CN114672306A - Near-infrared fluorescent powder, preparation method and LED device formed by same - Google Patents
Near-infrared fluorescent powder, preparation method and LED device formed by same Download PDFInfo
- Publication number
- CN114672306A CN114672306A CN202210311646.6A CN202210311646A CN114672306A CN 114672306 A CN114672306 A CN 114672306A CN 202210311646 A CN202210311646 A CN 202210311646A CN 114672306 A CN114672306 A CN 114672306A
- Authority
- CN
- China
- Prior art keywords
- infrared
- fluorescent powder
- infrared fluorescent
- glass
- visible
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 28
- 239000011521 glass Substances 0.000 claims description 71
- 239000011159 matrix material Substances 0.000 claims description 42
- 239000002994 raw material Substances 0.000 claims description 36
- 239000002241 glass-ceramic Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000005337 ground glass Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 9
- 238000005286 illumination Methods 0.000 abstract description 7
- 238000000701 chemical imaging Methods 0.000 abstract description 6
- 238000001514 detection method Methods 0.000 abstract description 4
- 230000004297 night vision Effects 0.000 abstract description 4
- 238000003384 imaging method Methods 0.000 abstract description 3
- 238000002329 infrared spectrum Methods 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- 239000011651 chromium Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 238000001194 electroluminescence spectrum Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000006064 precursor glass Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000006112 glass ceramic composition Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000018481 Hylocereus undatus Nutrition 0.000 description 1
- 244000157072 Hylocereus undatus Species 0.000 description 1
- -1 Rare earth ion Chemical class 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77344—Aluminosilicates
-
- 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
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
- C09K11/685—Aluminates; Silicates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
Abstract
The invention discloses near-infrared fluorescent powder, and the chemical general formula of the near-infrared fluorescent powder is A2Al4Si5O18:Cr3+Or A2Al4Si5O18:Eu2+,Cr3+Wherein A is one of Mg, Ca, Sr, Ba and Zn. The near-infrared fluorescent powder, the preparation method and the LED device formed by the near-infrared fluorescent powder can provide the near-infrared fluorescent powder and the visible-near-infrared fluorescent powder which have wider reflection range and continuous emission bands, and the LED device formed by the visible-near-infrared fluorescent powder, and can meet various application requirements of plant illumination, security night vision, biological detection and imaging, near-infrared spectrum technology, hyperspectral imaging technology and the like.
Description
Technical Field
The invention relates to the technical field of inorganic luminescent materials, in particular to near-infrared fluorescent powder, a preparation method and an LED device formed by the near-infrared fluorescent powder.
Background
Conventional near-infrared light sources such as halogen lamps can provide near-infrared emission with high brightness and a wide emission range. However, the near-infrared light sources have the disadvantages of high energy consumption, short service life, low photoelectric conversion efficiency, large volume, large heat productivity and the like, and cannot meet the requirements of future application scenes. Therefore, the development of a fluorescence conversion type LED having performance comparable to that of the conventional near infrared light source has received much attention.
Cr3+Ions can occupy a weak crystal field environment to realize 700-1100 nm short-wave near-infrared emission, and can be efficiently excited by a blue light LED chip. The near-infrared LED device prepared from the blue-light LED chip has wide application prospect in the fields of plant illumination, night vision illumination, biological imaging and biological detection, food monitoring and the like. However, most of Cr3+The emission wavelength of the doped near-infrared luminescent material is within the range of 700-800 nm, and the emission half-peak width is less than 200nm, so that the practical application range of the doped near-infrared luminescent material is limited.
Cr3+The doped near-infrared luminescent material has wide-range absorption in ultraviolet, blue light and red light regions, so that short-wave emission cannot be realized. However, commercial crops such as dragon fruits and the like have wide requirements on visible light and near infrared light, and meanwhile, a visible-near infrared light source emitting in an ultra-wide range is required by a hyperspectral imaging technology. The wide-range emission visible-near infrared light source formed by simply mixing multiple fluorescent powders has high cost, and can cause energy loss caused by reabsorption among multiple luminescent materials.
Rare earth ion and Cr3+Ion co-doping enables and may build efficient energy transfer, however, currently available Ce3+And Cr3+The wide-range visible-near infrared luminescent material codoped by ions has a narrow emission range and a discontinuous emission band, so that the application of the visible-near infrared luminescent material in plant illumination and hyperspectral imaging technologies is limited. The development of visible-near infrared luminescent materials emitting in an ultra-wide range has remarkable significance for visible-near infrared light sources used in plant illumination and hyperspectral imaging technologies.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the problems in the related art. Therefore, the invention aims to provide the near-infrared fluorescent powder, the preparation method and the LED device formed by the near-infrared fluorescent powder, the near-infrared fluorescent powder and the visible-near-infrared fluorescent powder which have wider reflection range and continuous emission bands, and the LED device formed by the fluorescent powder, so that various application requirements of plant illumination, security night vision, biological detection and imaging, near-infrared spectrum technology, hyperspectral imaging technology and the like can be met.
In order to achieve the purpose, the invention adopts the following technical scheme: a near-infrared fluorescent powder has a chemical general formula A2Al4Si5O18:Cr3+Or A2Al4Si5O18:Eu2+,Cr3+Wherein A is one of Mg, Ca, Sr, Ba and Zn.
Further, A2Al4Si5O18:Cr3+The emitted near infrared wavelength is 700-1300nm, wherein, Cr3+Is a near infrared luminescence center.
Further, A2Al4Si5O18:Eu2+,Cr3+The emitted visible-near infrared wavelength is 500-1200nm, wherein Eu2+Being the center of visible light emission, Cr3+Is a near infrared luminescence center.
A method for preparing near-infrared fluorescent powder is characterized by comprising the following steps:
s1: mixing and grinding glass matrix raw materials uniformly; the glass matrix raw materials comprise a simple substance or a compound containing an element A, a simple substance or a compound containing an element Al, a simple substance or a compound containing an element Si, and a simple substance or a compound containing an element Cr;
s2: the glass matrix raw material which is mixed and ground uniformly is insulated for 0.5 to 6 hours at the temperature of 1450 and 1650 ℃;
s3: taking out and then eliminating stress to obtain a glass substrate;
s4: and carrying out crystallization heat treatment on the glass substrate for 0.15-5 h to obtain near-infrared fluorescent glass ceramic, and crushing the near-infrared fluorescent glass ceramic to obtain the near-infrared fluorescent powder.
Further, in the step S2, the glass matrix raw material which is uniformly mixed and ground is loaded into a crucible and is placed into a tube furnace which is communicated with a reducing atmosphere, the temperature is preserved for 0.5 to 6 hours at 1450-1650 ℃, the blue glass matrix is obtained in the step S3, and the step S4 is used for placing the blue glass matrix into the tube furnace which is communicated with the reducing atmosphere for crystallization heat treatment for 0.15 to 5 hours.
Further, in the step S2, the glass substrate raw material mixed and ground uniformly is put into a high-temperature box furnace and is placed in the air; preserving the heat at 1450 and 1650 ℃ for 0.5 to 6 hours to obtain a green glass substrate in step S3; and S4, putting the green glass substrate into a high-temperature box furnace in the air for crystallization heat treatment for 0.15-5 h.
Further, the method for eliminating stress in step S3 includes: pouring the heat-insulated product into a graphite mould, or naturally cooling the heat-insulated product to 650-800 ℃ for heat insulation for 3-10 h.
Further, the molar ratio of the Al element, the Si element, the Cr element and the A element in the glass matrix raw material is 5-50: 40-80: 0.001-20: 1-70.
further, the glass matrix raw material also comprises a simple substance or a compound containing Eu element; the visible light-near infrared fluorescent glass ceramic is obtained in the step S4, and the visible light-near infrared fluorescent glass ceramic is crushed to obtain visible light-near infrared fluorescent powder;
the molar ratio of Al element, Si element, Cr element, A element and Eu element in the glass matrix raw material is as follows: 5-50: 40-80: 0.001-20: 1-70: 0.001-20.
a near-infrared LED device containing near-infrared fluorescent powder, which is characterized by comprising an LED chip, wherein the near-infrared fluorescent powder in any one of claims 1 to 3 is coated on the LED chip; the light-emitting wavelength of the LED chip is 250-750 nm.
Compared with the prior art, the application has the following advantages: in this application A2Al4Si5O18:Cr3+Formation of Cr3+The doped near-infrared fluorescent powder can be efficiently excited by ultraviolet light, blue light and red light and is converted into near-infrared light in the range of 700-1300nm, the emission peak value is about 867nm, and the half-peak width is about 237 nm; a. the2Al4Si5O18:Eu2+,Cr3+Formation of Eu2+And Cr3+The co-doped visible light-near infrared fluorescent powder can be efficiently excited by ultraviolet light and blue light, and is converted into visible light-near infrared light in the range of 500-1200nm, the emission peak value is about 615nm, and the half-peak width is about 450 nm; when Eu is used2+And Cr3+When codoped, from Cr3+The near infrared luminescence and heat-resistant quenching performance of ion transition can be remarkably improved.
The near-infrared fluorescent powder and the visible-near-infrared fluorescent powder have high luminous brightness, good physical and chemical stability, low cost of raw materials and simple preparation process. Meanwhile, two forms of the fluorescent powder and the fluorescent glass ceramic material can be realized in one step, and the problems that the luminous efficiency is reduced and the like caused by different refractive indexes of the fluorescent powder and the glass powder in the process of sintering the traditional fluorescent powder and the glass powder into the fluorescent glass ceramic composite material at low temperature are solved.
The LED device formed by the two kinds of fluorescent powder has the advantages of high luminous efficiency, low cost, long service life, wide emission range and small volume, and can meet various application requirements of plant illumination, security night vision, biological detection and imaging, near infrared spectrum technology, hyperspectral imaging technology and the like.
Drawings
FIG. 1 is an XRD pattern of the near infrared/visible-near infrared luminescent materials of examples 1 and 3 of the present invention;
FIG. 2 is Mg in example 1 of the present invention2Al4Si5O18:Cr3+A fluorescence spectrum of the near-infrared luminescent material;
FIG. 3 is Mg in example 3 of the present invention2Al4Si5O18:Eu2+,Cr3+A fluorescence spectrum of the visible-near infrared luminescent material;
FIG. 4 is an electroluminescence spectrum of a near-infrared LED device of example 7 of the present invention;
fig. 5 is an electroluminescence spectrum of a visible-near-infrared LED device of example 8 of the present invention.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. It is intended that all modifications or alterations to the methods, procedures or conditions of the present invention be made without departing from the spirit and substance of the invention. Unless otherwise specified, the experimental materials, reagents, instruments and the like used in the examples of the present invention are commercially available; unless otherwise specified, all technical means in the examples of the present invention are conventional means well known to those skilled in the art.
The application provides a near-infrared fluorescent powder, the chemical general formula of which is A2Al4Si5O18:Cr3+Or A2Al4Si5O18:Eu2+,Cr3+Wherein A is one of Mg, Ca, Sr, Ba and Zn.
Wherein, the chemical formula is A2Al4Si5O18:Cr3+The corresponding near-infrared fluorescent powder can be efficiently excited by ultraviolet light, blue light and red light, and the excitation band of the near-infrared fluorescent powder extends from 250nm to 750 nm; cr (chromium) component3+Is a near infrared luminescence center, the emitted near infrared wavelength is 700-1300nm, the emission peak value is about 867nm, and the half-peak width is about 237 nm.
Has a chemical formula of A2Al4Si5O18:Eu2+,Cr3+The corresponding visible light-near infrared fluorescent powder can be efficiently excited by ultraviolet light and blue light, and the excitation band of the visible light-near infrared fluorescent powder extends from 250nm to 750 nm; eu (Eu)2+Being the center of visible light emission, Cr3+Is near redThe wavelength of the emitted visible light-near infrared light is 500-1200nm, the emission peak is about 615nm, and the half-peak width is about 450 nm.
The near-infrared fluorescent powder and the visible-near-infrared fluorescent powder have high luminous brightness, good physical and chemical stability, low cost of raw materials and simple preparation process. Meanwhile, two forms of the fluorescent powder and the fluorescent glass ceramic material can be realized in one step, and the problems that the luminous efficiency is reduced and the like caused by different refractive indexes of the fluorescent powder and the glass powder in the process of sintering the traditional fluorescent powder and the glass powder into the fluorescent glass ceramic composite material at low temperature are solved.
The invention provides a method for preparing near-infrared fluorescent powder, which comprises the following steps:
s1: mixing and grinding glass matrix raw materials uniformly; the glass matrix raw materials comprise a simple substance or a compound containing an element A, a simple substance or a compound containing an element Al, a simple substance or a compound containing an element Si, and a simple substance or a compound containing an element Cr; the molar ratio of Al element, Si element, Cr element and A element in the glass matrix raw material is 5-50: 40-80: 0.001-20: 1-70. a is one of Mg, Ca, Sr, Ba and Zn. For example, the glass matrix raw materials may be: al (Al)2O3、SiO2、Cr2CO3And MgO, CaCO3、SrCO3、BaCO3And ZnO.
S2: putting the glass matrix raw material which is uniformly mixed and ground into a crucible and placing the crucible into a tube furnace which is introduced with reducing atmosphere, and preserving heat for 0.5-6 h at 1450-; or putting the glass matrix raw materials which are uniformly mixed and ground into a high-temperature box type furnace and placing the furnace in the air; preserving the heat for 0.5 to 6 hours at 1450 and 1650 ℃, wherein the original atmosphere is nitrogen-hydrogen mixed gas, argon-hydrogen mixed gas, carbon powder reduction or CO atmosphere.
S3: pouring the heat-insulated product into a graphite mold, or naturally cooling the heat-insulated product to 650 plus materials at 800 ℃ for 3-10 h to eliminate stress, thereby obtaining a blue glass matrix or a green glass matrix;
s4: and (3) putting the blue glass substrate into a tube furnace with a reducing atmosphere for crystallization heat treatment for 0.15-5 h, or putting the green glass substrate into a high-temperature box furnace in the air for crystallization heat treatment for 0.15-5 h to obtain near-infrared fluorescent glass ceramic, and crushing the near-infrared fluorescent glass ceramic to obtain the near-infrared fluorescent powder.
The invention provides a method for preparing visible light-near infrared fluorescent powder, which comprises the following steps:
s1: mixing and grinding glass matrix raw materials uniformly; the glass matrix raw materials comprise a simple substance or compound containing an A element, a simple substance or compound containing an Al element, a simple substance or compound containing an Si element, a simple substance or compound containing a Cr element and a simple substance or compound containing an Eu element; the molar ratio of Al element, Si element, Cr element, A element and Eu element in the glass matrix raw material is as follows: 5-50: 40-80: 0.001-20: 1-70: 0.001-20. for example, the glass matrix raw materials may be: al (Al)2O3、SiO2、Cr2CO3、Eu2CO3And MgO, CaCO3、SrCO3、BaCO3And ZnO.
S2: putting the glass matrix raw material which is uniformly mixed and ground into a crucible and placing the crucible into a tube furnace which is introduced with reducing atmosphere, and preserving heat for 0.5-6 h at 1450-; or putting the glass matrix raw materials which are uniformly mixed and ground into a high-temperature box type furnace and placing the furnace in the air; preserving the heat for 0.5 to 6 hours at 1450 and 1650 ℃; the original atmosphere is nitrogen-hydrogen mixed gas, argon-hydrogen mixed gas, carbon powder reduction or CO atmosphere.
S3: pouring the heat-insulated product into a graphite mold, or naturally cooling the heat-insulated product to 650 plus materials at 800 ℃ for 3-10 h to eliminate stress, thereby obtaining a blue glass matrix or a green glass matrix;
s4: and (2) putting the blue glass substrate into a tube furnace with a reducing atmosphere for crystallization heat treatment for 0.15-5 h, or putting the green glass substrate into a high-temperature box furnace in the air for crystallization heat treatment for 0.15-5 h to obtain the visible light-near infrared fluorescent glass ceramic, and crushing the visible light-near infrared fluorescent glass ceramic to obtain the near infrared fluorescent powder.
In the preparation process of the fluorescent powder, precursor glass prepared in the air is green, wherein Cr is3+The ion part is used as the main structure of the glass network, the ion part is used as the outer body of the network, and finally the glass network is manufacturedIn the prepared near-infrared phosphor, Cr3+Present in octahedra and tetrahedra. The precursor glass sintered in the reducing atmosphere is blue, Cr3+The glass network exists as a main body and hardly acts as a glass outer body, so that the prepared near-infrared fluorescent powder contains Cr3+Almost exclusively in tetrahedra. In terms of optical properties, the spectral properties of the fluorescent powder prepared from the precursor glass of the two colors are basically consistent.
The near-infrared LED device comprises an LED chip, a packaging substrate and infrared fluorescent powder or visible light-near infrared fluorescent powder, wherein the light-emitting wavelength of the LED chip is 250-750nm, preferably 400-480 nm.
As one embodiment, a specific process for preparing an LED device includes: mixing near-infrared fluorescent powder or visible-near-infrared fluorescent powder with epoxy resin, transparent silica gel or other liquid with curing capability; and uniformly coating the mixture on an LED chip, placing the LED chip in a blast drying oven, curing at high temperature, and basically packaging to successfully obtain the near-infrared device or the visible-near infrared LED device.
As another example, the LED device may be further fixed on the LED chip by using other fixing methods such as direct bonding of near-infrared fluorescent glass ceramic or visible light-near-infrared fluorescent glass ceramic, and then the near-infrared device or visible-near-infrared LED device is obtained through basic packaging.
The present disclosure is further explained below by means of specific examples:
example 1
Adding MgO and Al2O3、SiO2And Cr2O3The powder is weighed according to the formula of the molar ratio of Mg element, Al element, Si element and Cr element of 30:19:50:1, and then ground by an agate mortar for 0.5-1 h until the mixture is uniform. Putting an alumina crucible filled with glass matrix raw materials which are uniformly mixed and ground into a crucible containing 5 percent of H2And 95% N2Preserving the heat for 5 hours at 1550 ℃ in a tubular furnace with reducing atmosphere; the obtained melt is naturally cooled along with the tube furnace to obtain a blue glass matrix, namely a blue glass precursor, and thenPutting a blue glass substrate into a furnace with 5% H2And 95% N2And (3) preserving the heat for 1h at 1050 ℃ in a tubular furnace in a reducing atmosphere to obtain the near-infrared fluorescent glass ceramic, and crushing to obtain the near-infrared fluorescent powder. The XRD pattern of the finally obtained near-infrared fluorescent powder is shown in figure 1, and the near-infrared luminescent material is known to be a single pure phase. The emission spectrum of the near-infrared phosphor is shown in fig. 2, and it can be known that the near-infrared luminescent material can be efficiently excited by ultraviolet light, blue light and red light and exhibits broadband near-infrared emission with emission peaks of 867nm and 700-1300 nm.
Example 2
Adding MgO and Al2O3、SiO2And Cr2O3The powder is weighed according to the formula of the molar ratio of Mg element to Al element to Si element to Cr element of 30:19:50:1, and then ground by using an agate mortar for 0.5-1 h until the powder is uniformly mixed. Putting the alumina crucible filled with the glass matrix raw material which is uniformly mixed and ground into a high-temperature box type furnace in the atmospheric environment, and preserving heat for 4 hours at 1600 ℃; and naturally cooling the obtained melt along with a high-temperature box furnace to obtain a green glass matrix, namely a green glass precursor, then putting the green glass matrix into the high-temperature box furnace in the atmosphere, preserving the temperature for 1h at 1100 ℃ to obtain the near-infrared fluorescent glass ceramic, and crushing to obtain the near-infrared fluorescent powder.
Example 3
Mixing MgO and Al2O3、SiO2、Eu2O3And Cr2O3The powder is weighed according to the formula of the molar ratio of Mg element, Al element, Si element, Eu element and Cr element of 29.5:19:50:0.5:1, and then ground by an agate mortar for 0.5-1 h until the mixture is uniformly mixed. Putting an alumina crucible filled with glass matrix raw materials which are uniformly mixed and ground into a crucible filled with 5 percent of H2And 95% N2And (3) preserving the temperature for 5 hours at 1550 ℃ in a tubular furnace with a reducing atmosphere. The obtained melt was naturally cooled in a tube furnace to obtain a blue glass substrate, and then the blue glass substrate was placed in a tube furnace to which 5% H was passed2And 95% N2And (3) preserving the heat of the tube furnace in the reducing atmosphere at 1050 ℃ for 1h to obtain the visible-near infrared fluorescent glass ceramic, and crushing the visible-near infrared fluorescent glass ceramic to obtain the visible-near infrared fluorescent powder. Visible-near infrared fluorescence obtainedThe XRD pattern of the powder is shown in figure 1, and the visible-near infrared luminescent material is known to be a single pure phase. The emission spectrum of the visible-near infrared phosphor is shown in fig. 3, and it can be known that the visible-near infrared luminescent material can be efficiently excited by ultraviolet light and blue light and exhibits visible-near infrared emission in the ultra-wide emission range of 500-1200 nm.
Example 4
Adding MgO and Al2O3、SiO2、Eu2O3And Cr2O3The powder is weighed according to the formula of the molar ratio of Mg element, Al element, Si element, Eu element and Cr element of 29.5:19:50:0.5:1, and then ground by an agate mortar for 0.5-1 h until the mixture is uniformly mixed. And putting the alumina crucible filled with the raw material mixture into a high-temperature box furnace in an atmospheric environment, and preserving the heat for 4 hours at 1600 ℃. And naturally cooling the obtained melt along with a high-temperature box-type furnace to obtain a green glass substrate, then putting the green glass substrate into the high-temperature box-type furnace in the atmosphere, preserving the heat for 1h at 1100 ℃ to obtain the visible-near infrared fluorescent glass ceramic, and crushing to obtain the visible-near infrared fluorescent powder. Notably, Eu3+The ions can be self-reduced into Eu in the preparation process2+Ionic, showing a bright orange-yellow emission.
Example 5
Mixing CaCO3、Al2O3、SiO2And Cr2O3The powder is weighed according to the formula of the molar ratio of the Ca element to the Al element to the Si element to the Cr element of 70:50:80:20, and then ground by using an agate mortar for 0.5-1 h until the powder is uniformly mixed. Putting an alumina crucible filled with glass matrix raw materials which are uniformly mixed and ground into a crucible filled with 5 percent of H2And 95% N2Preserving the heat for 5 hours at 1550 ℃ in a tubular furnace with reducing atmosphere; naturally cooling the obtained melt along with a tube furnace to obtain a blue glass matrix, namely a blue glass precursor, and then putting the blue glass matrix into a furnace body which is filled with 5% of H2And 95% N2And (3) preserving the heat for 1h at 1050 ℃ in a tubular furnace in a reducing atmosphere to obtain the near-infrared fluorescent glass ceramic, and crushing to obtain the near-infrared fluorescent powder.
Example 6
ZnO and Al are mixed2O3、SiO2、Eu2O3And Cr2O3The powder is weighed according to the formula of the mol ratio of Zn element, Al element, Si element, Eu element and Cr element of 30:40:65:10:10, and then ground by an agate mortar for 0.5-1 h until the powder is uniformly mixed. And putting the alumina crucible filled with the raw material mixture into a high-temperature box furnace in an atmospheric environment, and preserving the heat for 4 hours at 1600 ℃. And naturally cooling the obtained melt along with a high-temperature box furnace to obtain a green glass matrix, then putting the green glass matrix into the high-temperature box furnace in the atmosphere, preserving the temperature for 1h at 1100 ℃ to obtain the visible-near infrared fluorescent glass ceramic, and crushing to obtain the visible-near infrared fluorescent powder.
Example 7
The multifunctional near-infrared LED device comprises a packaging substrate, an LED chip and near-infrared fluorescent powder from bottom to top. In this example, a blue LED chip with a wavelength of 450nm and Cr prepared in example 1 were selected3+A near-infrared fluorescent powder. Uniformly mixing the target fluorescent powder and the transparent silica gel according to the mass ratio of 1:1, covering the LED chip in a coating or dispensing manner, welding a circuit, and packaging to obtain the near-infrared LED device of the embodiment. The electroluminescence spectrum of the near-infrared LED device is shown in fig. 4.
Example 8
The multifunctional visible-near infrared LED device comprises a packaging substrate, an LED chip and visible-near infrared luminescent powder from bottom to top. In this embodiment, a blue LED chip with a wavelength of 450nm is selected, and Eu prepared in embodiment 33+And Cr3 +Co-doped visible-near infrared phosphor. Uniformly mixing the target fluorescent powder and the transparent silica gel according to the mass ratio of 1:1, covering the LED chip in a coating or dispensing manner, welding a circuit, and packaging to obtain the visible-near infrared LED device. The electroluminescence spectrum of the visible-near infrared LED device is shown in FIG. 5, and the emission range is 440-1050 nm, which is substantially consistent with that of a commercial halogen lamp.
It is to be understood that the foregoing examples, while indicating the preferred embodiments of the invention, are given by way of illustration and description, and are not to be construed as limiting the scope of the invention; it should be noted that, for those skilled in the art, the above technical features can be freely combined, and several changes and modifications can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention; therefore, all equivalent changes and modifications made within the scope of the claims of the present invention should be covered by the claims of the present invention.
Claims (10)
1. The near-infrared fluorescent powder is characterized in that the chemical general formula of the near-infrared fluorescent powder is A2Al4Si5O18:Cr3+Or A2Al4Si5O18:Eu2+,Cr3+Wherein A is one of Mg, Ca, Sr, Ba and Zn.
2. The near-infrared phosphor of claim 1, wherein A is2Al4Si5O18:Cr3+The emitted near infrared wavelength is 700-1300nm, wherein, Cr3+Is a near infrared luminescence center.
3. The near-infrared phosphor of claim 1, wherein A is2Al4Si5O18:Eu2+,Cr3+The visible-near infrared wavelength of the emission is 500-1200nm, wherein Eu2+Being the center of visible light emission, Cr3+Is a near infrared luminescence center.
4. A method of making the near-infrared phosphor of any of claims 1-3, comprising:
s1: mixing and grinding glass matrix raw materials uniformly; the glass matrix raw materials comprise a simple substance or a compound containing an element A, a simple substance or a compound containing an element Al, a simple substance or a compound containing an element Si, and a simple substance or a compound containing an element Cr;
s2: the glass matrix raw material which is mixed and ground uniformly is insulated for 0.5 to 6 hours at the temperature of 1450 and 1650 ℃;
s3: taking out and then eliminating stress to obtain a glass substrate;
s4: and carrying out crystallization heat treatment on the glass substrate for 0.15-5 h to obtain near-infrared fluorescent glass ceramic, and crushing the near-infrared fluorescent glass ceramic to obtain the near-infrared fluorescent powder.
5. The method as claimed in claim 4, wherein the step S2 comprises charging the uniformly mixed and ground glass substrate raw material into a crucible, placing the crucible into a tube furnace filled with a reducing atmosphere, maintaining the temperature at 1450-.
6. The method of claim 4, wherein the step S2 is carried out by charging the glass substrate raw material mixed and ground uniformly into a high temperature box furnace and placing the furnace in air; preserving the heat at 1450 and 1650 ℃ for 0.5 to 6 hours to obtain a green glass substrate in step S3; and S4, putting the green glass substrate into a high-temperature box furnace in the air for crystallization heat treatment for 0.15-5 h.
7. The method of claim 4, wherein the step S3 of eliminating stress comprises: and pouring the heat-insulated product into a graphite mold, or naturally cooling the heat-insulated product to 650-800 ℃ and insulating for 3-10 h.
8. The method for preparing a near-infrared phosphor of claim 4, wherein the molar ratio of the Al element, the Si element, the Cr element and the A element in the glass matrix raw material is 5 to 50: 40-80: 0.001-20: 1-70.
9. the method of claim 4, wherein the glass-matrix raw material further comprises a simple substance or a compound containing Eu element; the visible light-near infrared fluorescent glass ceramic is obtained in the step S4, and the visible light-near infrared fluorescent glass ceramic is crushed to obtain visible light-near infrared fluorescent powder;
the molar ratio of Al element, Si element, Cr element, A element and Eu element in the glass matrix raw material is as follows: 5-50: 40-80: 0.001-20: 1-70: 0.001-20.
10. a near-infrared LED device comprising the near-infrared phosphor of any one of claims 1 to 3, comprising an LED chip on which the near-infrared phosphor of any one of claims 1 to 3 is coated; the light-emitting wavelength of the LED chip is 250-750 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210311646.6A CN114672306A (en) | 2022-03-28 | 2022-03-28 | Near-infrared fluorescent powder, preparation method and LED device formed by same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210311646.6A CN114672306A (en) | 2022-03-28 | 2022-03-28 | Near-infrared fluorescent powder, preparation method and LED device formed by same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114672306A true CN114672306A (en) | 2022-06-28 |
Family
ID=82075796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210311646.6A Pending CN114672306A (en) | 2022-03-28 | 2022-03-28 | Near-infrared fluorescent powder, preparation method and LED device formed by same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114672306A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116376546A (en) * | 2023-03-15 | 2023-07-04 | 有研稀土新材料股份有限公司 | Near infrared fluorescent powder and optical device containing same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110857389A (en) * | 2018-08-23 | 2020-03-03 | 有研稀土新材料股份有限公司 | Near-infrared fluorescent powder and light-emitting device containing same |
| CN112194376A (en) * | 2020-09-29 | 2021-01-08 | 华南理工大学 | Red light emitting glass ceramic, preparation method thereof and LED/LD light emitting device |
| CN113308242A (en) * | 2021-05-26 | 2021-08-27 | 江西理工大学 | Novel Cr3+Doped broadband near-infrared fluorescent powder and light source made of same |
-
2022
- 2022-03-28 CN CN202210311646.6A patent/CN114672306A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110857389A (en) * | 2018-08-23 | 2020-03-03 | 有研稀土新材料股份有限公司 | Near-infrared fluorescent powder and light-emitting device containing same |
| CN112194376A (en) * | 2020-09-29 | 2021-01-08 | 华南理工大学 | Red light emitting glass ceramic, preparation method thereof and LED/LD light emitting device |
| CN113308242A (en) * | 2021-05-26 | 2021-08-27 | 江西理工大学 | Novel Cr3+Doped broadband near-infrared fluorescent powder and light source made of same |
Non-Patent Citations (1)
| Title |
|---|
| 雷炳富等: "面向植物应用的Eu2+/Cr3+共掺近红外荧光粉合成及能量传递研究", 《中国稀土学会2021学术年会论文摘要集》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116376546A (en) * | 2023-03-15 | 2023-07-04 | 有研稀土新材料股份有限公司 | Near infrared fluorescent powder and optical device containing same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104087292B (en) | A kind of Mn 4+the red illuminating material adulterated, preparation method and novel illumination light source | |
| CN105018080B (en) | A kind of preparation method of specular removal fluorescent material | |
| Pawar et al. | Eu2O3 doped bright orange-red luminescent lithium alumino-borate glasses for solid state lighting | |
| Wang et al. | Low-concentration Ce3+-activated ScCaO (BO3) blue-cyan phosphor with high efficiency toward full-spectrum white LED applications | |
| CN105199728B (en) | Novel Eu＜3+＞ and Mn＜2+＞ co-doped tungstate red fluorescent material | |
| WO2018001369A1 (en) | Fluorescent powder, preparation method for fluorescent powder, and light emitting device having fluorescent powder | |
| Xu et al. | Preparation and luminescence properties of Dy3+ doped BaO-Al2O3-SiO2 glass ceramics | |
| Zhao et al. | Synthesis and luminescence properties of color-tunable Ce, Mn co-doped LuAG transparent ceramics by sintering under atmospheric pressure | |
| CN114133930B (en) | Warm white garnet type fluorescent glass ceramic and preparation method thereof | |
| CN105349147A (en) | Ultraviolet-to-blue light excited phosphate-based red fluorescent powder and preparation method thereof | |
| Zhao et al. | Tuning emission color of Eu2+-activated phosphor through phase segregation | |
| CN114672306A (en) | Near-infrared fluorescent powder, preparation method and LED device formed by same | |
| WO2016127843A1 (en) | Fluorescent material used for solid light source, manufacturing method therefor and composition containing same | |
| Jiang et al. | Mn4+/Zn2+: YAG glass ceramic for light emitting devices | |
| CN110003908A (en) | White light LEDs silicate red fluorescent powder and preparation method and White LED light-emitting device | |
| CN102906043B (en) | White light emitting glass-ceramic and production method thereof | |
| CN111607397B (en) | Eu (Eu) 2+ -Eu 3+ Co-doped silicate fluorescent powder and preparation method and application thereof | |
| Zhang et al. | A single Mn2+ ions activated fluosilicate glass with continuously tunable broadband emission from 475 nm to 800 nm | |
| CN110240900B (en) | Eu (Eu)2+Doped narrow-band green luminescent material, preparation method and illumination and display light source | |
| CN111099826A (en) | Blue light excited yellow-green full-spectrum fluorescent glass and preparation method thereof | |
| CN101838535A (en) | Rare earth fluorescent powder and preparation method thereof | |
| CN109370588B (en) | Nitride fluorescent powder for semiconductor luminescence, preparation method thereof and luminescent device | |
| CN102381841B (en) | Yellow green luminescent glass ceramic material and preparation method thereof | |
| WO2015098814A1 (en) | Phosphor and light emitting device | |
| CN107163934B (en) | Quadrivalent manganese ion doped fluorine aluminum oxide lithium red fluorescent powder and preparation method 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220628 |
|
| RJ01 | Rejection of invention patent application after publication |