CN116536044A - Preparation method of broadband deep red-near infrared pc-LED fluorescent material and near infrared light source - Google Patents
Preparation method of broadband deep red-near infrared pc-LED fluorescent material and near infrared light source Download PDFInfo
- Publication number
- CN116536044A CN116536044A CN202310336420.6A CN202310336420A CN116536044A CN 116536044 A CN116536044 A CN 116536044A CN 202310336420 A CN202310336420 A CN 202310336420A CN 116536044 A CN116536044 A CN 116536044A
- Authority
- CN
- China
- Prior art keywords
- near infrared
- fluorescent material
- source
- deep red
- led fluorescent
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 238000004137 mechanical activation Methods 0.000 claims abstract description 6
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 230000003287 optical effect Effects 0.000 claims description 7
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 229910003443 lutetium oxide Inorganic materials 0.000 claims description 4
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 claims description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical group [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 2
- 239000002131 composite material Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 10
- 238000001228 spectrum Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005090 crystal field Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 238000004497 NIR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000004297 night vision Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7707—Germanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
-
- 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
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a broadband deep red-near infrared pc-LED fluorescent material, a preparation method thereof and a near infrared light source. The fluorescent material comprises a structural general formula A 3 B 2‑y C y D 3 O 12 :xCr 3+ Wherein A is Ca and/or Sr, B is at least one of Al, sc and Lu, C is at least one of Al, sc and Lu, and D is at least one of Ge, si and Sn, hf; the y is more than 0 and less than 2,0<x<0.3. The fluorescent material is prepared by uniformly mixing raw materials including an A source, a B source, a C source and a D source, and sequentially performing mechanical activation and sintering. The fluorescent powder has adjustable spectrum, high internal quantum efficiency and heatThe stability is good, and the manufacturing is simple, the cost is low, and the industrialization is easy to realize.
Description
Technical Field
The invention relates to a pc-LED fluorescent material, in particular to a preparation method of a broadband deep red-near infrared pc-LED fluorescent material and a near infrared light source, and belongs to the technical field of fluorescent materials.
Background
With the continuous maturation and improvement of the white light LED lighting technology (low cost) and efficiency (high photoelectric conversion efficiency up to 80%), scientific researchers began to put their eyes into the region of far-red-near infrared (650-1400 nm), and near infrared light sources were found to be widely used in many fields such as near infrared spectroscopy, plant artificial light supplement, night vision illumination, iris recognition, palm vein imaging, biomedical imaging, biological disease diagnosis and treatment, luminescent solar concentrators, optical communications, etc. This significant discovery led numerous researchers to develop research into deep red and near infrared light sources. At present, four main modes of a halogen tungsten lamp, a near infrared LED array, a silicon carbide heating element and a fluorescent powder converted LED which can generate a near infrared light source are adopted, and the halogen tungsten lamp, the near infrared LED array and the silicon carbide have the defects of short service life, low luminous efficiency, high cost, large volume and the like, so that the application of the halogen tungsten lamp, the near infrared LED array and the silicon carbide in near infrared is limited. Unlike conventional near infrared sources, phosphor-converted LEDs have the advantages of long life, small volume, low cost, etc. as novel near infrared sources, which provide a useful potential source for near infrared applications, but they still suffer from low output power, thermal stability, emission bands, etc.
The luminescence properties of phosphor-converted LEDs depend on the luminescence properties of near infrared phosphors, and many researchers have developed over the years a number of blue-excitable Cr 3+ Doped high-efficiency broadband deep red-near infrared fluorescent powder, but the near infrared fluorescent powder still has a lot of ways to get away in the face of requirements of practical high-power high efficiency, excellent stability, good device performance and the like. Currently, three main problems exist in the preparation of near infrared fluorescent powder with excellent efficiency and good thermal stability: first, cr 3+ The 3d-3d transition of (2) is a forbidden odd-even transition, resulting in lower electron absorptance and external quantum efficiency. Second is a weak crystal field 4 T 2 The energy level position is lower, and electrons in an excited state are easierThe non-radiative transition back to the ground state by multi-phonon emission or the like results in low internal quantum efficiency of the phosphor. Thirdly, along with the temperature rise, cr 3+ The probability of non-radiative transition of electrons in the fluorescent powder is increased, the luminous intensity of the fluorescent powder is obviously reduced, and thermal quenching is aggravated.
To overcome the existing Cr 3+ The problem faced by doping broadband near infrared depends on Cr 3+ The property of the luminescence property of the matrix lattice is deeply influenced by the crystal field intensity to regulate the crystal field intensity of the matrix lattice. In general, when external ions are doped into a host lattice, local lattices are distorted, and the degree of distortion of different lattice sites in the lattice is different, so that macroscopic distortion distribution phenomenon is caused, and the emission band of the fluorescent powder is widened and the luminous efficiency is reduced. However, doping with foreign ions also introduces an odd symmetric field, breaking Cr 3+ The 3d-3d electron transition of (2) is forbidden, and Cr is added 3+ The absorption of photons can improve the luminous intensity, internal quantum efficiency, external quantum efficiency and other luminous performances.
Chinese patent (CN 114292646B) discloses a near infrared luminescent material and a preparation method thereof and a near infrared light source using the same, wherein the chemical formula of the near infrared luminescent material is AB 2 M 2-x Cr x V 3 O 12 Wherein A is one of Li, na, K and Ag, B is one or more of Ca, sr and Ba, and M is one or more of Ca, mg and Zn; x is the mole fraction of Cr element, wherein x is more than or equal to 0 and less than or equal to 0.1. The near infrared luminescent material provided by the invention can be excited by ultraviolet light and near ultraviolet light with the spectrum range of 300-400 nm, emits visible light with the spectrum range of 400-700 nm and near infrared light with the spectrum range of 700-1100 nm, and can be used for a near infrared LED light source and improving the conversion efficiency of a solar battery; the preparation method adopts a solid phase method, is simple, green and pollution-free, and is suitable for large-scale production. However, the patent mainly aims at adjusting the emission bandwidth of the fluorescent material, and has great defects of light efficiency and suitability for excitation light, so that the performance requirement of using a high-power LED device is difficult to meet.
Disclosure of Invention
Aiming at the problems existing in the prior art, the first aim of the invention is to provide a broadband deep red-near infrared pc-LED fluorescent material, which is based on the synergistic effect among all the constituent elements, and can regulate and control the wavelength of emitted light by strictly controlling the addition proportion of all the constituent elements, thereby providing a plurality of optimal light source materials for near infrared application in different occasions.
The second aim of the invention is to provide a preparation method of the broadband dark red-near infrared pc-LED fluorescent material, which adopts a one-pot solid phase sintering process, improves the activation energy of the surface of the raw material through mechanical activation, and is convenient for the post sintering molding. The method has the advantages of simple process, low cost and the like, and is suitable for large-scale industrial production.
The third purpose of the invention is to provide a high-efficiency heat-resistant broadband deep red near infrared light source, which adopts a blue light chip as an excitation light source, and uses silica gel or resin to package the fluorescent powder and the blue light chip, and a filter is added to finally obtain the near infrared light source with the acquisition wave band of 650-1200 nm.
To achieve the technical purpose, the invention provides a broadband deep red-near infrared pc-LED fluorescent material, which comprises a structural general formula A 3 B 2-y C y D 3 O 12 :xCr 3+ Wherein A is Ca and/or Sr, B is at least one of Al and Lu, C is at least one of Al and Lu, and D is at least one of Ge, si, sn and Hf; the y is more than 0 and less than 2,0<x<0.3。
The fluorescent material provided by the invention is based on the synergistic effect of the components of the raw materials and Cr 3+ The luminous performance of the crystal is deeply influenced by the field intensity of the crystal to regulate the field intensity of the crystal of the matrix lattice, and Al is adopted by a crystal engineering regulation theory 3+ Substitution of Lu 3+ The lattice sites further improve the light emitting performance thereof.
A 3 B 2-y C y D 3 O 12 :xCr 3+ Is a garnet matrix material which is not luminous, A is coordinated with O to form dodecahedron, B/C is coordinated with O to form octahedron, D is coordinated with O to form tetrahedronThe octahedron in the matrix structure is Cr 3+ Providing occupiable or replaceable lattice points to act as a fixed Cr 3+ Cr (V) function 3+ As an activating ion, when Cr is doped 3+ When Cr 3+ Interact with the local environment surrounding the ligand to produce an emission band.
As a preferred embodiment, the space group of the fluorescent material is I-3ad.
As a preferable scheme, A in the fluorescent material is Ca, B and C are Lu and Al, and D is Ge.
As a preferred embodiment, the molar ratio of Al to Lu is 1.2 to 1.9:0.1 to 0.8. The addition amounts of Al and Lu are strictly carried out according to the above requirements, when a small amount of Al is doped 3+ The internal quantum efficiency of the sample gradually increases to about 100%, when Al 3+ When the doping content exceeds 1.4, the internal quantum efficiency starts to decrease significantly.
The invention also provides a preparation method of the broadband deep red-near infrared pc-LED fluorescent material, which comprises the steps of uniformly mixing raw materials including a source A, a source B and a source C, and sequentially carrying out mechanical activation and sintering.
As a preferred embodiment, the source a is at least one of calcium oxide, calcium hydroxide, strontium oxide, and strontium hydroxide.
As a preferred embodiment, the B source is at least one of alumina and lutetium oxide.
As a preferred embodiment, the C source is at least one of alumina and lutetium oxide.
As a preferred embodiment, the D source is germanium oxide.
As a preferred embodiment, the mechanical activation is performed by high-energy ball milling or mechanical grinding.
As a preferable scheme, the mode of mixing the raw materials is ball milling or mechanical grinding; the ball milling conditions are as follows: the time is 20-30 min, and the rotating speed is 150-300 r/min.
As a preferable scheme, the sintering mode is high-temperature sintering, and the conditions are as follows: heating from room temperature to 1300-1400 ℃ at 8-12 ℃/min, preserving heat for 5-8 h, and cooling to room temperature along with the furnace.
The invention also provides a high-efficiency heat-resistant broadband deep red near infrared light source, which comprises the near infrared pc-LED fluorescent material, a blue light LED chip and an optical filter, wherein the near infrared pc-LED fluorescent material, the blue light LED chip and the optical filter are any one of the preferable schemes; the blue LED chip and the fluorescent material are packaged by packaging adhesive, and the optical filter is fixedly covered on the packaging adhesive.
As a preferable embodiment, the light source has a light emission center of 700 to 900nm.
As a preferable scheme, the packaging adhesive is silica gel or epoxy resin, and the transmission wavelength of the filter plate is more than or equal to 500nm.
Compared with the prior art, the invention has the following beneficial effects:
1) The near infrared pc-LED fluorescent material provided by the invention is based on the synergistic effect among all the constituent elements, and the excitation light wavelength is regulated and controlled by strictly controlling the addition proportion of all the constituent elements, so that the optimal selection of the iris image acquisition wave band is realized.
2) In the preparation method provided by the invention, a one-pot solid-phase sintering process is adopted, the activation energy of the surface of the raw material is improved through mechanical activation, so that all elements can be uniformly embedded with each other, and the material is endowed with excellent medium entropy effect through high-temperature sintering molding. The method has the advantages of simple process, low cost and the like, and is suitable for large-scale industrial production.
3) In the technical scheme provided by the invention, the light source prepared by the fluorescent material provided by the invention has excellent optical performance, the light source adopts a blue light chip as an excitation light source, the fluorescent powder and the blue light chip can be packaged by silica gel or resin, and a filter with the transmission wavelength more than or equal to 500nm is additionally arranged, so that the broadband deep red-near infrared light source with the transmission wavelength of 650-1200 nm is finally obtained.
Drawings
FIG. 1 is an XRD pattern of the fluorescent materials obtained in examples 1 to 6;
FIG. 2 is a spectrum of a near infrared light source prepared from the fluorescent material obtained in comparative example 1;
FIG. 3 is a spectrum of a near infrared light source prepared from the fluorescent materials obtained in examples 1 to 6;
FIG. 4 is a schematic diagram of the structure of a near infrared light source prepared from the fluorescent materials according to examples 1 to 6 of the present invention;
FIG. 5 is a graph showing the internal quantum yield of an infrared light source prepared by using the fluorescent material provided in example 2 of the present invention.
Detailed Description
In the following description, it will be apparent that the described embodiments are merely some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw material used in the following examples is CaCO 3 、Lu 2 O 3 、Al 2 O 3 、GeO 2 And Cr (V) 2 O 3 The structural formula of the prepared fluorescent material is Ca 3 Lu 1.94-y Al y Ge 3 O 12 :xCr 3+ 。
Example 1
In the embodiment, y is 0.5, x is 0.06, raw materials are weighed according to stoichiometric number, fully ground in an agate mortar, then the materials are put into a corundum crucible, the temperature is raised from room temperature to 1350 ℃ at the temperature raising rate of 10 ℃ per minute, the temperature is kept for 6 hours, and the materials are cooled to the room temperature along with a furnace.
Example 2
In the embodiment, y is 0.7, x is 0.06, raw materials are weighed according to stoichiometric number, fully ground in an agate mortar, then the materials are put into a corundum crucible, the temperature is raised from room temperature to 1350 ℃ at the temperature raising rate of 10 ℃ per minute, the temperature is kept for 6 hours, and the materials are cooled to the room temperature along with a furnace.
Example 3
In the embodiment, y is 1.0, x is 0.06, raw materials are weighed according to stoichiometric number, fully ground in an agate mortar, then the materials are put into a corundum crucible, the temperature is raised from room temperature to 1350 ℃ at the temperature raising rate of 10 ℃ per minute, the temperature is kept for 6 hours, and the materials are cooled to the room temperature along with a furnace.
Example 4
In the embodiment, y is 1.2, x is 0.06, raw materials are weighed according to stoichiometric number, fully ground in an agate mortar, then the materials are put into a corundum crucible, the temperature is raised from room temperature to 1350 ℃ at a temperature raising rate of 10 ℃ per minute, the temperature is kept for 6 hours, and the materials are cooled to room temperature along with a furnace, so that the material is obtained.
Example 5
In the embodiment, y is 1.4, x is 0.06, raw materials are weighed according to stoichiometric number, fully ground in an agate mortar, then the materials are put into a corundum crucible, the temperature is raised from room temperature to 1350 ℃ at the temperature raising rate of 10 ℃ per minute, the temperature is kept for 6 hours, and the materials are cooled to the room temperature along with a furnace.
Example 6
In the embodiment, y is 1.6, x is 0.06, raw materials are weighed according to stoichiometric number, fully ground in an agate mortar, then the materials are put into a corundum crucible, the temperature is raised from room temperature to 1350 ℃ at the temperature raising rate of 10 ℃ per minute, the temperature is kept for 6 hours, and the materials are cooled to the room temperature along with a furnace.
The fluorescent materials obtained in examples 1 to 6 were prepared into near infrared light sources according to the following procedures: blue LEDs are used as excitation light sources, and fluorescent materials and silica gel are mixed according to the mass ratio of 1:1 are uniformly mixed and then covered on a blue LED chip, and are put into a drying oven to be dried for 12 hours at 100 ℃, and a filter with the transmission wavelength of more than or equal to 700nm is added, thus obtaining the LED chip.
The luminescence characteristics of the near infrared light sources prepared with the fluorescent materials obtained in examples 1 to 6 are shown in Table 1.
TABLE 1 luminescence characteristics of near-infrared light sources prepared with the fluorescent materials obtained in examples 1 to 6
It is understood from examples 1 to 6 that the internal quantum efficiency of the obtained fluorescent material was increased and then decreased with the increase of the content of Lu, and that an excessive amount of Lu did not bring about the internal quantum efficiency with a better effect, but rather brought about the increase of cost and the decrease of performance.
The excitation and emission patterns from the sample test were selected to optimize the emission wavelength, and all spectra were obtained from the material test.
Claims (9)
1. A broadband deep red-near infrared pc-LED fluorescent material is characterized in that: the fluorescent material comprises a structural general formula A 3 B 2-y C y D 3 O 12 :xCr 3+ Wherein A is Ca and/or Sr, B is at least one of Al and Lu, C is at least one of Al and Lu, and D is at least one of Ge, si, sn and Hf; the y is more than 0 and less than 2,0<x<0.3。
2. The broadband deep red-near infrared pc-LED fluorescent material of claim 1, wherein: the space group of the fluorescent material is I-3ad; a in the fluorescent material is Ca, B is Lu, C is Al, and D is Ge.
3. The broadband deep red-near infrared pc-LED fluorescent material of claim 2, wherein: the molar ratio of Al to Lu is 1.2-1.9: 0.1 to 0.8.
4. A method for preparing a broadband deep red-near infrared pc-LED fluorescent material according to any one of claims 1 to 3, characterized in that: uniformly mixing the raw materials including the source A, the source B, the source C and the source D, and sequentially performing mechanical activation and sintering to obtain the composite material.
5. The method for preparing the broadband deep red-near infrared pc-LED fluorescent material according to claim 4, wherein the method comprises the following steps: the source A is at least one of calcium oxide, calcium hydroxide, strontium oxide and strontium hydroxide; the source B is at least one of aluminum oxide and lutetium oxide; the C source is at least one of aluminum oxide and lutetium oxide; the D source is germanium oxide.
6. The method for preparing the broadband deep red-near infrared pc-LED fluorescent material according to claim 4, wherein the method comprises the following steps: the mode of mixing the raw materials is ball milling or mechanical grinding; the ball milling conditions are as follows: the time is 20-30 min, and the rotating speed is 150-300 r/min.
7. The method for preparing the broadband deep red-near infrared pc-LED fluorescent material according to claim 4, wherein the method comprises the following steps: the sintering mode is high-temperature sintering, and the conditions are as follows: heating from room temperature to 1300-1400 ℃ at 8-12 ℃/min, preserving heat for 5-8 h, and cooling to room temperature along with the furnace.
8.A high-efficiency heat-resistant broadband deep red near infrared light source is characterized in that: comprising the deep red near infrared pc-LED fluorescent material, blue LED chip and optical filter according to any one of claims 1 to 3; the blue LED chip and the fluorescent material are packaged by packaging adhesive, and the optical filter is fixedly covered on the packaging adhesive.
9. The efficient heat-resistant broadband deep red near infrared light source as claimed in claim 8, wherein: the packaging adhesive is silica gel or epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310336420.6A CN116536044A (en) | 2023-03-31 | 2023-03-31 | Preparation method of broadband deep red-near infrared pc-LED fluorescent material and near infrared light source |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310336420.6A CN116536044A (en) | 2023-03-31 | 2023-03-31 | Preparation method of broadband deep red-near infrared pc-LED fluorescent material and near infrared light source |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116536044A true CN116536044A (en) | 2023-08-04 |
Family
ID=87455028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310336420.6A Pending CN116536044A (en) | 2023-03-31 | 2023-03-31 | Preparation method of broadband deep red-near infrared pc-LED fluorescent material and near infrared light source |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116536044A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4648094A (en) * | 1984-06-08 | 1987-03-03 | Gte Laboratories Incorporated | Chromium (3+) doped germanate garnets as active media for tunable solid state lasers |
| CN105331364A (en) * | 2015-10-12 | 2016-02-17 | 杭州电子科技大学 | YAG:Mn red phosphor, preparation method and applications thereof |
| CN112552912A (en) * | 2020-12-16 | 2021-03-26 | 江西理工大学 | Novel Cr3+Doped broadband near-infrared fluorescent powder, preparation and application |
| CN115872445A (en) * | 2022-12-16 | 2023-03-31 | 广东工业大学 | Garnet type luminescent material and preparation method and application thereof |
-
2023
- 2023-03-31 CN CN202310336420.6A patent/CN116536044A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4648094A (en) * | 1984-06-08 | 1987-03-03 | Gte Laboratories Incorporated | Chromium (3+) doped germanate garnets as active media for tunable solid state lasers |
| CN105331364A (en) * | 2015-10-12 | 2016-02-17 | 杭州电子科技大学 | YAG:Mn red phosphor, preparation method and applications thereof |
| CN112552912A (en) * | 2020-12-16 | 2021-03-26 | 江西理工大学 | Novel Cr3+Doped broadband near-infrared fluorescent powder, preparation and application |
| CN115872445A (en) * | 2022-12-16 | 2023-03-31 | 广东工业大学 | Garnet type luminescent material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| JUNQIN FENG等: "The Near-infrared luminescence properties and applications of Ca3Lu2Ge3O12:Cr3+ phosphor", JOURNAL OF LUMINESCENCE, vol. 252, pages 119379 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106518037B (en) | A kind of silicate fluorescent ceramics of full spectral emissions and preparation method thereof | |
| CN112159220B (en) | High-thermal-stability high-quantum-efficiency fluorescent ceramic for white light LED/LD and preparation method thereof | |
| CN110041920A (en) | One plant growth LED light red fluorescence powder and preparation method thereof | |
| CN113248926B (en) | Red light conversion film capable of promoting plant growth and preparation method thereof | |
| CN112920801B (en) | Red light fluorescent powder material and preparation method thereof | |
| CN115838286B (en) | Preparation and application of fluorescent ceramic for high-apparent-finger white light LED/LD | |
| CN109370588B (en) | Nitride fluorescent powder for semiconductor luminescence, preparation method thereof and luminescent device | |
| CN114540013B (en) | Lifting CaO-Eu 2+ Method for preparing near infrared fluorescent powder with luminous intensity and thermal stability and application thereof | |
| CN116536044A (en) | Preparation method of broadband deep red-near infrared pc-LED fluorescent material and near infrared light source | |
| CN109294568A (en) | A kind of nitride red fluorescent powder for white light LED and preparation method thereof | |
| CN104059640A (en) | Preparation methods of borate fluorescent powder matrix and fluorescent powder | |
| CN110041931B (en) | Near-infrared fluorescent film, preparation method thereof and near-infrared LED | |
| CN103045258B (en) | Red fluorescent powder for white LED and preparation method thereof | |
| CN111072384A (en) | Ultraviolet excited fluorescent ceramic and preparation method thereof | |
| CN109749741A (en) | A kind of fluorescence membrane of the powder containing near-infrared fluorescent and application | |
| CN105238401B (en) | White emitting fluorescent powder based on ultraviolet light or near ultraviolet excitation and preparation method thereof | |
| CN110343523A (en) | A kind of Mn4+Tantalates red fluorescence powder of doping and its preparation method and application | |
| CN103361045B (en) | Nitrogen oxide fluorescent powder used in white-light LED, and preparation method thereof | |
| CN114806559B (en) | Eu (Eu) 2+ Activated ultra-wideband visible-near infrared luminescent material, preparation method and application | |
| CN117143600B (en) | Sodium-indium garnet-based near infrared fluorescent powder and preparation method thereof | |
| CN114686228B (en) | Red light fluorescent powder and preparation method and application thereof | |
| CN115572600B (en) | Sm (Sm) 2+ Activated broadband near infrared luminescent material and preparation method and application thereof | |
| CN117209276A (en) | Dark red fluorescent ceramic for plant illumination and preparation method thereof | |
| CN117383830A (en) | High-thermal-conductivity high-strength red fluorescent glass ceramic material and preparation method thereof | |
| CN116200190A (en) | Ultra-wideband near infrared fluorescent powder and preparation method and application thereof |
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 |