CN115806821A - Synthesis method and application of infrared light fluorescent material for improving eyesight of old people - Google Patents
Synthesis method and application of infrared light fluorescent material for improving eyesight of old people Download PDFInfo
- Publication number
- CN115806821A CN115806821A CN202211486326.0A CN202211486326A CN115806821A CN 115806821 A CN115806821 A CN 115806821A CN 202211486326 A CN202211486326 A CN 202211486326A CN 115806821 A CN115806821 A CN 115806821A
- Authority
- CN
- China
- Prior art keywords
- fluorescent material
- light
- precursor
- near infrared
- deep red
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention provides a synthesis method and application of an infrared fluorescent material for improving the eyesight of old people. The chemical composition of the infrared fluorescent material is Ba 3‑x Eu x Cu 3 Sc 4 O 12 Wherein 0 is<x is less than or equal to 0.1; under the excitation of blue light, the deep red light-near infrared light fluorescent material can generate an emission wavelength range from 550 to 1480nm, two peaks exist in an emission spectrum, and peak wavelengths are respectively near 680nm and 1010 nm. Compared with the prior art, the infrared fluorescent material for improving the eyesight of the old has a brand-new chemical composition, can be excited by blue light to emit deep red light-near infrared light, and thus, the infrared fluorescent material is applied to a light source beneficial to eye health.
Description
Technical Field
The invention relates to the technical field of luminescent material preparation, in particular to a synthesis method and application of an infrared light fluorescent material for improving eyesight of old people.
Background
Among the elderly over 60 years old, the visual organ aging causes 47.9% of the patients with impaired vision. Both the metabolism and senescence of organisms are regulated by mitochondria. Mitochondrial membrane potential decreases with age, resulting in decreased ATP (the major source of cellular energy) production. For people around age 40, retinal cells begin to age, at a rate that is caused, in part, by the initial decline of mitochondria that produce energy and enhance cellular function.
The retina photoreceptor cells have a high mitochondrial density and a high energy demand. Thus, the retina ages at a faster rate than other organs, and when ATP is reduced by 70%, photoreceptor (cone cell) function is significantly reduced.
The reduced cone function is ultimately due to the effects of cellular metabolism, which is regulated by mitochondria. Mitochondria can absorb light of longer wavelengths. Non-patent document 1 (harpreset shinhom, christ Hogg, magella nevu, glen Jeffery, weeklong improved color coherent rear filter single 670nm ex situ associated with red light), and non-patent document 2 (harpreset shinhom, manjgrewal, sobha sivasad, christ Hogg, victor Chong, magella neu, glen Jeffery, optical enhanced red function repair human subclaim, joint of Journals of Biological, scientific) show that the function of infrared light irradiation is significantly increased by light irradiation of infrared light in the range of 1000nm, and the wavelength of infrared light irradiation of the eye is significantly increased by light irradiation of infrared light in the range of 1000nm, thus increasing the function of the eye (75 nm) of the aged human eye (see light irradiation, infrared light irradiation of 1000 nm).
Patent document 1 (li hong jiang, a red light or a flashlight that improves or prevents the eyesight of the elderly from declining, CN 111803338A) discloses a red light or a flashlight that improves or prevents the eyesight of the elderly from declining. The method is that a common white light lamp is changed into a red light lamp by coating a dark red coating, or a light-gathering cup in the head of the flashlight is coated into the dark red color, so that light with the wavelength of 670nm can be generated to irradiate human eyes, and the effect of preventing the vision of the old is achieved. However, it should be noted that in the technical solution provided in patent document 1, because a conventional white light lamp is used, the spectrum components of the white light lamp contain less deep red light, and the energy of the generated deep red light is too low, the resulting effect is relatively poor; meanwhile, the spectrum does not contain a near infrared spectrum, so that after the coating with the deep red paint is adopted, only non-deep red light in the lamp can be absorbed, and then the rest deep red light is reflected.
Further, it is more advantageous if the deep red and near infrared light sources are directly used. Patent document 2 (yang feng jian, yangxing, a deep red vision improving device, CN 217219904U) discloses a deep red vision improving device, which is characterized in that a light cylinder is arranged on a body, an LED light source is arranged in the light cylinder, 2 paths of deep red light of 670nm can be output, and irradiation is performed on two eyes, so that the device has the beneficial effect of improving vision. However, it should be noted that, in the technical solution provided in patent document 2, although deep red light with a considerable power can be obtained, the spectrum does not contain near infrared spectrum at all, and the overall effect is poor.
Further, a near infrared light source may be added to the deep red light source to provide more advantageous effects. Patent document 3 (L · lin, system and device for non-invasive neurostimulation treatment of the brain, CN 106413810B) discloses a light-emitting device whose emission spectrum contains at least cellular energy molecules with a preselected wavelength from the group consisting of near-infrared wavelength and visible red wavelength, photoreceptors (cones) sensitive to light in the visible red and near-infrared regions of the spectrum and capable of converting these red and near-infrared wavelength absorbed light into Adenosine Triphosphate (ATP). When these visible red and near infrared wavelengths of light enter living cells (including nerve cells) at low energy levels, light can modulate the metabolic activity of the cell by modulating internal mitochondrial function, intracellular signaling systems, and redox states (photobiomodulation). However, it should be noted that, although the technical solution disclosed in patent document 3 can obtain deep red light-near infrared light with comparable power, it is obvious that purchasing a light source with only a single function of emitting a spectrum including a wavelength band of 670nm to 1000nm for each elderly person who needs to improve eyesight is not an optimal solution.
Non-patent document 3 (plum, frame, measurement and evaluation of photometric and colorimetric characteristics of white LED light source, master's academic paper of china university of oceans, 2007) considers that the human eye is very insensitive to deep red light. And for near infrared light, the human eye is obviously unable to recognize. Therefore, the visual effect of the white light source cannot be obviously influenced by adding the deep red light spectrum components with proper proportion to the common white light source; of course, the addition of near infrared spectral components in a common light source does not affect the visual effect of a white light source.
Therefore, the most ideal light source for improving the vision decline of the elderly, which contains (at least) deep red light-near infrared light, is obviously to add a component or structure capable of emitting deep red light-near infrared light to the common white light source.
In view of this, further, patent document 4 (rue, an eye-protecting lamp with a function of repairing retina, CN 215489232U) discloses an eye-protecting lamp with a function of repairing retina. The LED module structurally comprises a first substrate, a second substrate and a third substrate, wherein conventional (white light) LED modules are arranged on the three types of substrates; particularly, a red LED module is further arranged on the third substrate. However, it should be noted that in the technical solution given in patent document 4, although deep red light with a comparable power can be obtained, near infrared light is not contained; in addition, since the driving voltage of the red LED module is different from that of the white LED module, it is necessary to separately configure a power supply for the red LED module, which undoubtedly increases the complexity and reliability of the light source.
Further, patent document 5 (wuxin, xuri, grandson, yangdui, wangshuai, petrolite, zhouyan, a full spectrum LED lighting lamp, CN 106907582A) discloses a full spectrum LED lighting lamp, characterized in that the LED array includes white LEDs, cyan LEDs and deep red LEDs; the white light LED has the excitation emission peak value of the blue light LED
The blue light LED is excited by the blue light LED to emit a peak value
Blue light, deep red light LED with blue lightLED excitation emission peak at
Deep red phosphor. However, although patent document 5 overcomes the technical disadvantage of patent document 4, the light source does not include near infrared light in the light.
Patent document 6 (zhangjia Ye, xiao, zhanliang, wuhao, zhangxia, near infrared fluorescent powder, preparation and application method, near infrared light source and near infrared white light source preparation method, CN 111073644B) mentions that: mixing the near-infrared fluorescent powder, the visible light fluorescent powder and glue to obtain slurry; and coating the slurry on a blue light LED chip to finally obtain the white light-near infrared LED light source.
Obviously, if the technical means of patent document 5 and patent document 6 are combined, that is, the blue light chip is combined with the deep red light phosphor powder capable of being excited by blue light and the near infrared phosphor powder capable of being excited by blue light, an LED light source containing white light-deep red light-near infrared light can be obtained, so that the deep red light-near infrared light emitted from the light source can improve the eyesight of the old under the condition of meeting the daily illumination.
However, for a white light-deep red light-near infrared light emitting device excited by a blue light LED, when multiple phosphors (such as yellow phosphor, deep red phosphor, and near infrared phosphor for realizing white light) are mixed and packaged in a single device, the mutual light absorption between the phosphors is difficult to control; the fluorescent powder particles have different sedimentation rates in the packaging glue due to the difference of particle size and density, and the light color characteristics of the packaged device are unstable finally. Therefore, the ideal and operational technical scheme is that the blue light LED combines yellow fluorescent powder to realize white light, and a fluorescent material which can be effectively excited by blue light and can emit deep red light-near infrared light is added, so that the LED light source containing the white light-deep red light-near infrared light is finally obtained, and the deep red light-near infrared light emitted by the light source can improve the eyesight of the old under the condition of meeting the daily illumination.
For this reason, patent document 7 (qiao juan, jiazhen, a deep red-near infrared light emitting device, CN 113097403A) discloses a deep red-near infrared light emitting device, and more particularly, to a device based on a near infrared light conversion film, which includes a deep red-near infrared light emitting quantum dot material having an emission spectrum covering a wavelength range of 650 to 2000nm and being excitable by light having a wavelength of 500 to 650 nm. However, it should be noted that although the material disclosed in patent document 7 can emit deep red light to near infrared light at the same time, its excitation spectrum is not blue light, and the material itself is a quantum dot material with unstable chemical properties, and thus it is difficult to apply the material in practice.
And patent document 8 (shore over, pengem, naohao, dug rock, jiang qing, a far-red and near-infrared emission fluoride fluorescent material and preparation and application thereof, CN 109913214B) discloses a far-red and near-infrared emission fluoride fluorescent material, the chemical expression of which is R x Al 1-y F x+3 In the formula, yCr is selected from at least one of Li, na, K, rb or Cs, x is more than or equal to 1 and less than or equal to 3, and y is more than or equal to 0.005 and less than or equal to 0.2. The fluorescent material can be excited by a blue light or red light LED chip, but the emission waveband is between 700nm and 900nm, the contained near infrared light is less, and the fluorescent powder is of a fluoride structure. Fluoride, in contrast, is not a chemically stable compound.
Further, patent document 9 (Chenxiaxia, liuyuanhong, liuronghui, schumann, CN 110330970A) discloses that the molecular formula is aSc 2 O 3 ·Ga 2 O 3 ·bR 2 The compound of O, wherein the R element comprises one or two of Cr, ni, fe, yb, nd or Er elements, a is more than or equal to 0.001 and less than or equal to 0.6, and b is more than or equal to 0.001 and less than or equal to 0.1. The luminescent material can be excited by spectrum with rich wavelength range (ultraviolet or purple light or blue light) to generate
Broad spectrum or multiple spectra. However, it should be noted that the material disclosed in patent document 9 can emit deep red light-near infrared light at the same time, but the material is about 1000nmNear infrared light comes from Yb, nd, or Er that emits in a narrow band, and therefore the full width at half maximum of the near infrared spectrum is narrow (typically, the full width at half maximum at 1000nm in the near infrared is 33nm as given in example 8 thereof), and it is clear that the intensity of the near infrared band is insufficient and the need for improving the visual decline of the elderly cannot be satisfied.
Therefore, in the current technical scheme, no available deep red light-near infrared fluorescent material is available, and the fluorescent material is further packaged into a specific light source for improving the vision degradation of the old.
In the synthesis process of the fluorescent material, a secondary sintering process is usually adopted. The secondary sintering process is adopted, sometimes because the reactivity/stability of the initial raw materials is poor, so that the target fluorescent material is synthesized by firstly decomposing at low temperature, grinding and mixing for the second time and then carrying out high-temperature synthesis reaction. Typically, for example, patent document 10 (yuxue, huolong, wangting, xuxuxuhui, qijianbi, a red phosphor and its preparation method, CN 103450897A) discloses a compound with a chemical formula of Ca 2.95 Sn 2 SiO 9 :Eu 0.05 Li x (x is more than or equal to 0 and less than or equal to 0.05) red fluorescent powder, and the raw material is CaCO 3 、SnO 2 、SiO 2 、Eu 2 O 3 、Li 2 CO 3 And an appropriate amount of H 3 BO 3 . The synthesis is divided into two steps, the first sintering is carried out for 1 to 4 hours at 800 to 1000 ℃; re-grinding and sintering at 1300-1500 deg.c
Hours (without fresh addition of any starting material). It is clear that in this case the purpose of the second sintering is to synthesize the material itself.
And patent document 11 (chenyili, lingjin zhu, wuyu, tian qi, li zhen jilong, near infrared phosphor, preparation method thereof, light emitting device, CN 112322283A) discloses a phosphor having a chemical formula of a 1-y MgM 10-x-z R x O 17-x N x :yEu 2+ ，zCr 3+ Wherein the A site comprises at least one of Ca, sr and Ba, the M site comprises at least one of Al, ga and Sc, and the R site comprises at least one of Si, ge and SnOne of the two is more, y is more than or equal to 0 and less than or equal to 0.05, x is more than or equal to 0 and less than or equal to 3, and z is more than or equal to 0.01 and less than or equal to 0.1. The fluorescent material also adopts a secondary sintering process, and the conditions of the primary sintering treatment comprise: sintering for 4-6 hours at 1200-1600 ℃ in a mixed atmosphere containing hydrogen; the conditions of the second sintering treatment comprise: sintering at 1500-1800 deg.c in hydrogen-containing mixed atmosphere for 4-6 hr. This patent document uses a secondary sintering process, which aims at adding new raw materials during the secondary sintering process, and the disclosed chemical composition is not obtained until the secondary sintering process.
Another case of the secondary sintering is to obtain a better luminous intensity. For example, patent document 12 (He Jinhua, yinyang, liangchao, teng-Xiao, a crimson fluorescent powder and its preparation method, CN 1025812A) discloses a compound of formula Mg 4-x-y GO 5.5 J:Mn X ，R y G is Si, ge and Sn, J is F and Cl, R is Li, bi, pr, na and K, x is more than or equal to 0.005 and less than or equal to 0.1, y is more than or equal to 0.0005 and less than or equal to 0.05, the fluorescent material is synthesized by a secondary sintering mode, and the conditions of the primary sintering are as follows: air atmosphere/1100 ℃ -1250 ℃/4-8 hours, and the conditions of the second sintering are as follows: air atmosphere/1900-1100 deg.c/1-4 hr. According to the general principle of chemical reaction thermodynamics, the first sintering temperature is higher than that of the second sintering temperature, so that the sample is synthesized during the first sintering, the luminous property of the sample is determined, and the significance of the second sintering is to repair/eliminate the defects on the surface or in the fluorescent material particles during the first sintering process, so that the luminous intensity of the sample is further improved.
As analyzed above, the existing fluorescent material for improving the visual deterioration of the elderly (which can be effectively excited by blue light) is lacked; the fluorescent material adopts a secondary sintering process, generally aims at obtaining the disclosed chemical composition through secondary sintering, or improves the luminous intensity of the synthesized fluorescent material, and does not disclose the change of the spectral shape (the number of luminous peaks and the spectral broadening).
Disclosure of Invention
In order to overcome the deficiency (single material realization) of deep red-near infrared light in the prior artProblemsin a first object of the present invention, there is provided a deep red-near infrared fluorescent material for improving the eyesight of the elderly. The chemical general formula of the deep red light-near infrared light fluorescent material for improving the vision decline of the old is as follows: ba 3-x Eu x Cu 3 Sc 4 O 12 Wherein 0 is<x is less than or equal to 0.1. Under the excitation of blue light, the deep red light-near infrared light fluorescent material can generate an emission wavelength range from 550 to 1480nm, two peaks exist in an emission spectrum, and peak wavelengths are respectively near 680nm and 1010 nm. Preferably, in the chemical formula of the deep red light-near infrared light fluorescent material for improving the vision deterioration of the elderly, x =0.05.
The second purpose of the invention is to provide a preparation method of the deep red light-near infrared light fluorescent material for improving the vision decline of the old people. The preparation method comprises the following steps: a) Mixing a Ba precursor, a Eu precursor, a Cu precursor and a Sc precursor, and carrying out high-temperature solid-phase reaction in a reducing atmosphere to obtain a precursor;
b) And grinding and mixing the precursor again, and then carrying out high-temperature solid-phase reaction in an air atmosphere to obtain the deep red light-near infrared light fluorescent material for improving the vision decline of the old. Specifically, the molar ratio of the Ba precursor to the Eu precursor to the Cu precursor to the Sc precursor is (3-x) x: 3: 4, and the obtained deep red light-near infrared light fluorescent material has a chemical general formula as follows: ba 3- x Eu x Cu 3 Sc 4 O 12 Wherein, 0<x≤0.1。
The invention also provides a light-emitting device, which comprises an excitation light source and a fluorescent material, wherein the fluorescent material comprises the deep red light-near infrared light fluorescent material or the deep red light-near infrared light fluorescent material and Y 3 Al 5 O 12 :Ce 3+ A yellow fluorescent material. The excitation light source is preferably a blue laser diode.
The specific scheme is as follows:
deep red light-near infrared light fluorescent material for improving vision deterioration of old peopleHas the chemical general formula: ba 3-x Eu x Cu 3 Sc 4 O 12 Wherein, 0<x≤0.1。
Further, in the chemical general formula of the deep red light-near infrared light fluorescent material for improving the visual deterioration of the elderly, x =0.05;
optionally, the preparation method of the deep red light-near infrared light fluorescent material for improving the vision deterioration of the elderly comprises the following steps: a) Mixing a Ba precursor, a Eu precursor, a Cu precursor and a Sc precursor, and carrying out high-temperature solid-phase reaction in a reducing atmosphere to obtain a precursor; b) And grinding and mixing the precursor again, and then carrying out high-temperature solid-phase reaction in an air atmosphere to obtain the deep red light-near infrared light fluorescent material for improving the vision decline of the old. Preferably, in the step a), the temperature of the high-temperature solid-phase reaction is 1000-1100 ℃, the time of the high-temperature solid-phase reaction is 4-10 h, and the reducing atmosphere is ammonia gas or mixed gas of nitrogen and hydrogen; preferably, in step b), the temperature of the high temperature solid phase reaction is 900 to 1000 ℃ and the time of the high temperature solid phase reaction is 4 to 10 hours.
Further, under the excitation of blue light, the deep red light-near infrared light fluorescent material for improving the vision decline of the elderly generates an emission wavelength range between 550 and 1480nm, two peaks exist in an emission spectrum, and peak wavelengths are respectively positioned near 680nm and 1010 nm.
The invention also provides a preparation method of the deep red light-near infrared light fluorescent material for improving the vision decline of the old, which comprises the following steps: a) Mixing a Ba precursor, a Eu precursor, a Cu precursor and a Sc precursor, and carrying out high-temperature solid-phase reaction in a reducing atmosphere to obtain a precursor; b) And grinding and mixing the precursor again, and then carrying out high-temperature solid-phase reaction in an air atmosphere to obtain the deep red light-near infrared light fluorescent material for improving the vision decline of the old.
Further, the Ba precursor is selected from at least one of a carbonate of Ba, an oxalate of Ba, and a nitrate of Ba;
optionally, the Eu precursor is selected from Eu oxides;
optionally, the Cu precursor is selected from at least one of basic carbonate salt of Cu, oxide of Cu, oxalate of Cu and nitrate of Cu;
optionally, the Sc precursor is an oxide of Sc;
optionally, the purities of the Ba precursor, the Eu precursor, the Cu precursor and the Sc precursor are not lower than 99.5wt%.
Optionally, the molar ratio of the Ba precursor, the Eu precursor, the Cu precursor and the Sc precursor is (3-x): x: 3: 4, and the obtained deep red light-near infrared light fluorescent material has a chemical general formula: ba 3-x Eu x Cu 3 Sc 4 O 12 Wherein 0 is<x≤0.1。
Further, in the step a), the temperature of the high-temperature solid-phase reaction is 1000-1100 ℃, the time of the high-temperature solid-phase reaction is 4-10 h, and the reducing atmosphere is ammonia gas or nitrogen-hydrogen mixed gas; in the step b), the temperature of the high-temperature solid-phase reaction is 900-1000 ℃, and the time of the high-temperature solid-phase reaction is 4-10 h.
Optionally, in the step a), the reducing atmosphere is ammonia gas or a nitrogen-hydrogen mixed gas, and preferably, the volume content of hydrogen in the nitrogen-hydrogen mixed gas is 10-25%.
The invention also protects a light-emitting device, which comprises an excitation light source and a fluorescent material, wherein the excitation light source is a blue light LED chip, and the fluorescent material comprises the deep red light-near infrared light fluorescent material or the deep red light-near infrared light fluorescent material and Y 3 Al 5 O 12 :Ce 3+ A combination of yellow fluorescent materials; the fluorescent material is excited by the blue LED chip to emit at least deep red light-near infrared light.
Advantageous effects
The invention provides a deep red light-near infrared light fluorescent material for improving the vision decline of old people, a synthetic method and application thereof. The chemical composition of the deep red light-near infrared light fluorescent material is Ba 3-x Eu x Cu 3 Sc 4 O 12 Wherein, 0<x is less than or equal to 0.1; under the excitation of blue light, the deep red light-near infrared light fluorescent material can generate emission light with the emission wavelength range of 550-1480 nmThere are two peaks in the spectrum and the peak wavelengths are located around about 680nm and about 1010nm, respectively. Compared with the prior art, the deep red light-near infrared light fluorescent material for improving the vision decline of the old has a brand new chemical composition, can be excited by blue light to emit deep red light-near infrared light, and thus the fluorescent material is applied to a light source beneficial to eye health.
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 graph showing an emission spectrum of a luminescent material obtained in comparative example 9 of the present invention;
FIG. 3 is a graph showing an emission spectrum of a luminescent material obtained in example 6 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 following examples are set forth herein. 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, in the present application, the embodiments and features of the embodiments 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 deep red light-near infrared light fluorescent material for improving the vision decline of the old is as follows:
Ba 3-x Eu x Cu 3 Sc 4 O 12 ，
wherein 0< -x is less than or equal to 0.1. In some embodiments provided herein, the x is preferably 0.005; in some embodiments provided herein, the x is preferably 0.01; in some embodiments provided herein, the x is preferably 0.02; in some embodiments provided herein, x is preferably 0.03; in some embodiments provided herein, the x is preferably 0.04; in some embodiments provided herein, the x is preferably 0.05; in some embodiments provided herein, the x is preferably 0.06; in some embodiments provided herein, the x is preferably 0.07; in some embodiments provided herein, the x is preferably 0.08; in some embodiments provided herein, the x is preferably 0.09; in other embodiments provided by the present invention, x is preferably 0.1.
The preparation method of the deep red light-near infrared light fluorescent material for improving the vision decline of the old comprises the following specific steps:
a) Mixing a Ba precursor, a Eu precursor, a Cu precursor and a Sc precursor, and carrying out high-temperature solid-phase reaction in a reducing atmosphere to obtain a precursor; b) And grinding and mixing the precursor again, and then carrying out high-temperature solid-phase reaction in an air atmosphere to obtain the deep red light-near infrared light fluorescent material for improving the vision decline of the old.
In the step a), the molar ratio of the Ba precursor, the Eu precursor, the Cu precursor and the Sc precursor is (3-x): x: 3: 4, and the chemical general formula of the obtained material is Ba 3-x Eu x Cu 3 Sc 4 O 12 Wherein, 0<x≤0.1。
In the step a), the Ba precursor may be a compound containing Ba, which is well known in the art, and is not particularly limited, and in the present invention, at least one of a carbonate of Ba, an oxalate of Ba, and a nitrate of Ba is preferred, and more preferably a carbonate of Ba (i.e., barium carbonate); the Eu precursor is selected from oxides of Eu (i.e. europium oxide); the Cu precursor is at least one selected from Cu basic carbonate, cu oxide, cu oxalate and Cu nitrate, and is more preferably Cu basic carbonate (namely basic copper carbonate); the Sc precursor is selected from Sc oxides (i.e., scandia).
The purity of the Ba precursor, the purity of the Eu precursor, the purity of the Cu precursor and the purity of the Sc 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 step a) is a dry atmosphere known to those skilled in the art, and is not particularly limited, and a nitrogen-hydrogen mixture is preferred in the present invention.
The temperature of the high-temperature solid-phase reaction in the step a) is preferably 1000-1100 ℃, and the atmosphere is nitrogen-hydrogen mixed gas, and in some embodiments provided by the invention, the temperature of the high-temperature solid-phase reaction is preferably 1050 ℃.
The time of the high-temperature solid-phase reaction in the step a) is preferably 4 to 10 hours, and more preferably 5 to 8 hours; in some embodiments provided herein, the time for the high temperature solid phase reaction is preferably 6 hours.
The temperature of the high-temperature solid-phase reaction in the step b) is preferably 900-1000 ℃, the atmosphere is air atmosphere, and in some embodiments provided by the invention, the temperature of the high-temperature solid-phase reaction is preferably 950 ℃.
The time of the high-temperature solid-phase reaction in the step b) is preferably 4 to 10 hours, and more preferably 5 to 8 hours; in some embodiments provided herein, the time for the high temperature solid phase reaction 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 deep red light-near infrared light fluorescent material for improving the visual decline of the old people can be obtained.
The invention adopts high-temperature solid-phase reaction to successfully prepare the deep red light-near infrared light fluorescent material for improving the visual deterioration of the old.
The light-emitting device made of the deep red light-near infrared light fluorescent material for improving the vision decline of the old people at least comprises an excitation light source and the fluorescent material. The excitation light source is a blue light LED chip, and the fluorescent material comprises Ba 3-x Eu x Cu 3 Sc 4 O 12 (wherein, 0)<x is less than or equal to 0.1), and can be used for improving the vision decline of the old; or the fluorescent material comprises a compound with a chemical formula of Ba 3-x Eu x Cu 3 Sc 4 O 12 (wherein, 0<x is less than or equal to 0.1) and can be used for improving the vision decline of the old and Y 3 Al 5 O 12 :Ce 3+ A yellow fluorescent material.
In order to further illustrate the present invention, the following will describe in detail a deep red-near infrared fluorescent material and a device for improving the visual deterioration of the elderly provided by the present invention with reference to the examples.
The reagents used in the following comparative examples and examples are all commercially available.
In the nitrogen-hydrogen mixed atmosphere used in the following comparative examples and examples, the hydrogen content was 20% by volume.
The Ba precursor, eu precursor, cu precursor, and Sc precursor used in the comparative examples and examples are only examples, and do not limit the raw materials of the precursors, and the purity of the precursors is not less than 99.5wt%.
Comparative example 1
The material of this comparative example, comprising a compound of the formula: ba 3 Cu 3 Sc 4 O 12 . With BaCO 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 As a raw material, the component is Ba 3 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1050 ℃ in air atmosphere, and cooled to obtain the material with the nominal chemical composition of Ba 3 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in comparative example 1 did not emit light under excitation of blue light at 450 nm.
Comparative example 2
A material according to this comparative example comprising a compound of formula: ba 3 Cu 3 Sc 4 O 12 . With BaCO 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 As a raw material, the component is Ba 3 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 950 ℃ in air atmosphere, and cooled to obtain the material with the nominal chemical composition of Ba 3 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, comparative example 2 produced a material inThe light does not emit light under the excitation of the blue light with the wavelength of 450 nm.
Comparative example 3
The material of this comparative example, comprising a compound of the formula: ba 3 Cu 3 Sc 4 O 12 . With BaCO 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 As a raw material, the component is Ba 3 Cu 3 Sc 4 O 12 Accurately weighing the raw materials according to the stoichiometric ratio, sintering the raw materials for 6 hours at 1050 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooling to obtain the material with the nominal chemical composition of Ba 3 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in comparative example 3 did not emit light under excitation of 450nm blue light.
Comparative example 4
A material according to this comparative example comprising a compound of formula: ba 3 Cu 3 Sc 4 O 12 . With BaCO 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 As a raw material, the component is Ba 3 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 950 ℃ in a nitrogen-hydrogen mixed atmosphere, and cooled to obtain the material with the nominal chemical composition of Ba 3 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in comparative example 4 did not emit light under excitation of 450nm blue light.
Comparative example 5
A material according to this comparative example comprising a compound of formula: ba 3 Cu 3 Sc 4 O 12 . With BaCO 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 As a raw material, the component is Ba 3 Cu 3 Sc 4 O 12 Accurately weighing the raw materials according to the stoichiometric ratio, sintering for 6 hours at 950 ℃ in air atmosphereCooling, grinding again, sintering at 1050 deg.C for 6 hr in air atmosphere to obtain Ba 3 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in comparative example 5 did not emit light under excitation of blue light at 450 nm. It is apparent that in comparative example 5, the secondary sintering did not exhibit the effect of increasing the luminescence of the newly added material or the luminescence intensity of the material.
Comparative example 6
A material according to this comparative example comprising a compound of formula: ba 3 Cu 3 Sc 4 O 12 . With BaCO 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 Is used as raw material and comprises Ba 3 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours in a reducing atmosphere at 950 ℃, cooled, re-ground to obtain the material, and sintered for 6 hours at 1050 ℃ in the reducing atmosphere again to obtain the material with the nominal chemical composition of Ba 3 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in comparative example 6 did not emit light under excitation of blue light at 450 nm. It is apparent that in comparative example 6, the secondary sintering did not exhibit the effect of increasing the luminescence of the newly added material or the luminescence intensity of the material.
Comparative example 7
A material according to this comparative example comprising a compound of formula: ba 3 Cu 3 Sc 4 O 12 . With BaCO 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 As a raw material, the component is Ba 3 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 950 ℃ in the air atmosphere, cooled, ground again to obtain the material, and then the obtained raw materials are put in a reducing atmosphereSintering at 1050 ℃ for 6h to obtain the material with the nominal chemical composition of Ba 3 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in comparative example 7 did not emit light under excitation of blue light at 450 nm. It is apparent that comparative example 7 does not exhibit the effect of increasing the luminescence of the newly added material or the luminescence intensity of the material by the secondary sintering.
Comparative example 8
The material of this comparative example, comprising a compound of the formula: ba 3 Cu 3 Sc 4 O 12 . With BaCO 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 Is used as raw material and comprises Ba 3 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1050 ℃ in the air atmosphere, cooled, reground to obtain the material, and then sintered for 6 hours at 950 ℃ in the reducing atmosphere to obtain the material with the nominal chemical composition of Ba 3 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in comparative example 8 did not emit light under excitation of 450nm blue light. It is apparent that comparative example 8 does not exhibit the effect of increasing the luminescence of the newly added material or the luminescence intensity of the material by the secondary sintering.
Comparative example 9
A material according to this comparative example comprising a compound of formula: ba 2.95 Eu 0.05 Cu 3 Sc 4 O 12 . With BaCO 3 、Eu 2 O 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 Is used as raw material and comprises Ba 2.95 Eu 0.05 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours at 1050 ℃ in the air atmosphere, cooled, re-ground to obtain the material, and sintered for 6 hours at 950 ℃ in the reducing atmosphere, namelyThe nominal chemical composition of the material is Ba 2.95 Eu 0.05 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in comparative example 9 has a main peak of emission spectrum approximately around 650nm under the excitation of 450nm blue light.
Comparative example 10
A material according to this comparative example comprising a compound of formula: ba 2.95 Eu 0.05 Cu 3 Sc 4 O 12 . With BaCO 3 、Eu 2 O 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 Is used as raw material and comprises Ba 2.95 Eu 0.05 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours in a reducing atmosphere at 1050 ℃, cooled, reground to obtain the material, and then sintered for 6 hours at 950 ℃ in the reducing atmosphere to obtain the material with the nominal chemical composition of Ba 2.95 Eu 0.05 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak 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 10 is approximately around 650nm under the excitation of 450nm blue light, and the luminous intensity is improved compared with that of comparative example 9. It is obvious that in comparative example 10, the same reducing atmosphere is used in both sintering, which can improve the luminous intensity of the material to some extent.
Example 1
The material described in this example comprises a compound of the formula: ba 2.995 Eu 0.005 Cu 3 Sc 4 O 12 . With BaCO 3 、Eu 2 O 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 Is used as raw material and comprises Ba 2.995 Eu 0.005 Cu 3 Sc 4 O 12 Accurately weighing the raw materials according to the stoichiometric ratio, sintering the raw materials at 1050 ℃ in a reducing atmosphere for 6 hours, cooling the raw materials, and then grinding the raw materials againSintering the obtained raw material in air atmosphere at 950 ℃ for 6h to obtain the material with the nominal chemical composition of Ba 2.995 Eu 0.005 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in example 1 has two emission peaks under the excitation of 450nm blue light, which are respectively about 672nm and about 998 nm. Moreover, in example 1, compared with comparative examples 9 and 10, the sample exhibited a completely new luminescence phenomenon by the secondary sintering of the reducing atmosphere first and then the oxidizing atmosphere.
Example 2
The material described in this example, comprising a compound of the formula: ba 2.99 Eu 0.01 Cu 3 Sc 4 O 12 . With BaCO 3 、Eu 2 O 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 As a raw material, the component is Ba 2.99 Eu 0.01 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours in a reducing atmosphere at 1050 ℃, cooled, reground to obtain the material, and then sintered for 6 hours at 950 ℃ in an air atmosphere to obtain the material with the nominal chemical composition of Ba 2.99 Eu 0.01 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in example 2 has two emission peaks respectively at 676nm and about 1000nm under the excitation of 450nm blue light. Moreover, in example 2, compared with comparative examples 9 and 10, the sample exhibited a completely new luminescence phenomenon by the secondary sintering of the reducing atmosphere first and then the oxidizing atmosphere.
Example 3
The material described in this example, comprising a compound of the formula: ba 2.98 Eu 0.02 Cu 3 Sc 4 O 12 . With BaCO 3 、Eu 2 O 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 As a raw material, the component is Ba 2.98 Eu 0.02 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours in a reducing atmosphere at 1050 ℃, cooled, reground to obtain the material, and then sintered for 6 hours at 950 ℃ in an air atmosphere to obtain the material with the nominal chemical composition of Ba 2.98 Eu 0.02 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in example 3 has two emission peaks respectively about 676nm and about 1003nm under the excitation of 450nm blue light. Moreover, in example 3, compared with comparative examples 9 and 10, the sample exhibited a completely new luminescence phenomenon by the secondary sintering of the reducing atmosphere and then the oxidizing atmosphere.
Example 4
The material described in this example comprises a compound of the formula: ba 2.97 Eu 0.03 Cu 3 Sc 4 O 12 . With BaCO 3 、Eu 2 O 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 Is used as raw material and comprises Ba 2.97 Eu 0.03 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours in a reducing atmosphere at 1050 ℃, cooled, re-ground to obtain the material, and sintered for 6 hours at 950 ℃ in an air atmosphere to obtain the material with the nominal chemical composition of Ba 2.97 Eu 0.03 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in example 4 has two emission peaks, about 679nm and about 1007nm, under the excitation of 450nm blue light. Moreover, in example 4, compared with comparative examples 9 and 10, the sample exhibited a completely new luminescence phenomenon by the secondary sintering of the reducing atmosphere first and then the oxidizing atmosphere.
Example 5
The material described in this example, comprising a compound of the formula: ba 2.96 Eu 0.04 Cu 3 Sc 4 O 12 . With BaCO 3 、Eu 2 O 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 Is used as raw material and comprises Ba 2.96 Eu 0.04 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours in a reducing atmosphere at 1050 ℃, cooled, re-ground to obtain the material, and sintered for 6 hours at 950 ℃ in an air atmosphere to obtain the material with the nominal chemical composition of Ba 2.96 Eu 0.04 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in example 5 has two emission peaks, namely 680nm and about 1010nm, under the excitation of 450nm blue light. Moreover, in example 5, compared with comparative examples 9 and 10, the sample exhibited a completely new luminescence phenomenon by the secondary sintering of the reducing atmosphere and then the oxidizing atmosphere.
Example 6
The material described in this example comprises a compound of the formula: ba 2.95 Eu 0.05 Cu 3 Sc 4 O 12 . With BaCO 3 、Eu 2 O 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 Is used as raw material and comprises Ba 2.95 Eu 0.05 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours in a reducing atmosphere at 1050 ℃, cooled, reground to obtain the material, and then sintered for 6 hours at 950 ℃ in an air atmosphere to obtain the material with the nominal chemical composition of Ba 2.95 Eu 0.05 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in example 6 has two emission peaks, 680nm and 1010nm respectively, under the excitation of 450nm blue lightAbout nm. Moreover, in example 6, compared with comparative examples 9 and 10, the sample exhibited a completely new luminescence phenomenon by the secondary sintering of the reducing atmosphere first and then the oxidizing atmosphere.
Example 7
The material described in this example comprises a compound of the formula: ba 2.94 Eu 0.06 Cu 3 Sc 4 O 12 . With BaCO 3 、Eu 2 O 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 Is used as raw material and comprises Ba 2.94 Eu 0.06 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours in a reducing atmosphere at 1050 ℃, cooled, re-ground to obtain the material, and sintered for 6 hours at 950 ℃ in an air atmosphere to obtain the material with the nominal chemical composition of Ba 2.94 Eu 0.06 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in example 7 has two emission peaks, respectively about 680nm and about 1011nm, under the excitation of 450nm blue light. Moreover, in example 7, compared with comparative examples 9 and 10, the sample exhibited a completely new luminescence phenomenon by the secondary sintering of the reducing atmosphere first and then the oxidizing atmosphere.
Example 8
The material described in this example, comprising a compound of the formula: ba 2.93 Eu 0.07 Cu 3 Sc 4 O 12 . With BaCO 3 、Eu 2 O 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 Is used as raw material and comprises Ba 2.93 Eu 0.07 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours in a reducing atmosphere at 1050 ℃, cooled, reground to obtain the material, and then sintered for 6 hours at 950 ℃ in an air atmosphere to obtain the material with the nominal chemical composition of Ba 2.93 Eu 0.07 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in example 8 has two emission peaks, respectively 682nm and 1012nm, under the excitation of 450nm blue light. Moreover, in example 8, compared with comparative examples 9 and 10, the sample exhibited a completely new luminescence phenomenon by the secondary sintering of the reducing atmosphere and then the oxidizing atmosphere.
Example 9
The material described in this example, comprising a compound of the formula: ba 2.92 Eu 0.08 Cu 3 Sc 4 O 12 . With BaCO 3 、Eu 2 O 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 Is used as raw material and comprises Ba 2.92 Eu 0.08 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours in a reducing atmosphere at 1050 ℃, cooled, reground to obtain the material, and then sintered for 6 hours at 950 ℃ in an air atmosphere to obtain the material with the nominal chemical composition of Ba 2.92 Eu 0.08 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in example 9 has two emission peaks under the excitation of 450nm blue light, and the two emission peaks are respectively about 686nm and about 1012 nm. Moreover, in example 9, compared with comparative examples 9 and 10, the sample exhibited a completely new luminescence phenomenon by the secondary sintering of the reducing atmosphere first and then the oxidizing atmosphere.
Example 10
The material described in this example comprises a compound of the formula: ba 2.91 Eu 0.09 Cu 3 Sc 4 O 12 . With BaCO 3 、Eu 2 O 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 Is used as raw material and comprises Ba 2.91 Eu 0.09 Cu 3 Sc 4 O 12 Accurately weighing the raw materials according to the stoichiometric ratioSintering the materials at 1050 ℃ in a reducing atmosphere for 6h, cooling, re-grinding the obtained materials, and sintering the obtained raw materials in an air atmosphere at 950 ℃ for 6h to obtain the Ba-based composite material with the nominal chemical composition 2.91 Eu 0.09 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in example 10 has two emission peaks, respectively about 689nm and about 1015nm, under the excitation of the 450nm blue light. Moreover, in example 10, compared with comparative examples 9 and 10, the sample exhibited a completely new luminescence phenomenon by the secondary sintering of the reducing atmosphere and then the oxidizing atmosphere.
Example 11
The material described in this example, comprising a compound of the formula: ba 2.9 Eu 0.1 Cu 3 Sc 4 O 12 . With BaCO 3 、Eu 2 O 3 、CuCO 3 ·Cu(OH) 2 And Sc 2 O 3 As a raw material, the component is Ba 2.9 Eu 0.1 Cu 3 Sc 4 O 12 The raw materials are accurately weighed according to the stoichiometric ratio, sintered for 6 hours in a reducing atmosphere at 1050 ℃, cooled, reground to obtain the material, and then sintered for 6 hours at 950 ℃ in an air atmosphere to obtain the material with the nominal chemical composition of Ba 2.9 Eu 0.1 Cu 3 Sc 4 O 12 . The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, and the position of the main peak of the emission spectrum is shown in table 1. As can be seen from Table 1, the material prepared in example 11 has two emission peaks under the excitation of 450nm blue light, which are respectively about 690nm and 1015 nm. Moreover, in example 11, compared with comparative examples 9 and 10, the sample exhibited a completely new luminescence phenomenon by the secondary sintering of the reducing atmosphere first and then the oxidizing atmosphere.
TABLE 1 emission spectra data sheet of materials
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 (10)
1. An infrared light fluorescent material for improving the eyesight of old people, which is characterized in that the chemical general formula of the fluorescent material is as follows: ba 3-x Eu x Cu 3 Sc 4 O 12 Wherein, 0<x≤0.1。
2. The infrared light fluorescent material for improving eyesight of the elderly according to claim 1, wherein: in the chemical general formula of the infrared fluorescent material for improving the vision of the elderly, x = 0.04-0.08, preferably, x =0.05.
3. The method of claim 1 for synthesizing an infrared fluorescent material for improving eyesight of elderly people, comprising the steps of:
a) Mixing a Ba precursor, a Eu precursor, a Cu precursor and a Sc precursor, and carrying out high-temperature solid-phase reaction in a reducing atmosphere to obtain a precursor;
b) And grinding and mixing the precursor again, and then carrying out high-temperature solid-phase reaction in an air atmosphere to obtain the infrared fluorescent material for improving the eyesight of the old.
4. The method of claim 3, wherein in step a), the Ba precursor is selected from at least one of a carbonate of Ba, an oxalate of Ba and a nitrate of Ba; the Eu precursor is selected from Eu oxides; the Cu precursor is selected from at least one of basic carbonate of Cu, oxide of Cu, oxalate of Cu and nitrate of Cu; the Sc precursor is selected from Sc oxides; the purities of the Ba precursor, the Eu precursor, the Cu precursor and the Sc precursor are not lower than 99.5%; the molar ratio of the Ba precursor to the Eu precursor to the Cu precursor to the Sc precursor is (3-x): x: 3: 4, and the chemical general formula of the obtained deep red light-near infrared light fluorescent material is as follows: ba 3- x Eu x Cu 3 Sc 4 O 12 Wherein, 0<x≤0.1。
5. The method for synthesizing a deep red-near infrared fluorescent material according to claim 3, wherein: in the step a), the temperature of the high-temperature solid-phase reaction is 1000-1100 ℃, and the time of the high-temperature solid-phase reaction is 4-10 h.
6. The method for synthesizing a deep red-near infrared fluorescent material according to claim 3, wherein: in step a), the reducing atmosphere is ammonia gas or a nitrogen-hydrogen mixed gas.
7. The method for synthesizing a deep red-near infrared fluorescent material according to claim 3, wherein: in the step b), the temperature of the high-temperature solid-phase reaction is 900-1000 ℃, and the time of the high-temperature solid-phase reaction is 4-10 h.
8. The deep red-near infrared fluorescent material for improving eyesight of the elderly as set forth in claim 1 or 2, wherein: under the excitation of blue light, the deep red light-near infrared light fluorescent material can generate an emission wavelength range from 550 to 1480nm, two peaks exist in an emission spectrum, and peak wavelengths are respectively near 680nm and 1010 nm.
9. A light emitting device, characterized in that: the light emitting device comprises an excitation light source and a fluorescent material, wherein the excitation light source is a blue light LED chip, the fluorescent material comprises the deep red light-near infrared light fluorescent material for improving the vision deterioration of the old, and the fluorescent material is excited by the blue light LED chip to emit deep red light-near infrared light.
10. A light-emitting device according to claim 9, wherein: the fluorescent material contains Y 3 Al 5 O 12 :Ce 3+ Yellow fluorescent material and a deep red-near infrared fluorescent material for improving the eyesight of the elderly as claimed in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211486326.0A CN115806821B (en) | 2022-11-24 | 2022-11-24 | Synthesis method and application of infrared light fluorescent material for improving eyesight of old people |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211486326.0A CN115806821B (en) | 2022-11-24 | 2022-11-24 | Synthesis method and application of infrared light fluorescent material for improving eyesight of old people |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115806821A true CN115806821A (en) | 2023-03-17 |
| CN115806821B CN115806821B (en) | 2023-09-26 |
Family
ID=85484033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211486326.0A Active CN115806821B (en) | 2022-11-24 | 2022-11-24 | Synthesis method and application of infrared light fluorescent material for improving eyesight of old people |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115806821B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6231998B1 (en) * | 1999-05-04 | 2001-05-15 | Siemens Westinghouse Power Corporation | Thermal barrier coating |
| CN101268211A (en) * | 2005-09-20 | 2008-09-17 | 出光兴产株式会社 | Sputtering target, transparent conductive film, and transparent electrode |
| WO2018220168A2 (en) * | 2017-06-02 | 2018-12-06 | Nexdot | Ink comprising encapsulated nanoparticles |
| JP2021027344A (en) * | 2019-07-31 | 2021-02-22 | 京セラ株式会社 | Member for semiconductor manufacturing device, and semiconductor manufacturing device using the same |
| CN112646576A (en) * | 2020-12-21 | 2021-04-13 | 厦门大学 | Ultra-wide spectrum near-infrared fluorescent material, near-infrared fluorescent ceramic, and preparation method and device thereof |
| CN113191208A (en) * | 2021-04-09 | 2021-07-30 | 湖北工业大学 | Feature extraction method and computer equipment for remote sensing image instance segmentation |
| CN115200735A (en) * | 2021-06-01 | 2022-10-18 | 南京航空航天大学 | High-temperature space temperature and pressure field joint test method based on hollow inorganic phosphorescent beads |
-
2022
- 2022-11-24 CN CN202211486326.0A patent/CN115806821B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6231998B1 (en) * | 1999-05-04 | 2001-05-15 | Siemens Westinghouse Power Corporation | Thermal barrier coating |
| CN101268211A (en) * | 2005-09-20 | 2008-09-17 | 出光兴产株式会社 | Sputtering target, transparent conductive film, and transparent electrode |
| WO2018220168A2 (en) * | 2017-06-02 | 2018-12-06 | Nexdot | Ink comprising encapsulated nanoparticles |
| JP2021027344A (en) * | 2019-07-31 | 2021-02-22 | 京セラ株式会社 | Member for semiconductor manufacturing device, and semiconductor manufacturing device using the same |
| CN112646576A (en) * | 2020-12-21 | 2021-04-13 | 厦门大学 | Ultra-wide spectrum near-infrared fluorescent material, near-infrared fluorescent ceramic, and preparation method and device thereof |
| CN113191208A (en) * | 2021-04-09 | 2021-07-30 | 湖北工业大学 | Feature extraction method and computer equipment for remote sensing image instance segmentation |
| CN115200735A (en) * | 2021-06-01 | 2022-10-18 | 南京航空航天大学 | High-temperature space temperature and pressure field joint test method based on hollow inorganic phosphorescent beads |
Non-Patent Citations (2)
| Title |
|---|
| S E DUTTON等: "Dominant ferromagnetism in the spin-1/2 half-twist ladder 334 compounds, Ba3Cu3In4O12 and Ba3Cu3Sc4O12", 《JOURNAL OF PHYSICS: CONDENSED MATTER》, vol. 24, pages 166001 - 1, XP020221137, DOI: 10.1088/0953-8984/24/16/166001 * |
| 温芳等: "长余辉发光材料在应急疏散标识中的应用形态", 《化工进展》, vol. 41, pages 282 - 292 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115806821B (en) | 2023-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20200347999A1 (en) | Full Spectrum White Light Emitting Devices | |
| US6987353B2 (en) | Light emitting device having sulfoselenide fluorescent phosphor | |
| US7109648B2 (en) | Light emitting device having thio-selenide fluorescent phosphor | |
| Kumar et al. | Color tunable emission and temperature dependent photoluminescence properties of Eu3+ co-doped Gd2Zr2O7: Dy3+ phosphors | |
| TW201343876A (en) | Oxynitride phosphor powder | |
| US11578267B2 (en) | Near-infrared light-emitting phosphor, phosphor mixture, light-emitting element, and light-emitting device | |
| EP3997733A1 (en) | Full spectrum white light emitting devices | |
| EP1887068B1 (en) | Ce, pr-coactivated yttrium phosphate phosphor and lamp containing same | |
| CN113583676A (en) | Broadband near-infrared luminescent material and preparation method and application thereof | |
| CN110437832B (en) | Eu (Eu)2+Doped silicate near-infrared fluorescent powder, preparation method thereof and conversion type LED light-emitting device | |
| CN114106828B (en) | Cr (chromium) 3+ Doped near-infrared fluorescent powder with broadband emission and preparation method thereof | |
| CN111434749B (en) | Near-ultraviolet excited warm white light fluorescent powder and preparation method and application thereof | |
| WO2021007123A1 (en) | Full spectrum white light emitting devices | |
| CN109370580A (en) | A kind of titanium aluminate fluorescent powder and the preparation method and application thereof of bismuth ion activation | |
| CN111187622B (en) | Single matrix phosphate fluorescent powder for white light LED and preparation method thereof | |
| CN115806821B (en) | Synthesis method and application of infrared light fluorescent material for improving eyesight of old people | |
| TWI432555B (en) | Aluminate phosphor | |
| Bedekar et al. | White light emission from spin coated Gd2O3: Dy nano phosphors synthesized using polyol technique | |
| Prakash et al. | Spectral properties of Dy3+ doped ZnAl2O4 phosphor | |
| CN107652973B (en) | White light LEDs Mn ion doping garnet structure red illuminating material and its preparation method and application | |
| JP5216993B2 (en) | Phosphor and lamp | |
| KR20160051628A (en) | Red phosphor | |
| Wang et al. | Luminescence properties and energy transfer of the near-infrared phosphor Ca 3 In 2 Ge 3 O 12: Cr 3+, Nd 3+ | |
| CN114940904A (en) | Yb-based short-wave infrared luminescent material and preparation method and application thereof | |
| CN108531179A (en) | A kind of borate doped salt blue colour fluorescent powder of bismuth and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |