparation method thereof in detail with reference to examples.
The reagents used in the following comparative examples and examples are all commercially available.
The thermal quenching characteristic of the fluorescent powder is tested by adopting a fluorescent powder thermal quenching measuring instrument, and the measuring temperature range is as follows: 25-225 ℃ and the temperature control precision is +/-1 ℃. The intensity of the phosphor emission at 25 ℃ was recorded, then the temperature of the sample was raised to 225 ℃ and the intensity of the phosphor emission was recorded again. It is generally considered that if the light emission intensity of the phosphor at 225 ℃ reaches or exceeds 50% of the light emission intensity of the sample at 25 ℃, the phosphor is considered to have better thermal quenching characteristics.
In the nitrogen-hydrogen mixed atmosphere used in the following comparative examples and examples, the hydrogen content was 20% by volume.
The Ba precursor, the Mg precursor, the Al precursor and the Cr precursor used in the comparative examples and the examples are only examples, and do not limit the raw materials of the precursors, and the purity of the precursors is not lower than 99.5 wt%.
Comparative example 1
A material according to this comparative example comprising a compound of formula: BaO 0.4MgO 4Al2O3·0.1Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.4 MgO.4 Al is used according to the composition2O3·0.1Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.4 MgO.4Al2O3·0.1Cr2O3. The emission spectrum of the resulting luminescent material was measured using a fluorescence spectrometer, as shown in fig. 1. As can be seen from FIG. 1, the emission spectrum of the material prepared in comparative example 1 is near 692nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is only about 8nm, as shown in Table 1. It can be seen that the material obtained in comparative example 1 is not a broad-spectrum near-infrared fluorescent material.
Comparative example 2
A material according to this comparative example comprising a compound of formula: BaO 0.4MgO 4.9Al2O3·0.1Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.4 MgO.4.9 Al is used according to the composition2O3·0.1Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.4 MgO.4.9 Al2O3·0.1Cr2O3. Measuring the emission spectrum of the obtained luminescent material by using a fluorescence spectrometerThe full width at half maximum of the spectrum is shown in Table 1. As can be seen from Table 1, the emission spectrum of the material prepared in comparative example 2 is near 692nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is only about 9 nm. It can be seen that the material obtained in comparative example 2 is not a broad-spectrum near-infrared fluorescent material.
Comparative example 3
A material according to this comparative example comprising a compound of formula: BaO MgO 4.9Al2O3·0.1Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO-MgO-4.9 Al is used according to the component2O3·0.1Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO-MgO-4.9 Al2O3·0.1Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in comparative example 3 is near 692nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is only about 9 nm. It can be seen that the material obtained in comparative example 3 is not a broad-spectrum near-infrared fluorescent material.
Comparative example 4
A material according to this comparative example comprising a compound of formula: BaO MgO 4.9Al2O3·0.1Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO-MgO-4.9 Al is used according to the component2O3·0.1Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO-MgO-4.9 Al2O3·0.1Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in comparative example 4 has an emission spectrum around 692nm under the excitation of 450nm blue light, and the emission spectrum is half of that of the materialThe height and width are only about 9 nm. It can be seen that the material obtained in comparative example 4 is not a broad-spectrum near-infrared fluorescent material.
Comparative example 5
A material according to this comparative example comprising a compound of formula: BaO 0.5MgO 3.8Al2O3·0.1Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.5 MgO.3.8 Al is used according to the composition2O3·0.1Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.5 MgO.3.8 Al2O3·0.1Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in comparative example 5 is near 692nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is only about 9 nm. It can be seen that the material obtained in comparative example 5 is not a broad-spectrum near-infrared fluorescent material.
Comparative example 6
A material according to this comparative example comprising a compound of formula: BaO 0.9MgO 3.8Al2O3·0.1Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.9 MgO.3.8 Al is used according to the composition2O3·0.1Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.9 MgO.3.8 Al2O3·0.1Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in comparative example 6 is near 692nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is only about 9 nm. It can be seen that the material obtained in comparative example 6 is not a broad-spectrum near-infrared fluorescent material.
Comparative example 7
A material according to this comparative example comprising a compound of formula: BaO 0.5MgO 5Al2O3·0.8Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, according to the composition, BaO.0.5 MgO.5 Al2O3·0.8Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.5 MgO.5 Al2O3·0.8Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in comparative example 7 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is about 95 nm. It can be seen that the material obtained in comparative example 7 is a broad-spectrum near-infrared fluorescent material.
FIG. 2 shows the thermal quenching characteristic data of the material obtained in comparative example 7, which has a luminescence intensity of only about 10% at room temperature at 225 ℃, and it is apparent that the material obtained in comparative example 7 is a broad-spectrum near-infrared fluorescent material having extremely poor thermal quenching characteristics.
Comparative example 8
A material according to this comparative example comprising a compound of formula: BaO 0.9MgO 5Al2O3·0.8Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, the component is BaO.0.9 MgO.5 Al2O3·0.8Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.9 MgO.5 Al2O3·0.8Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in comparative example 8 is near 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is about 96nmAnd (4) right. It can be seen that the material obtained in comparative example 8 is a broad-spectrum near-infrared fluorescent material. Fig. 3 shows the thermal quenching characteristic data of the material obtained in comparative example 8, and the material has a luminous intensity at 225 ℃ of only about 10% of that at room temperature, and it is clear that the material obtained in comparative example 8 is a wide-spectrum near-infrared fluorescent material with extremely poor thermal quenching characteristic.
Comparative example 9
A material according to this comparative example comprising a compound of formula: BaO 0.4MgO 4Al2O3·0.05Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.4 MgO.4 Al is used according to the composition2O3·0.05Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.4 MgO.4Al2O3·0.05Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in comparative example 9 is near 692nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is only about 9 nm. It can be seen that the material obtained in comparative example 9 is not a broad-spectrum near-infrared fluorescent material.
Comparative example 10
A material according to this comparative example comprising a compound of formula: BaO 0.5MgO 4.9Al2O3·0.05Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.5 MgO.4.9 Al is used according to the composition2O3·0.05Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.5 MgO.4.9 Al2O3·0.05Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, comparative example 10 produced a materialUnder the excitation of 450nm blue light, the emission spectrum is near 692nm, and the full width at half maximum of the emission spectrum is only about 9 nm. It can be seen that the material obtained in comparative example 10 is not a broad-spectrum near-infrared fluorescent material.
Comparative example 11
A material according to this comparative example comprising a compound of formula: BaO 0.5MgO 5Al2O3·Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, according to the composition, BaO.0.5 MgO.5 Al2O3·Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.5 MgO.5 Al2O3·Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in comparative example 11 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is around 100 nm. It can be seen that the material obtained in comparative example 11 is a broad-spectrum near-infrared fluorescent material. Fig. 4 shows the thermal quenching characteristic data of the material obtained in comparative example 11, which has a luminous intensity of only about 10% at room temperature at 225 ℃, and it is apparent that the material obtained in comparative example 11 is a broad-spectrum near-infrared fluorescent material having extremely poor thermal quenching characteristics.
Comparative example 12
A material according to this comparative example comprising a compound of formula: BaO 0.9MgO 5Al2O3·Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, the component is BaO.0.9 MgO.5 Al2O3·Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.9 MgO.5 Al2O3·Cr2O3. Measuring the emission spectrum of the obtained luminescent material by using a fluorescence spectrometerSee table 1 for full width at half maximum. As can be seen from Table 1, the emission spectrum of the material prepared in comparative example 12 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is about 100 nm. It can be seen that the material obtained in comparative example 12 is a broad-spectrum near-infrared fluorescent material. Fig. 5 shows the thermal quenching characteristic data of the material obtained in comparative example 12, which has a luminous intensity of only about 10% at room temperature at 225 ℃, and it is apparent that the material obtained in comparative example 12 is a broad-spectrum near-infrared fluorescent material having extremely poor thermal quenching characteristics.
Comparative example 13
Comparative example BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.9 MgO.4.9 Al is used according to the composition2O3·0.8Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1300 ℃ in a nitrogen-hydrogen mixed atmosphere, taken out after being cooled, and the emission spectrum of the obtained luminescent material is measured by using a fluorescence spectrometer, so that the obtained sample is found to be fluffy. The emission spectrum of the obtained material was measured by using a fluorescence spectrometer, and it was found that the material prepared in comparative example 13 did not show any significant emission peak in the measurement range of 500nm to 1700nm under the excitation of the blue light of 450 nm. It is apparent that comparative example 13 is not a luminescent material, and comparative example 13 does not synthesize a luminescent material at the synthesis temperature used.
Example 1
The material described in this example comprises a compound of the formula: BaO 0.5MgO 4Al2O3·0.1Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.5 MgO.4 Al is used according to the composition2O3·0.1Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.5 MgO.4Al2O3·0.1Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the material obtained in example 1Under the excitation of 450nm blue light, the emission spectrum is near 700nm (see figure 6), and the full width at half maximum of the emission spectrum is about 95 nm. It can be seen that the material obtained in example 1 is a broad-spectrum near-infrared fluorescent material. Fig. 7 shows thermal quenching characteristic data of the material obtained in example 1, and the material has a luminous intensity of about 56% at room temperature at 225 ℃, and it is obvious that the material obtained in example 1 is a broad-spectrum near-infrared fluorescent material with better thermal quenching characteristic.
Example 2
The material described in this example comprises a compound of the formula: BaO 0.6MgO 4.5Al2O3·0.1Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.6 MgO.4.5 Al is used according to the composition2O3·0.1Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.6 MgO.4.5 Al2O3·0.1Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 2 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is about 95 nm. It can be seen that the material obtained in example 2 is a broad-spectrum near-infrared fluorescent material.
Example 3
The material described in this example comprises a compound of the formula: BaO 0.6MgO 4.5Al2O3·0.12Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.6 MgO.4.5 Al is used according to the composition2O3·0.12Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.6 MgO.4.5 Al2O3·0.12Cr2O3. Measurement of the resulting luminescent Material Using a fluorescence spectrometerThe emission spectrum of the material, the full width at half maximum of the emission spectrum is shown in Table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 3 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is about 96 nm. It can be seen that the material obtained in example 3 is a broad-spectrum near-infrared fluorescent material.
Example 4
The material described in this example comprises a compound of the formula: BaO 0.6MgO 4.5Al2O3·0.15Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.6 MgO.4.5 Al is used according to the composition2O3·0.15Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.6 MgO.4.5 Al2O3·0.15Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 4 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is about 96 nm. It can be seen that the material obtained in example 4 is a broad-spectrum near-infrared fluorescent material.
Example 5
The material described in this example comprises a compound of the formula: BaO 0.6MgO 4.5Al2O3·0.18Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.6 MgO.4.5 Al is used according to the composition2O3·0.18Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.6 MgO.4.5 Al2O3·0.18Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in example 5 emits light under the excitation of 450nm blue lightThe spectrum is near 700nm, and the full width at half maximum of the emission spectrum is about 98 nm. It can be seen that the material obtained in example 5 is a broad-spectrum near-infrared fluorescent material.
Example 6
The material described in this example comprises a compound of the formula: BaO 0.6MgO 4.5Al2O3·0.25Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.6 MgO.4.5 Al is used according to the composition2O3·0.25Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.6 MgO.4.5 Al2O3·0.25Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 6 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is about 100 nm. It can be seen that the material obtained in example 6 is a broad-spectrum near-infrared fluorescent material.
Example 7
The material described in this example comprises a compound of the formula: BaO 0.6MgO 4.5Al2O3·0.3Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.6 MgO.4.5 Al is used according to the composition2O3·0.3Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.6 MgO.4.5 Al2O3·0.3Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 7 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is about 105 nm. It can be seen that the material obtained in example 7 is a broad spectrum near infrared fluorescent material.
Example 8
The material described in this example comprises a compound of the formula: BaO 0.6MgO 4.5Al2O3·0.4Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.6 MgO.4.5 Al is used according to the composition2O3·0.4Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.6 MgO.4.5 Al2O3·0.4Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 8 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is about 107 nm. It can be seen that the material obtained in example 8 is a broad-spectrum near-infrared fluorescent material.
Example 9
The material described in this example comprises a compound of the formula: BaO 0.6MgO 4.5Al2O3·0.5Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.6 MgO.4.5 Al is used according to the composition2O3·0.5Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.6 MgO.4.5 Al2O3·0.5Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 9 is around 701nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is about 108 nm. It can be seen that the material obtained in example 9 is a broad spectrum near infrared fluorescent material.
Example 10
The material described in this example comprises a compound of the formula:BaO·0.6MgO·4.5Al2O3·0.6Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.6 MgO.4.5 Al is used according to the composition2O3·0.6Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.6 MgO.4.5 Al2O3·0.6Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 10 is near 702nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is about 110 nm. It can be seen that the material obtained in example 10 is a broad-spectrum near-infrared fluorescent material.
Example 11
The material described in this example comprises a compound of the formula: BaO 0.6MgO 4.5Al2O3·0.7Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.6 MgO.4.5 Al is used according to the composition2O3·0.7Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.6 MgO.4.5 Al2O3·0.7Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 11 under the excitation of 450nm blue light is near 706nm, and the full width at half maximum of the emission spectrum is about 111 nm. It can be seen that the material obtained in example 11 is a broad spectrum near infrared fluorescent material.
Example 12
The material described in this example comprises a compound of the formula: BaO 0.6MgO 4.5Al2O3·0.8Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.6 MgO.4.5 Al is used according to the composition2O3·0.8Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.6 MgO.4.5 Al2O3·0.8Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 12 is around 708nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is around 115 nm. It can be seen that the material obtained in example 12 is a broad-spectrum near-infrared fluorescent material.
Example 13
The material described in this example comprises a compound of the formula: BaO 0.7MgO 4.5Al2O3·0.15Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.7 MgO.4.5 Al is used according to the composition2O3·0.15Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.7 MgO.4.5 Al2O3·0.15Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 13 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is about 95 nm. It can be seen that the material obtained in example 13 is a broad spectrum near infrared fluorescent material.
Example 14
The material described in this example comprises a compound of the formula: BaO 0.8MgO 4.5Al2O3·0.15Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.8 MgO.4.5 Al is used according to the composition2O3·0.15Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.8 MgO.4.5 Al2O3·0.15Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 14 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is around 95 nm. It can be seen that the material obtained in example 14 is a broad spectrum near infrared fluorescent material.
Example 15
The material described in this example comprises a compound of the formula: BaO 0.9MgO 4.5Al2O3·0.15Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.9 MgO.4.5 Al is used according to the composition2O3·0.15Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.9 MgO.4.5 Al2O3·0.15Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 15 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is about 95 nm. It can be seen that the material obtained in example 15 is a broad spectrum near infrared fluorescent material.
Example 16
The material described in this example comprises a compound of the formula: BaO 0.8MgO 4.6Al2O3·0.15Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.8 MgO.4.6 Al is used according to the composition2O3·0.15Cr2O3Accurately weighing the raw materials according to the stoichiometric ratio, sintering for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooling to obtain the materialThe nominal chemical composition of the material is BaO.0.8 MgO.4.6 Al2O3·0.15Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 16 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is around 95 nm. It can be seen that the material obtained in example 16 is a broad spectrum near infrared fluorescent material.
Example 17
The material described in this example comprises a compound of the formula: BaO 0.8MgO 4.7Al2O3·0.15Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.8 MgO.4.7 Al is used according to the composition2O3·0.15Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.8 MgO.4.7 Al2O3·0.15Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 17 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is around 95 nm. It can be seen that the material obtained in example 17 is a broad-spectrum near-infrared fluorescent material.
Example 18
The material described in this example comprises a compound of the formula: BaO 0.8MgO 4.8Al2O3·0.15Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.8 MgO.4.8 Al is used according to the composition2O3·0.15Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.8 MgO.4.8 Al2O3·0.15Cr2O3. Measurement using fluorescence spectrometerThe emission spectrum of the obtained luminescent material, the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 18 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is around 95 nm. It can be seen that the material obtained in example 18 is a broad spectrum near infrared fluorescent material.
Example 19
The material described in this example comprises a compound of the formula: BaO 0.8MgO 4.9Al2O3·0.15Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.8 MgO.4.9 Al is used according to the composition2O3·0.15Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.8 MgO.4.9 Al2O3·0.15Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 19 is around 700nm under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is about 95 nm. It can be seen that the material obtained in example 19 is a broad-spectrum near-infrared fluorescent material.
Example 20
The material described in this example comprises a compound of the formula: BaO 0.9MgO 4.9Al2O3·0.15Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.9 MgO.4.9 Al is used according to the composition2O3·0.15Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.9 MgO.4.9 Al2O3·0.15Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, example 20 produced a material that was blue at 450nmUnder excitation, the emission spectrum is near 700nm, and the full width at half maximum of the emission spectrum is about 95 nm. It can be seen that the material obtained in example 20 is a broad spectrum near infrared fluorescent material.
Example 21
The material described in this example comprises a compound of the formula: BaO 0.9MgO 4.9Al2O3·0.8Cr2O3. With BaCO3、MgO、Al2O3And Cr2O3As a raw material, BaO.0.9 MgO.4.9 Al is used according to the composition2O3·0.8Cr2O3The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1600 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of BaO.0.9 MgO.4.9 Al2O3·0.8Cr2O3. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the full width at half maximum of the emission spectrum is shown in table 1. As can be seen from Table 1, the emission spectrum of the material prepared in example 21 is near 710nm (see FIG. 8) under the excitation of 450nm blue light, and the full width at half maximum of the emission spectrum is about 118 nm. It can be seen that the material obtained in example 1 is a broad-spectrum near-infrared fluorescent material. Fig. 9 shows thermal quenching characteristic data of the material obtained in example 21, and the material has a light emission intensity at 225 ℃ of about 52% at room temperature, which is obvious that the material obtained in example 21 is a broad-spectrum near-infrared fluorescent material with good thermal quenching characteristics.
Example 22
The chemical composition synthesized in example 4 was selected to be BaO 0.6MgO 4.5Al2O3·0.15Cr2O3Near infrared fluorescent material. Mixing the above materials with low-melting-point glass powder according to the mass ratio of 1:1, placing the mixture in a flat-bottom crucible made of metal titanium and having the bottom diameter of 10mm, sintering for 0.5h at 700 ℃ in an air atmosphere, and cooling a sample to obtain the near-infrared fluorescent glass. The near-infrared fluorescent glass is packaged with a blue laser diode with the emission wavelength of 450nm to obtain a near-infrared light source. FIG. 10 shows an emission spectrum of a near-infrared light source obtained in example 22. It is obvious that the light source can emitA broader near infrared spectrum.
TABLE 1 emission spectra data sheet of materials
Figure BDA0002774400070000221
Figure BDA0002774400070000231
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (12)

1. The wide-spectrum near-infrared fluorescent material is characterized in that the chemical general formula of the wide-spectrum near-infrared fluorescent material is as follows: BaO, aMgO, bAl2O3·cCr2O3Wherein a is more than or equal to 0.5 and less than or equal to 0.9, b is more than or equal to 4 and less than or equal to 4.9, and c is more than or equal to 0.1 and less than or equal to 0.8; under the excitation of blue light, the wide-spectrum near-infrared fluorescent material generates near-infrared light with the emission wavelength range of 600-1100 nm, the main peak of the emission spectrum of more than or equal to 700nm, and the full width at half maximum of the emission spectrum of more than or equal to 90 nm.
2. The broad spectrum near infrared fluorescent material of claim 1, wherein: in the chemical general formula of the wide-spectrum near-infrared fluorescent material, a is more than or equal to 0.6 and less than or equal to 0.8, b is more than or equal to 4.5 and less than or equal to 4.8, and c is more than or equal to 0.12 and less than or equal to 0.15;
optionally, the preparation method of the wide-spectrum near-infrared fluorescent material comprises the steps of mixing a Ba precursor, a Mg precursor, an Al precursor and a Cr precursor, and carrying out high-temperature solid-phase reaction under a reducing atmosphere to obtain the wide-spectrum near-infrared fluorescent material, wherein the preferable temperature of the high-temperature solid-phase reaction is 1500-1700 ℃, and the time of the high-temperature solid-phase reaction is 4-10 hours.
3. The broad spectrum near infrared fluorescent material according to claim 1 or 2, characterized in that: the luminous intensity of the wide-spectrum near-infrared fluorescent material at 200-250 ℃ is not lower than 50% of that at room temperature.
4. A method for preparing the wide-spectrum near-infrared fluorescent material according to any one of claims 1 to 3, which is characterized in that: and mixing the Ba precursor, the Mg precursor, the Al precursor and the Cr precursor, and carrying out high-temperature solid-phase reaction in a reducing atmosphere to obtain the wide-spectrum near-infrared fluorescent material.
5. The method for preparing the broad spectrum near infrared fluorescent material according to claim 4, wherein: the Ba precursor is selected from one or more of carbonate of Ba, oxide of Ba or nitrate of Ba;
optionally, the Mg precursor is selected from one or more of a carbonate of Mg, an oxide of Mg or a nitrate of Mg;
optionally, the Al precursor is Al2O3；
Optionally, the Cr precursor is Cr2O3；
Optionally, the purity of the Ba precursor, the Mg precursor, the Al precursor and the Cr precursor is not lower than 99.5 wt%.
6. The method for preparing a broad spectrum near infrared fluorescent material according to claim 4 or 5, wherein: the temperature of the high-temperature solid-phase reaction is 1500-1700 ℃, and the time of the high-temperature solid-phase reaction is 4-10 h;
optionally, the reducing atmosphere is ammonia gas or a nitrogen-hydrogen mixed gas.
7. The method for preparing the broad spectrum near infrared fluorescent material according to claim 6, wherein: the volume content of hydrogen in the nitrogen-hydrogen mixed gas is 10-25%.
8. A near-infrared fluorescent glass is characterized in that: the near-infrared fluorescent glass is obtained by mixing the wide-spectrum near-infrared fluorescent material according to any one of claims 1 to 3 or the wide-spectrum near-infrared fluorescent material prepared by the preparation method according to any one of claims 4 to 7 with glass powder and then carrying out high-temperature solid phase reaction.
9. The near-infrared fluorescent glass according to claim 8, characterized in that: the mass ratio of the wide-spectrum near-infrared fluorescent material to the glass powder is 1: 1-1: 4; the melting point of the glass powder is 500-800 DEG C
10. A method for producing the near-infrared fluorescent glass according to claim 8 or 9, characterized in that: mixing the wide-spectrum near-infrared fluorescent material according to any one of claims 1 to 3 or the wide-spectrum near-infrared fluorescent material prepared by the preparation method according to any one of claims 4 to 7 with glass powder, and carrying out high-temperature solid-phase reaction in an air atmosphere to obtain the near-infrared fluorescent glass.
11. The method for preparing near-infrared fluorescent glass according to claim 10, characterized in that: the temperature of the high-temperature solid-phase reaction is 500-800 ℃, and the time of the high-temperature solid-phase reaction is 0.1-1 h;
optionally, the mass ratio of the wide-spectrum near-infrared fluorescent material to the glass powder is 1: 1-1: 4; the melting point of the glass powder is 500-800 ℃.
12. A laser near-infrared device is characterized in that: the laser near-infrared device comprises a blue laser diode and a light-emitting layer, wherein the light-emitting layer comprises the near-infrared fluorescent glass of claim 8 or 9, or comprises the near-infrared fluorescent glass prepared by the preparation method of claim 10 or 11.
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