CN112126426A - Aluminum nitride fluorescent material, preparation method and application thereof, and light-emitting device - Google Patents
Aluminum nitride fluorescent material, preparation method and application thereof, and light-emitting device Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 18
- 230000005284 excitation Effects 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 17
- 150000004767 nitrides Chemical class 0.000 claims description 13
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- 229910052788 barium Inorganic materials 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052712 strontium Inorganic materials 0.000 claims description 10
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- 239000001301 oxygen Substances 0.000 claims description 9
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- 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
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 229910052772 Samarium Inorganic materials 0.000 claims description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 7
- 230000003595 spectral effect Effects 0.000 description 7
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- 238000001228 spectrum Methods 0.000 description 6
- 229910052582 BN Inorganic materials 0.000 description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229930002868 chlorophyll a Natural products 0.000 description 2
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 2
- 229930002869 chlorophyll b Natural products 0.000 description 2
- NSMUHPMZFPKNMZ-VBYMZDBQSA-M chlorophyll b Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C=O)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 NSMUHPMZFPKNMZ-VBYMZDBQSA-M 0.000 description 2
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- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 1
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- 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
- C09K11/0883—Arsenides; Nitrides; Phosphides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G7/00—Botany in general
- A01G7/04—Electric or magnetic or acoustic treatment of plants for promoting growth
- A01G7/045—Electric or magnetic or acoustic treatment of plants for promoting growth with electric lighting
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- 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
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
- C09K11/7721—Aluminates
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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Abstract
The invention discloses an aluminum nitride fluorescent material, a preparation method and application thereof and a light-emitting device, belonging to the fields of lighting technology, display and photoelectron; the fluorescent material has the excitation wavelength range of 320-450 nm, and has the advantages of high luminous efficiency, complete crystallization, stable chemical performance, simple preparation method, no pollution, easy operation and low cost.
Description
Technical Field
The invention belongs to the fields of lighting technology, display and photoelectron, and particularly relates to an aluminum nitride fluorescent material, a preparation method and application thereof, and a light-emitting device.
Background
White light LED is a new green energy-saving solid-state electric light source which is rapidly developed in recent years. With the development of LED (light Emitting diode) technology, 1996 japanese incorporated by japan proposed white light LEDs. The white light LED has the advantages of energy conservation, no pollution (no mercury and no toxicity), long service life (about 10 ten thousand hours), high power, low light decay, high light efficiency (50-200lm/W), no stroboflash, quick response (microsecond level), soft and comfortable light emission, low working voltage, small volume, all solid state, low heat productivity, shock resistance, strong designability, easy connection with a solar cell by using low voltage and the like. And the vigorous development of the white light LED technology is an effective way for energy conservation and environmental protection. In recent years, with the development of new luminescent materials, white light LED technology has been widely focused and emphasized by countries and regions such as the united states, japan, and the european union as an important strategic technology, and has become one of the most intense areas of global scientific and technological competition.
Currently, in the prior art, two approaches are mainly used to realize white LEDs: firstly, combining three LEDs of red, green and blue to generate white light; and secondly, exciting a corresponding fluorescent material through an ultraviolet chip or a blue light chip to realize white light. The second method is superior to the first method in view of practicality and low cost commercialization. Therefore, the synthesis of fluorescent materials with good luminescent properties is the key to the realization of white LEDs. However, the prior art has certain limitations due to the limitation of fluorescent materials.
Nitride matrix materials are a novel matrix material with excellent physicochemical properties and light-emitting properties discovered in recent years, and most covalent bond nitrides are insulators or semiconductors and have larger bandwidth. Further, covalent bonding of the covalent-bond nitride is strong, and thus a strong electron cloud expansion (nephelacytic) effect may be generated, which may result in a decrease in excited-state energy of the 5d electron of the dopant ion. Has unique stable, firm and diversified crystal structures and has proper lattice positions occupied by activator atoms, so that the material is an ideal host material of a luminescent material. The nitrogen (oxide) compound fluorescent powder has high light conversion efficiency and light color stability, is insensitive to the change of temperature and driving current, and the color drift of the packaged device is very small. For example, Eu2+、Ce3+The doped nitrogen (oxide) phosphor emits light by occupying a matrixRare earth activators of cation sites in crystals under excitation light with 4f65d→4f 7The transition effects fluorescence emission. Due to the diversity of the nitrogen (oxide) material system and N3-The fluorescent material has stronger covalency and good spectrum cutting performance. The crystal field structure can be changed through different ion substitution, rare earth ion energy level splitting of different degrees is formed, and the adjustment of the position of emitted light can be realized.
The aluminum nitride luminescent materials developed recently have excellent luminescent properties and chemical stability, and have attracted the attention of researchers. For example, a red luminescent material SrLiAl is reported in Nature Materials 2014,13(9),891-8963N4:Eu2+Due to its narrow emission bandwidth (FWHM 1180 cm)-150nm) and excellent color rendering properties (CRI)>90) And is considered to be a promising next-generation nitride phosphor. The silicon-free aluminum-based nitride can be prepared under mild conditions (1000-1300 ℃), energy is saved, and the product has a small particle size (2-5 micrometers) and excellent thermal stability.
For example, CN1311055C, CN102282235A and CN105368451A are mainly based on silicon aluminum nitride, and the synthesis conditions of this kind of nitride are harsh, and the requirements for preparation equipment due to high temperature and high pressure are relatively high. And most of the activator ions adopt Eu2+Ions. In addition, we also note that the red light absorption region of chlorophyll a and chlorophyll b in the plant is in the range of 600-690 nm. There is therefore a need for a lighting device having an emission in deep red and as broad a spectrum as possible to improve the efficient growth of living organisms. Therefore, it is desirable to provide a low-cost light-emitting device which is capable of emitting light with a wavelength in the range of 600 to 690nm at a lower cost.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems in the prior art, the invention provides an aluminum nitride fluorescent material, a preparation method, application and a light-emitting device, and provides a fluorescent material which has high light-emitting efficiency and can be effectively excited by ultraviolet, purple light or blue light to emit deep red light of 550-800 nm and a preparation method thereof.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
A fluorescent material is excited to emit 550-800 nm deep red light by light with a wavelength of 320-450 nm.
Preferably, the chemical composition general formula of the fluorescent material is Ma-eAlbNcOd:Re(ii) a Wherein M is at least one element of Ca, Mg, Sr and Ba; al is aluminum element; n is nitrogen element; o is oxygen element; r is at least one element selected from Ce, Nd, Dy, Pr, Sm, Yb and Mn; a. b, c, d and e are molar coefficients, a is more than or equal to 2 and less than or equal to 3, b is 3, c is more than or equal to 4 and less than or equal to 5, d is more than or equal to 0 and less than or equal to 1, and e is more than or equal to 0.001 and less than or equal to 1.
In the existing fluorescent material, silicon-aluminum nitride is basically taken as a main material, the synthesis conditions of the nitride are harsh, and the requirements on preparation equipment due to high temperature and high pressure are relatively high. And most of the activator ions adopt Eu2+Ions. In general, Ce is affected by the cleavage of the 5d level under the action of a crystal field and the electron cloud diffusion effect (nephelacytic effect)3+Activated phosphors, whose luminescence is strongly dependent on the host lattice, can emit in the entire ultraviolet to red region of the spectrum. However, to date, Ce3+Activated aluminum nitride red or deep red phosphors have been very difficult and are now overcome by the present invention.
Preferably, M is one or more of Ca, Mg, Sr and Ba, a + e is 3, wherein a is more than or equal to 2 and less than or equal to 3, and e is more than or equal to 0.001 and less than or equal to 1.
Preferably, R is at least one or any of Ce, Nd, Dy, Pr, Sm, Yb and Mn, and at least Ce is selected.
Preferably, N is nitrogen, O is oxygen, and c + d is 5, wherein c is not less than 4 and not more than 5, and d is not less than 0 and not more than 1.
A preparation method of a fluorescent material comprises the following steps:
(1) taking simple substances, nitrides, borides or hydrides containing M and Al, nitrides, oxides and borides containing R as raw materials, adding fluxing agent, and grinding uniformly;
(2) the fluxing agent in the step (1) is fluoride or chloride containing M;
(3) calcining the mixture obtained in the step (2) in nitrogen at high temperature;
(4) cooling the calcined product obtained in the step (3), crushing and sieving to obtain the fluorescent material;
m is at least one element of Ca, Mg, Sr and Ba.
Preferably, the weight ratio of the fluxing agent in the step (1) is 0.001-12 Wt% of the total weight of the fluorescent material to be prepared.
Preferably, the high-temperature calcination in the step (2) is carried out one or more times; the high-temperature calcination temperature is 800-1300 ℃, and the calcination time is 1-15 hours.
The fluorescent material or the fluorescent material prepared by the preparation method is applied to luminescent materials or luminescent devices.
A light-emitting device comprising or employing the fluorescent material or excitation light source prepared by the preparation method as described above, wherein the light-emitting device emits light with a wavelength of 550 to 800 nm. The device is particularly suitable for application in agricultural planting.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
compared with silicon nitride, the aluminum nitride matrix material provided by the invention has the advantages of lower sintering temperature, smaller sintered powder particles, easily obtained raw materials, simple preparation process and low cost. And the physical and chemical properties are more stable, and the lattice site occupied by the rare earth ions can be better provided. The excitation spectrum peak position can be adjusted by changing the types of the alkaline earth metals in the M in the compound, and meanwhile, the emission peak position can also be changed, so that the output of different light-emitting wave bands is realized. When the oxygen-containing compound is not used in the raw materials, an oxygen-free aluminum nitride luminescent material can be obtained, and specific fluorescence is enhanced. The aluminum nitride material belongs to a high-temperature phase product, so that a luminescent material with higher crystallinity can be obtained by properly adding a cosolvent to improve the luminescent brightness.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of the fluorescent material of example 1 of the present invention.
FIG. 2 shows the excitation and emission spectra of the fluorescent material of example 1 of the present invention.
FIG. 3 is a schematic diagram of an LED structure using the fluorescent material of example 4;
in the figure: 1. a semiconductor light emitting chip; 2. a fluorescent material; 3. packaging materials; 4. a pin; 5. a cathode electrode; 6. a lead wire; 7. an anode electrode; 8. a light reflecting cup.
Fig. 4 is an emission spectrum of the red LED in example 4.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific examples, but the present invention is not limited to the following examples
A fluorescent material is excited to emit 550-800 nm deep red light by light with a wavelength of 320-450 nm.
The chemical composition general formula of the fluorescent material is Ma-eAlbNcOd:Re(ii) a Wherein M is at least one element of Ca, Mg, Sr and Ba; al is aluminum element; n is nitrogen element; o is oxygen element; r is at least one element selected from Ce, Nd, Dy, Pr, Sm, Yb and Mn; a. b, c, d and e are molar coefficients, a is more than or equal to 2 and less than or equal to 3, b is 3, c is more than or equal to 4 and less than or equal to 5, d is more than or equal to 0 and less than or equal to 1, and e is more than or equal to 0.001 and less than or equal to 1.
M is selected from one or more of Ca, Mg, Sr and Ba, a + e is 3, wherein a is more than or equal to 2 and less than or equal to 3, and e is more than or equal to 0.001 and less than or equal to 1.
R is at least one or any of Ce, Nd, Dy, Pr, Sm, Yb and Mn, and at least Ce is selected.
N is nitrogen element, O is oxygen element, c + d is 5, wherein c is more than or equal to 4 and less than or equal to 5, and d is more than or equal to 0 and less than or equal to 1.
A preparation method of a fluorescent material comprises the following steps:
(1) taking simple substances, nitrides, borides or hydrides containing M and Al, nitrides, oxides and borides containing R as raw materials, adding fluxing agent, and grinding uniformly;
(2) the fluxing agent in the step (1) is fluoride or chloride containing M;
(3) calcining the mixture obtained in the step (2) in nitrogen at high temperature;
(4) cooling the calcined product obtained in the step (3), crushing and sieving to obtain the fluorescent material;
m is at least one element of Ca, Mg, Sr and Ba.
The weight ratio of the fluxing agent in the step (1) is 0.001-12 Wt% of the total weight of the prepared fluorescent material.
The high-temperature calcination in the step (2) is carried out for one or more times; the high-temperature calcination temperature is 800-1300 ℃, and the calcination time is 1-15 hours.
A light-emitting device comprising or employing the fluorescent material or excitation light source prepared by the preparation method as described above, wherein the light-emitting device emits light with a wavelength of 550 to 800 nm. The device is particularly suitable for application in agricultural planting. This is based on the particular focus of the invention on the rare earth ion Ce3+Doped M3Al3N5(M ═ Ca, Ba, Sr, Mg) based aluminum nitrides. The luminescent material is simple to prepare, and does not need high-temperature sintering at a temperature of more than 1500 ℃. The material can be effectively excited by an ultraviolet to blue light chip, the red-most emission wavelength can reach 690nm (peak wavelength), and the full-length half-height FWHM of the spectrum can reach 145nm (-3263 cm)-1) And the problem of low-cost agricultural light is solved.
The specific preparation process is exemplified as follows:
example 1: ca3-xAl3N5：CexPreparation of fluorescent materials
Weighing various raw materials Ca according to stoichiometric composition3N2，AlN，CeN，NH4F, wherein NH is weighed4The mass of F was measured to be 0.02% of the total mass. CeN, the weighed mole number is 0.005, 0.01, 0.015, 0.02, 0.04, namely the x value is 0, 0.005, 0.01, 0.015, 0.02, 0.04. The raw materials are fully ball-milled and uniformly mixed, then are put into a boron nitride crucible, are kept warm for 1 hour at 500 ℃ under the nitrogen atmosphere, are pressurized to 0.5MPa, are kept warm for 6 hours at 1300 ℃, and are cooled, crushed, sieved and classified to obtain the chemical composition Ca of the invention3-xAl3N5：CexThe fluorescent material of (1). Wherein Ca3-xAl3N5：CexThe excitation spectrum and the emission are shown in fig. 2, the maximum emission is at 674nm, and the width of the emission spectrum reaches 142 nm.
Example 2: ca2.98-xSrxAl3N5：Ce0.02Preparation of fluorescent materials
Weighing various raw materials Ca according to stoichiometric composition3N2，Sr3N2，AlN，CeN，Dy2O3，NH4F, wherein NH is weighed4The mass of F was measured to be 0.02% of the total mass. CeN, the weighed mole number is 0.02, Sr3N2The mole number is 0.1, 0.2, 0.5, 0.7 and 0.99, namely the x value is 0.3, 0.6, 1.5, 2.1 and 2.98. The raw materials are fully ball-milled and uniformly mixed, then are put into a boron nitride crucible, are kept warm for 1 hour at 500 ℃ under the nitrogen atmosphere, are pressurized to 0.5MPa, are kept warm for 6 hours at 1300 ℃, and are cooled, crushed, sieved and classified to obtain the chemical composition Ca of the invention2.98-xSrxAl3N5：Ce0.02The fluorescent material of (1). The obtained crystal structure X-ray diffraction pattern, excitation and emission spectral characteristics were substantially identical to those of example 1 except that the light emission intensity was weakened.
Example 3: ca2.98Al3N5：Ce0.02Dy0.01Preparation of fluorescent materials
Weighing various raw materials Ca according to stoichiometric composition3N2，AlN，CeN，Dy2O3，NH4F, wherein NH is weighed4The mass of F was measured to be 0.02% of the total mass. CeN, 0.02 mol number of Dy2O3The molar number of the compound (2) is 0.01. The raw materials are fully ball-milled and uniformly mixed, then are put into a boron nitride crucible, are kept warm for 1 hour at 500 ℃ under the nitrogen atmosphere, are pressurized to 0.5MPa, are kept warm for 6 hours at 1300 ℃, and are cooled, crushed, sieved and classified to obtain the chemical composition Ca of the invention2.98Al3N5：Ce0.02Dy0.01The fluorescent material of (1). The obtained crystal structure X-ray diffraction pattern, excitation and emission spectral characteristics were substantially identical to those of example 1, except that the luminescence intensity was slightly increased.
Example 4: ca2.98Al3N4.98O0.02：Ce0.02Preparation of fluorescent materials
Weighing various raw materials Ca according to stoichiometric composition3N2，AlN，CeO，NH4F, wherein NH is weighed4The mass of F was measured to be 0.02% of the total mass. The molar number of CeO weighed was 0.02. The raw materials are fully ball-milled and uniformly mixed, then are put into a boron nitride crucible, are kept warm for 1 hour at 500 ℃ under the nitrogen atmosphere, are pressurized to 0.5MPa, are kept warm for 6 hours at 1300 ℃, and are cooled, crushed, sieved and classified to obtain the chemical composition Ca of the invention2.98Al3N4.98O0.02：Ce0.02The fluorescent material of (1). The obtained crystal structure X-ray diffraction pattern, excitation and emission spectral characteristics were substantially identical to those of example 1 except that the luminescence intensity was decreased by the introduction of oxygen.
Example 5: ca2.98Al3N4.965O0.035：Ce0.02Dy0.01Preparation of fluorescent materials
Weighing various raw materials Ca according to stoichiometric composition3N2，AlN，CeO，Dy2O3，NH4F, wherein NH is weighed4The mass of F was measured to be 0.02% of the total mass. CeO was weighed in a molar amount of 0.02，Dy2O3The molar number of the compound (1) was 0.005. The raw materials are fully ball-milled and uniformly mixed, then are put into a boron nitride crucible, are kept warm for 1 hour at 500 ℃ under the nitrogen atmosphere, are pressurized to 0.5MPa, are kept warm for 6 hours at 1300 ℃, and are cooled, crushed, sieved and classified to obtain the chemical composition Ca of the invention2.98Al3N4.965O0.035：Ce0.02Dy0.01The fluorescent material of (1). The obtained crystal structure X-ray diffraction pattern, excitation and emission spectral characteristics were substantially identical to those of example 1 except that the luminescence intensity was decreased by the introduction of oxygen.
Example 6-example 16
According to the main raw materials in table 1, the preparation process was the same as that of example 1, and a fluorescent material having a chemical structural formula shown in table 2 was synthesized. And gives the emission spectral intensity of these materials at 420nm excitation. The crystal structure and spectral characteristics thereof were substantially in accordance with example 1.
Table 1 starting materials for examples 6-16
| Examples | Main |
| 6 | Ca3N2，Ba3N2，AlN，CeN，NH4F |
| 7 | Ca3N2，Mg3N2，AlN，CeN，NH4F |
| 8 | Ca3N2，AlN，CeO，Nd2O3，NH4Cl |
| 9 | Ca3N2，AlN，CeO，Pr6O11，NH4Cl |
| 10 | Ca3N2，AlN，CeN，SmO3，NH4Cl |
| 11 | Ca3N2，AlN，CeO，Yb2O3，NH4F |
| 12 | Ca3N2，AlN，CeO，Mn3O4，NH4Cl |
| 13 | Sr3N2，Mg3N2，AlN，CeN，NH4F |
| 14 | CaB6，Sr3N2，AlN，CeN，NH4F |
| 15 | CaB6，Sr3N2，AlN，CeN，NdB6，NH4F |
| 16 | Ca3N2，Mg3N2，AlN，CeB6，NH4F |
TABLE 2 chemical formulae of examples 6 to 16 and their luminescence characteristics (excitation wavelength 340nm)
The spectral characteristics of the fluorescent material of the above chemical structural formula are substantially the same as those of example 1.
The present invention also relates to an illumination device using any one or more of the fluorescent materials of the present invention, and more particularly, to a red LED packaged by using a semiconductor LED having an emission main peak in the range of 320 to 450nm of a light emitting element used as an excitation light source. In the present invention, the packaging manner may be as shown in fig. 4, which is a manner that the fluorescent material is in direct contact with a single semiconductor light emitting chip, and the fluorescent material is uniformly coated on the semiconductor light emitting chip and in the reflective cup after being mixed with the transparent resin.
The following description will be given by way of specific examples.
Example 17: fabrication of red LED light emitting devices
The red LED light emitting device was fabricated by uniformly mixing the red phosphor material described in example 1 with an epoxy resin at a mass ratio of 0.6:1, and coating the mixture on a semiconductor light emitting chip. The red LED has a structure as described in fig. 3. FIG. 4 is an emission spectrum of a red LED, and when 398-400 nm luminous excitation light is adopted, the red LED has higher emission efficiency and a wider spectrum compared with the conventional red phosphor.
In conclusion, the fluorescent material provided by the invention has high luminous efficiency, complete crystallization and stable chemical performance, and the red light LED device provided by the invention has a wide spectrum range and a longer luminous wavelength and covers the red light absorption range of plant chlorophyll a and b. Therefore, the LED lighting lamp can be popularized and applied to the field of LED lighting for plant growth.
The examples of the present invention are only for describing the preferred embodiments of the present invention, and do not limit the concept and scope of the present invention, and the engineers in the art should make various modifications and improvements to the technical solution of the present invention without departing from the design concept of the present invention, for example, applying the luminescent material or the light emitting device to other application ranges requiring 550 to 800nm light, should fall into the protection scope of the present invention.
Claims (10)
1. A fluorescent material is excited to emit 550-800 nm deep red light by light with a wavelength of 320-450 nm.
2. A fluorescent material according to claim 1, wherein: the chemical composition general formula of the fluorescent material is Ma-eAlbNcOd:Re(ii) a Wherein M is at least one element of Ca, Mg, Sr and Ba; al is aluminum element; n is nitrogen element; o is oxygen element; r is at least one element selected from Ce, Nd, Dy, Pr, Sm, Yb and Mn; a. b, c, d and e are molar coefficients, a is more than or equal to 2 and less than or equal to 3, b is 3, c is more than or equal to 4 and less than or equal to 5, d is more than or equal to 0 and less than or equal to 1, and e is more than or equal to 0.001 and less than or equal to 1.
3. A fluorescent material according to claim 2, wherein: m is selected from one or more of Ca, Mg, Sr and Ba, a + e is 3, wherein a is more than or equal to 2 and less than or equal to 3, and e is more than or equal to 0.001 and less than or equal to 1.
4. A fluorescent material according to claim 2, wherein: r is at least one or any of Ce, Nd, Dy, Pr, Sm, Yb and Mn, and at least Ce is selected.
5. A fluorescent material according to claim 2, wherein: n is nitrogen element, O is oxygen element, c + d is 5, wherein c is more than or equal to 4 and less than or equal to 5, and d is more than or equal to 0 and less than or equal to 1.
6. A preparation method of a fluorescent material comprises the following steps:
(1) taking simple substances, nitrides, borides or hydrides containing M and Al, nitrides, oxides and borides containing R as raw materials, adding fluxing agent, and grinding uniformly;
(2) the fluxing agent in the step (1) is fluoride or chloride containing M;
(3) calcining the mixture obtained in the step (2) in nitrogen at high temperature;
(4) cooling the calcined product obtained in the step (3), crushing and sieving to obtain the fluorescent material;
m is at least one element of Ca, Mg, Sr and Ba.
7. The method for preparing a fluorescent material according to claim 6, wherein: the weight ratio of the fluxing agent in the step (1) is 0.001-12 Wt% of the total weight of the prepared fluorescent material.
8. The method for preparing a fluorescent material according to claim 6, wherein: the high-temperature calcination in the step (2) is carried out for one or more times; the high-temperature calcination temperature is 800-1300 ℃, and the calcination time is 1-15 hours.
9. Use of the fluorescent material as claimed in claims 1 to 5 or the fluorescent material prepared in claims 6 to 9 in a luminescent material or a luminescent device or in agricultural planting.
10. A light emitting device, characterized in that: a light emitting device comprising or using the fluorescent material according to any one of claims 1 to 5 or the fluorescent material or excitation light source prepared according to any one of claims 6 to 9, wherein the light emitting device emits light with a wavelength of from 550 to 800nm and a wavelength of from 320 to 450 nm.
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|---|---|---|---|---|
| US3531245A (en) * | 1968-04-01 | 1970-09-29 | Du Pont | Magnesium-aluminum nitrides |
| CN104087293A (en) * | 2014-07-23 | 2014-10-08 | 中国科学院上海硅酸盐研究所 | Red fluorophor as well as carbothermal reduction nitridation preparation method and application of red fluorophor |
| CN109973842A (en) * | 2019-03-25 | 2019-07-05 | 昆明理工大学 | A kind of long afterglow type LED plant lamp |
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| US3531245A (en) * | 1968-04-01 | 1970-09-29 | Du Pont | Magnesium-aluminum nitrides |
| CN104087293A (en) * | 2014-07-23 | 2014-10-08 | 中国科学院上海硅酸盐研究所 | Red fluorophor as well as carbothermal reduction nitridation preparation method and application of red fluorophor |
| CN109973842A (en) * | 2019-03-25 | 2019-07-05 | 昆明理工大学 | A kind of long afterglow type LED plant lamp |
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