CN114316961A - Nitrogen oxide luminescent particle, preparation method and luminescent device - Google Patents
Nitrogen oxide luminescent particle, preparation method and luminescent device Download PDFInfo
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 282
- 239000002245 particle Substances 0.000 title claims abstract description 197
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 76
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 48
- 239000001301 oxygen Substances 0.000 claims abstract description 47
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 43
- 150000004767 nitrides Chemical group 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000006104 solid solution Substances 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 94
- 239000012298 atmosphere Substances 0.000 claims description 61
- 239000002994 raw material Substances 0.000 claims description 45
- 239000007789 gas Substances 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 35
- 239000000047 product Substances 0.000 claims description 33
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 31
- 238000005303 weighing Methods 0.000 claims description 29
- 238000007873 sieving Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 19
- PWKWDCOTNGQLID-UHFFFAOYSA-N [N].[Ar] Chemical compound [N].[Ar] PWKWDCOTNGQLID-UHFFFAOYSA-N 0.000 claims description 19
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims description 19
- 239000012792 core layer Substances 0.000 claims description 13
- 239000011265 semifinished product Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- 238000009877 rendering Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims 1
- 230000003712 anti-aging effect Effects 0.000 abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 34
- 229910052750 molybdenum Inorganic materials 0.000 description 34
- 239000011733 molybdenum Substances 0.000 description 34
- 238000010438 heat treatment Methods 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 229910052581 Si3N4 Inorganic materials 0.000 description 23
- 238000003756 stirring Methods 0.000 description 23
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 238000011068 loading method Methods 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 20
- 238000000967 suction filtration Methods 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 14
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- 238000000295 emission spectrum Methods 0.000 description 11
- 238000000695 excitation spectrum Methods 0.000 description 10
- 238000010791 quenching Methods 0.000 description 10
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- 230000001976 improved effect Effects 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- -1 nitrogen ions Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
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- 102100032047 Alsin Human genes 0.000 description 3
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- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
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- 239000004065 semiconductor Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910004647 CaMoO4 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910016644 EuCl3 Inorganic materials 0.000 description 1
- 229910016653 EuF3 Inorganic materials 0.000 description 1
- 229910005987 Ge3N4 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910003443 lutetium oxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium (III) oxide Inorganic materials [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- 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
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- 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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- 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
- C09K11/7734—Aluminates
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7792—Aluminates
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- 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
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Abstract
The application discloses a nitrogen oxide luminescent particle, a preparation method thereof, a nitrogen oxide luminous body and a luminescent device, and belongs to the technical field of fluorescent materials. The structure of the nitrogen oxide luminescent particle comprises a crystal nucleus layer and a crystal nucleus outer layer, wherein the main body of the crystal nucleus layer is a nitride luminescent crystal or an oxygen-containing solid solution thereof, and the main body of the crystal nucleus outer layer is an oxide material. The nitrogen oxide luminescent particles have the advantages of good chemical stability, good anti-aging light decay performance, high luminous efficiency and the like, and are suitable for various luminescent devices; the manufacturing method is simple and reliable, and is suitable for industrial mass production and manufacturing.
Description
The application is divisional application with application number 201610069857.8, application date 2016.01.29, and title of the invention is an oxynitride luminescent particle and its preparation method, oxynitride luminescent body and luminescent device.
Technical Field
The invention belongs to the technical field of LED (light emitting diode) fluorophors and luminescent devices, and particularly relates to a nitrogen oxide luminescent particle capable of being effectively excited by ultraviolet light, purple light or blue light, a preparation method thereof and a luminescent device.
Background
Semiconductor lighting electric light sources typified by Light Emitting Diodes (LEDs) are nowadays known as fourth generation lighting electric light sources following incandescent, fluorescent and energy saving lamps, and are called "green light sources in the 21 st century".
With the semiconductor illumination entering the field of general illumination, the rapid development of white light LEDs with high color rendering, aging resistance and low light attenuation is imminent. The existing method for manufacturing the white light LED mainly comprises the following steps: firstly, yellow fluorescent powder (YAG) is coated on a blue LED chip to realize white light emission, but the YAG fluorescent powder has the defects of higher coloring temperature and lower color rendering index, and can not meet the requirements of semiconductor illumination; although the emission spectrum of the YAG phosphor is very wide, the emission intensity in the red light region is very weak, which causes a phenomenon of lack of red light after mixing with a blue LED chip, thereby affecting the correlated color temperature and color rendering index of the white LED. Secondly, the green and red phosphors are coated on the blue LED chip to solve the above problems, however, the red phosphor also has many problems, such as CaS: Eu2+Large light decay, poor chemical stability, CaMoO4:Eu2+Narrow excitation range, Y2O3:Eu3+And Y2O2S:Eu3+Low conversion efficiency of absorbing weak energy in blue region, M2Si5N8:Eu2+The anti-light-decay performance is poor, and the LED chip can not be perfectly matched with the anti-light-decay performance, which are bottlenecks that restrict the technical development of the white light LED. Third, reference is made to CaAlSiN3The nitride fluorescent powder with the crystal structure has better comprehensive performance than the YAG fluorescent powderAnd common red phosphors, but there are also the following significant drawbacks: firstly, because the internal rules of component diffusion, nucleation, preferred growth orientation and primary grain size in the fluorescent powder synthesis process are not completely researched, the luminous efficiency of the fluorescent powder is low, and the luminous efficiency needs to be further improved; secondly, the fluorescent powder can be degraded under the combined action of three factors of high optical density, high temperature and high humidity, the light effect of the whole lamp is directly reduced, and particularly, the color coordinate is greatly drifted, so the durability of the fluorescent powder can not completely meet the requirement of common illumination.
Chinese patent 200480040967.7 discloses a phosphor comprising an inorganic compound having a chemical structure with CaAlSiN3The same crystal structure. This proposal is based on a phosphor using an inorganic compound containing a nitride and oxygen as a matrix, and particularly emphasizes that since the emission luminance decreases as the addition amount of oxygen increases, it is preferable to make up in a range where the addition amount of oxygen is small, and in order to obtain better high-temperature durability, the number of atoms of O and N contained in the inorganic compound satisfies 0.5. ltoreq. N/(N + O). ltoreq.1 (see paragraph 161, paragraph 271 of the specification). This proposal has a significant disadvantage in that the range of the oxygen content is limited in order to maintain the phosphor light emission luminance, so that the durability of the phosphor is rather lowered.
Published in the journal of electrochemistry in 2008 "Synthetic methods and luminescence properties of SrxCa1-xAlSiN3:Eu2+The use of alloying methods for the preparation of (Sr, Ca) AlSiN is proposed in the text given in mixed nitride phosphors3Compared with the fluorescent powder synthesized by adopting nitride raw materials, the red fluorescent powder has lower oxygen content, so that the (Sr, Ca) AlSiN is prepared by the alloy method3The red fluorescent powder has better consistency and phase purity and better stability. However, the method has obvious defects because the (Sr, Ca) AlSiN is prepared by adopting an alloy method3The red phosphor emphasizes that higher consistency and phase purity are achieved by controlling lower oxygen content, so that the durability of the phosphor is obviously reduced, the practicability is poor, and the application of the phosphor is limited.
Journal of Ma 2015"Reduced thermal degradation of the red-emitting Sr published by tertiary Chemistry C2Si5N8:Eu2+Phor via thermal treatment in nitrogen "for Sr2Si5N8:Eu2+The thermal degradation mechanism of Eu is considered to be that Eu is prevented from forming an oxide protective film on the surface of the phosphor by baking2+Improves the thermal deterioration property, and thus it is presumed that Sr can be improved2Si5N8:Eu2+The application performance in the LED is not supported by experimental data, and the Sr is not solved fundamentally2Si5N8:Eu2+Long-term aging problems. In fact, in this system, due to Sr2Si5N8:Eu2+The stability of the fluorescent powder is poor, and the surface crystal structure is damaged in the roasting process, so that the luminous intensity of the fluorescent powder is obviously reduced, and the fluorescent powder has no practical application value.
In summary, in the prior art, there is a contradiction in solving the problems of the nitride phosphor powder in terms of anti-aging light decay and improving the phosphor powder luminous efficiency, and the basic rule is to improve the phosphor powder anti-aging light decay performance at the cost of reducing the phosphor powder luminous efficiency or improve the phosphor powder luminous efficiency at the cost of reducing the phosphor powder anti-aging light decay performance, and at present, there is no comprehensive solution scheme for improving the phosphor powder anti-aging light decay performance without reducing the phosphor powder luminous efficiency. Therefore, how to overcome the deficiencies of the prior art has become a major problem to be solved in the technical field of LED phosphors and light emitting devices.
Disclosure of Invention
The invention aims to provide the nitrogen oxide luminescent particles, the preparation method thereof, the nitrogen oxide luminophor and the luminescent device for overcoming the defects in the prior art, and the nitrogen oxide luminescent particles have the advantages of good chemical stability, good anti-aging light decay performance, high luminous efficiency and the like, and are suitable for various luminescent devices; the manufacturing method is simple and reliable, and is suitable for industrial mass production and manufacturing.
According to the inventionAn oxynitride luminescent particle comprises a crystal nucleus layer and a crystal nucleus outer layer in the structure, wherein the main body of the crystal nucleus layer is a nitride luminescent crystal or an oxygen-containing solid solution thereof, and the main body of the crystal nucleus outer layer is an oxynitride material or an oxide material; the chemical general formula of the nitride luminescent crystal or the oxygen-containing solid solution thereof is Mm- m1Aa1Bb1Oo1Nn1:Rm1The chemical general formula of the oxynitride material or the oxide material is Mm-m2Aa2Bb2Oo2Nn2:Rm2(ii) a The thickness range of the outer layer of the core is within 500nm, and the inner side of the outer layer of the core of the nitrogen oxide luminescent particle is a crystal core layer.
Optionally, the content of the nitride luminescent crystal or its oxygen-containing solid solution in the core layer is not less than 90%, and the content of the oxynitride material or the oxide material in the core outer layer is not less than 50%.
Optionally, the core outer layer has a moderate amount of oxygen content therein from the outer surface to the inner surface with a tunable height distribution.
Optionally, the core layer further includes an oxynitride luminescent crystal, and the core outer layer further includes a nitride material.
Optionally, the red light with the peak wavelength of 600-670nm is emitted after the excitation within the range of the excitation light wavelength of 300-500 nm.
The invention provides an oxynitride luminescent body, which comprises a mixture of the oxynitride luminescent particles and other crystalline grains or amorphous particles, wherein the proportion of the oxynitride luminescent particles in the mixture is not less than 50 wt%.
The invention provides a preparation method 1 of nitrogen oxide luminescent particles, which comprises the following basic steps:
step 1: m, A, B, R nitride, oxide or halide is used as raw material and has the chemical formula Mm-m1Aa1Bb1OO1Nn1:Rm1Weighing the required raw materials according to the stoichiometric ratio of cations in the composition;
step 2: uniformly mixing the raw materials weighed in the step 1 in a nitrogen atmosphere to form a mixture;
and step 3: carrying out high-temperature roasting on the mixture obtained in the step 2 in a roasting atmosphere, then cooling to a preset temperature, and introducing nitrogen-oxygen mixed gas or air for carrying out low-temperature roasting to obtain a nitrogen oxide luminescent particle semi-finished product;
and 4, step 4: and (4) carrying out post-treatment on the nitrogen oxide luminous particle semi-finished product obtained in the step (3) to obtain a nitrogen oxide luminous particle finished product.
The invention provides a preparation method 2 of nitrogen oxide luminescent particles, which comprises the following basic steps:
step 1: m, A, B, R nitride, oxide or halide is used as raw material and has the chemical formula Mm-m1Aa1Bb1OO1Nn1:Rm1Weighing the required raw materials according to the stoichiometric ratio of the formed medium cations;
step 2: uniformly mixing the raw materials weighed in the step 1 in a nitrogen atmosphere to form a mixture;
and step 3: carrying out high-temperature roasting on the mixture obtained in the step 2 in roasting atmosphere to obtain a nitrogen oxide luminescent particle semi-finished product;
and 4, step 4: carrying out post-treatment on the nitrogen oxide luminescent particle semi-finished product obtained in the step 3;
and 5: and (4) roasting the nitrogen oxide luminescent particle semi-finished product obtained after the post-treatment in the step (4) at a low temperature in a nitrogen-oxygen mixed gas or air atmosphere to obtain a nitrogen oxide luminescent particle finished product.
The light-emitting device at least comprises an LED chip of ultraviolet light, purple light or blue light and fluorescent powder, wherein the fluorescent powder at least uses the nitrogen oxide light-emitting particles.
The light-emitting device at least comprises an ultraviolet light, purple light or blue light LED chip and fluorescent powder, wherein the fluorescent powder at least uses the nitrogen oxide light-emitting body.
The realization principle of the invention is as follows: the invention emphasizes the structural design of the oxynitride luminescent particle, the oxynitride luminescent particle has a structure with a crystal nucleus layer and a crystal nucleus outer layer, and the crystal nucleus layer and the crystal nucleus outer layer are cooperated to form a whole body connected by chemical bonds. The original atomic composition of the mixture is kept in the crystal nucleus layer, which is beneficial to the efficient luminescence of the formed crystal nucleus; because a proper amount of oxygen exists in the nitrogen oxide material or the oxide material of the outer layer of the core, the oxygen content distribution in the outer layer of the core can be gradually increased from the inner surface to the outer surface of the outer layer of the core, and the distribution of the proper amount of oxygen content from the outer surface to the inner surface of the outer layer of the core can be adjusted according to the defect distribution in the crystal, so that the defect which is not beneficial to high-efficiency luminescence and is formed on the outer layer of the core can be effectively reduced, and the luminous efficiency of the whole particle is ensured to be obviously improved; compared with nitrogen ions, the nitrogen oxide luminescent particle has the advantages that the radius of the oxygen ions is small, the electronegativity is high, the binding force among the ions is stronger, and in the structure of the nitrogen oxide luminescent particle, due to the enrichment of oxygen ions on the outer layer of the core, the chemical and thermal stability of the outer layer of the core is improved, so that the crystal core layer of the luminescent particle is effectively protected and shielded, and the thermal stability and durability of the nitrogen oxide luminescent particle in an LED application environment can be effectively improved. Meanwhile, the crystal nucleus layer is subjected to the barrier effect of the nucleus outer layer, so that the stability of the luminescence center of the crystal nucleus layer is obviously improved, oxidation and hydrolysis are not easy to occur, and the luminous efficiency is obviously improved.
Compared with the prior art, the invention has the remarkable advantages that:
firstly, the chemical stability of the nitrogen oxide luminophor is good. According to the invention, a proper amount of oxygen is introduced into the outer layer of the core of the nitrogen oxide luminescent particle, so that the growth requirements of the substrate crystal of the nitrogen oxide luminescent particle from the nucleation to the molding and densification processes are met, and the crystal structure is firmer and more stable.
And secondly, the anti-aging light decay performance is good. The structure of the nitrogen oxide luminescent particle is divided into a crystal nucleus layer and a nucleus outer layer, and through the introduction of oxygen, oxygen ions with smaller radius than nitrogen ions can replace more nitrogen ions so as to enhance the binding force among the ions in the luminescent particle structure; meanwhile, the stability of the luminescence center of the crystal nucleus layer is obviously improved due to the barrier effect of the outer layer of the nucleus, so that the luminescent particles have extremely excellent ageing-resistant light decay resistance and high-temperature durability.
Thirdly, the luminous efficiency is high. The original atomic composition of the mixture is kept in the crystal nucleus layer, so that the formed crystal nucleus can efficiently emit light; because the nitrogen oxide material or the oxide material of the outer layer of the core has a proper amount of oxygen, the oxygen content distribution in the outer layer of the core can be gradually increased from the inner surface to the outer surface of the outer layer of the core, and the oxygen content distribution from the outer surface to the inner surface of the outer layer of the core can be adjusted according to the defect distribution in the crystal, so that the defect which is not beneficial to high-efficiency luminescence and is formed on the outer layer of the core can be effectively reduced, and the luminous efficiency of the whole particle is obviously improved.
Fourthly, the application range is wide. The nitrogen oxide luminescent particles of the present invention are suitable for manufacturing various light emitting devices.
Fifthly, the manufacturing method is simple and reliable. The manufacturing method of the invention is simple and easy to implement, and is suitable for industrial mass production and manufacturing.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic structural cross-sectional view of an oxynitride luminescent particle according to the present invention.
Fig. 2 is an emission spectrum of the oxynitride light-emitting particles of examples 1 to 3 of the present invention and comparative example 1.
Fig. 3 is a graph showing the excitation spectra of the oxynitride luminescent particles of examples 1 to 3 of the present invention and comparative example 1.
Fig. 4 is thermal quenching spectra of the oxynitride luminescent particles of examples 1 to 3 of the present invention and comparative example 1.
Fig. 5 is an emission spectrum of the oxynitride light-emitting particles of examples 4 to 7 of the present invention and comparative example 2.
Fig. 6 is an X-ray diffraction pattern of the oxynitride luminescent particles of examples 4 to 7 of the present invention and comparative example 2.
FIG. 7 is a scanning electron microscope photograph of oxynitride luminescent particles in example 8 of the present invention.
FIG. 8 is a scanning electron microscope photograph of oxynitride luminescent particles in comparative example 3 of the present invention.
FIG. 9 is a graph showing the excitation spectra of the oxynitride luminescent particles of examples 16 to 18 of the present invention and comparative example 5.
FIG. 10 is thermal quenching spectra of oxynitride luminescent particles of examples 16 to 18 of the present invention and comparative example 6.
Detailed Description
The following detailed description of embodiments of the invention is provided in connection with the accompanying drawings and examples.
With reference to fig. 1, the oxynitride luminescent particle provided by the present invention includes a core layer and an outer core layer, wherein a main body of the core layer is a nitride luminescent crystal or an oxygen-containing solid solution thereof, and a main body of the outer core layer is an oxynitride material or an oxide material; the chemical general formula of the nitride luminescent crystal or the oxygen-containing solid solution thereof is Mm- m1Aa1Bb1Oo1Nn1:Rm1The chemical general formula of the oxynitride material or the oxide material is Mm-m2Aa2Bb2Oo2Nn2:Rm2(ii) a The thickness range of the outer layer of the core is within 500nm, and the inner side of the outer layer of the core of the nitrogen oxide luminescent particle is a crystal core layer.
An oxynitride luminescent particle, wherein the content of nitride luminescent crystals or an oxygen-containing solid solution thereof in the core layer is not less than 90%, and the content of oxynitride material or oxide material in the core outer layer is not less than 50%.
The outer layer of the core has a proper amount of oxygen content with adjustable height distribution from the outer surface to the inner surface.
The oxygen content in the outer layer of the core is distributed in a structure which gradually increases from the inner surface to the outer surface.
The chemical formula Mm-m1Aa1Bb1Oo1Nn1:Rm1And Mm-m2Aa2Bb2Oo2Nn2:Rm2The M element is Mg, Ca, Sr, Ba, Zn, LiThe element A is at least one of B, Al, Ga and In, the element B is at least one of C, Si, Ge and Sn, R is at least one of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, wherein m is more than or equal to 0.5 and less than or equal to 1.5, m1 is more than or equal to 0.001 and less than or equal to 0.2, a1 is more than or equal to 0.5 and less than or equal to 1.5, B5 is more than or equal to 0.5 and less than or equal to 1.5, o1 is more than or equal to 0.5 and less than or equal to 3.5, m2 is more than or equal to 0.2, a2 is more than or equal to 0.5 and less than or equal to 1.5, B2 is more than or equal to 0.1 and less than or equal to 2 and less than or equal to 5, and n2 is more than or equal to 0 and less than or equal to 3.
Preferably, the oxynitride luminescent particle comprises a crystal nucleus layer and a crystal nucleus outer layer in the structure, the main body of the crystal nucleus layer is nitride luminescent crystal or oxygen-containing solid solution thereof, the main body of the crystal nucleus outer layer is oxide material, and the material of the structure of the oxynitride luminescent particle is mixture;
the chemical general formula of the nitride luminescent crystal or the oxygen-containing solid solution thereof is Mm-m1Aa1Bb1Oo1Nn1：Rm1；
The chemical general formula of the oxide material is Mm-m2Aa2Bb2Oo2：Rm2；
Wherein, the M element is at least one of Mg, Ca, Sr, Ba, Zn, Li, Na, K, Y and Sc;
the element A is at least one of B, Al, Ca and In;
the B element is at least one of C, Si, Ge and Sn;
the R element is at least one of Ce, Rr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu;
0.5≤m≤1.5；
0.001≤m1≤0.2，0.5≤a1≤1.5，0.5≤b1≤1.5，0≤o1≤0.5，2.5≤n1≤3.5；
0＜m2≤0.2，0.5≤a2≤1.5，0.5≤b2≤1.5，0.1≤o2≤5；
the thickness range of the outer layer of the core is within 500nm, and the inner side of the outer layer of the core of the nitrogen oxide luminescent particle is a crystal core layer.
The oxynitride luminescent crystal is (Sr)xCa1-x-y1)AlSiN3:y1EuOr an oxygen-containing solid solution thereof, the oxynitride material being (Sr)xCa1-x-y1)AlSiN3-z1O1.5z1Y1Eu, the oxide material being (Sr)xCa1-x-y1)AlSiO4.5Y1Eu, wherein x is more than or equal to 0 and less than or equal to 0.99, y1 is more than or equal to 0.001 and less than or equal to 0.2, and y1 is more than or equal to 0.1<z1<3。
The crystal nucleus layer also comprises an oxynitride luminescent crystal, and the outer layer of the crystal nucleus also comprises a nitride material.
The material of the structure of the nitrogen oxide luminescent particles is a compound or a mixture.
The oxynitride luminescent particle provided by the invention is excited in the range of the excitation light wavelength of 300-500nm to emit red light with the peak wavelength of 600-670 nm.
The invention provides an oxynitride luminescent body, which comprises a mixture of any one of the oxynitride luminescent particles and other crystalline grains or amorphous particles, and the proportion of the oxynitride luminescent particles in the mixture is not less than 50 wt%.
The invention provides a nitrogen oxide luminescent particle and a preparation method 1 of a preferred scheme thereof, which comprises the following specific steps:
step 1: m, A, B, R nitride, oxide or halide is used as raw material and has the chemical formula Mm-m1Aa1Bb1OO1Nn1:Rm1Weighing the required raw materials according to the stoichiometric ratio of cations in the composition;
step 2: uniformly mixing the raw materials weighed in the step 1 in a nitrogen atmosphere to form a mixture; wherein the mixing time of the raw materials is 1-5 h;
and step 3: carrying out high-temperature roasting on the mixture obtained in the step 2 in a roasting atmosphere, then cooling to a preset temperature, and introducing nitrogen-oxygen mixed gas or air for carrying out low-temperature roasting to obtain a nitrogen oxide luminescent particle semi-finished product; wherein:
the roasting temperature is 1400-2000 ℃, and the roasting time is 6-18 h; the roasting atmosphere is nitrogen atmosphere, nitrogen-argon mixed gas atmosphere, other inert gas atmosphere, nitrogen-hydrogen mixed gas atmosphere or other reducing gas atmosphere; the pressure of the roasting atmosphere is 1-100 atmospheric pressures;
the low-temperature roasting temperature is 200-450 ℃, and the low-temperature roasting time is 1-24 h; the volume percentage of oxygen in the nitrogen-oxygen mixed gas atmosphere is within 20 percent; the speed of introducing nitrogen-oxygen mixed gas or air in the low-temperature roasting is 0.1-10L/min;
and 4, step 4: carrying out post-treatment on the semi-finished product of the nitrogen oxide luminescent particles obtained in the step (3) to obtain a finished product of the nitrogen oxide luminescent particles; wherein the post-treatment comprises grinding, sieving, washing and drying, wherein the washing is carried out until the conductivity of the finished product of the nitrogen oxide luminescent particles is less than 10 mu s/cm.
The invention provides a nitrogen oxide luminescent particle and a preparation method 2 of a preferred scheme thereof, which comprises the following specific steps:
step 1: m, A, B, R nitride, oxide or halide is used as raw material and has the chemical formula Mm-m1Aa1Bb1OO1Nn1:Rm1Weighing the required raw materials according to the stoichiometric ratio of cations in the composition;
step 2: uniformly mixing the raw materials weighed in the step 1 in a nitrogen atmosphere to form a mixture;
and step 3: carrying out high-temperature roasting on the mixture obtained in the step 2 in roasting atmosphere to obtain a nitrogen oxide luminescent particle semi-finished product; wherein: the high-temperature roasting temperature is 1400-2000 ℃, and the high-temperature roasting time is 6-18 h; the high-temperature roasting atmosphere is pure nitrogen atmosphere, nitrogen-argon mixed gas atmosphere, other inert gas atmosphere, nitrogen-hydrogen mixed gas atmosphere or other reducing gas atmosphere; the pressure of the high-temperature roasting is normal pressure or 1-100 atmospheric pressures;
and 4, step 4: carrying out post-treatment on the nitrogen oxide luminescent particle semi-finished product obtained in the step (3); and the post-treatment comprises grinding, sieving, washing and drying, wherein the washing is carried out until the conductivity of the finished product of the nitrogen oxide luminescent particles is less than 10 mu s/cm.
And 5: roasting the nitrogen oxide luminescent particles obtained after the post-treatment in the step 4 at low temperature in a nitrogen-oxygen mixed gas or air atmosphere to obtain nitrogen oxide luminescent particle finished products; the low-temperature roasting temperature is 200-450 ℃, and the low-temperature roasting time is 1-24 h; the volume percentage of oxygen in the nitrogen-oxygen mixed gas atmosphere is within 20 percent.
The light-emitting device at least comprises an ultraviolet light, purple light or blue light LED chip and fluorescent powder, wherein the fluorescent powder at least uses the nitrogen oxide light-emitting particles in any one of the light-emitting devices.
The light-emitting device at least comprises an ultraviolet light, purple light or blue light LED chip and fluorescent powder, wherein the fluorescent powder at least uses the nitrogen oxide light-emitting body provided by the invention.
The invention provides a further preferable scheme of the light-emitting device, which is as follows: the method also comprises mixing other types of fluorescent powder to meet the illumination requirement through the complementation of the luminous colors or be applied to a high-color-rendering backlight white LED.
Specific examples and comparative examples of the nitrogen oxide luminescent particles and the preparation method thereof provided by the present invention are further disclosed below, wherein: the embodiment refers to that the finished product of the nitrogen oxide luminescent particles is obtained according to the structure and the preparation method of the nitrogen oxide luminescent particles provided by the invention; the comparative example refers to the luminescent particles and the preparation method disclosed in the prior art to obtain the finished luminescent particles. And testing by a nitrogen-oxygen analyzer to obtain the average oxygen atom content and nitrogen atom content in the luminous particles containing nitrogen and oxygen.
Example 1:
weighing Ca3N20.319g，Sr3N29.288g，AlN4.412g，Si3N45.033g，Eu2O30.947g, fully mixing the raw materials in nitrogen atmosphere for 2h, loading into a molybdenum crucible, quickly transferring into a tubular furnace, gradually heating to 1800 ℃ under the protection of nitrogen atmosphere, and preserving heat for 10 h; cooling to 400 deg.C, introducing nitrogen-oxygen mixed gas (oxygen volume percentage content is 20%) at 2L/min speed, calcining for 4 hr, pulverizing the obtained luminescent particles, sieving, adding the sieved luminescent particles into deionized water, stirring for 30min, vacuum filtering, washing to conductivity of 7.21 μ s/cm, and oven dryingAnd obtaining the finished product of the nitrogen oxide luminescent particles. The emission spectrum is shown in FIG. 2, the excitation spectrum is shown in FIG. 3, the luminescence intensity is shown in Table 1, which is higher than that of comparative example 1, and the thermal quenching spectrum is shown in FIG. 4. The crystal nucleus layer of the nitrogen oxide luminescent particles is Ca0.06Sr0.89AlSiN30.05Eu, the outer layer of the core is Ca0.06Sr0.89AlSiO0.9N2.40.05Eu, and the thickness is 380 nm.
Example 2:
weighing Ca3N20.537g，Sr3N28.963g，AlN4.457g，Si3N45.085g，Eu2O30.957g, fully mixing the raw materials in nitrogen atmosphere for 2h, loading into a molybdenum crucible, rapidly transferring into a tubular furnace, gradually heating to 1800 ℃ under the protection of nitrogen atmosphere, and keeping the temperature for 10 h; and (3) cooling to 400 ℃, introducing nitrogen-oxygen mixed gas (15% of oxygen volume percentage) at the speed of 2L/min for roasting, wherein the roasting time is 4h, crushing and sieving the obtained luminescent particles, putting the sieved luminescent particles into deionized water for stirring, stirring for 30min, then performing suction filtration, finally washing until the conductivity is 6.12 mu s/cm, and drying to obtain the finished product of the nitrogen oxide luminescent particles. The emission spectrum is shown in FIG. 2, the excitation spectrum is shown in FIG. 3, and the thermal quenching spectrum is shown in FIG. 4. The crystal nucleus layer of the nitride luminescent particles is Ca0.1Sr0.85AlSiN30.05Eu, the outer layer of the core is Ca0.1Sr0.85AlSi0.75ON20.05Eu, with a thickness of 450 nm.
Example 3:
weighing Ca3N20.648g，Sr3N28.797g，AlN4.481g，Si3N45.112g，Eu2O30.962g, fully mixing the raw materials in nitrogen atmosphere for 2h, loading into a molybdenum crucible, quickly transferring into a tubular furnace, gradually heating to 1800 ℃ under the protection of nitrogen atmosphere, and keeping the temperature for 10 h; cooling to 400 deg.C, introducing nitrogen-oxygen mixed gas (oxygen volume percentage content is 10%) at 2L/min speed, calcining for 4 hr, pulverizing the obtained luminescent particles, sieving, adding the sieved luminescent particles into deionized water, stirring, and stirringAnd (3) performing suction filtration for 30min, finally washing until the conductivity is 7.68 mu s/cm, and drying to obtain the finished product of the nitrogen oxide luminescent particles. The emission spectrum is shown in FIG. 2, the excitation spectrum is shown in FIG. 3, and the thermal quenching spectrum is shown in FIG. 4. The crystal nucleus layer of the nitrogen oxide luminescent particles is Ca0.12Sr0.83AlSiN30.05Eu, the outer layer of the core is Ca0.12Sr0.83AlSi0.7O1.3N1.7The thickness is 200 nm.
Comparative example 1:
weighing Ca3N20.648g，Sr3N28.797g，AlN4.481g，Si3N45.112g，Eu2O30.962g, fully mixing the raw materials in nitrogen atmosphere for 2h, loading into a molybdenum crucible, quickly transferring into a tubular furnace, gradually heating to 1800 ℃ under the protection of pure nitrogen atmosphere, and keeping the temperature for 10 h; and crushing the obtained luminescent particles, sieving, putting the sieved luminescent particles into deionized water, stirring for 30min, then carrying out suction filtration, finally washing until the conductivity is 4.34 mu s/cm, and drying to obtain the finished product of the luminescent particles. The emission spectrum is shown in FIG. 2, the excitation spectrum is shown in FIG. 3, and the thermal quenching spectrum is shown in FIG. 4. The luminescent particles are Ca0.12Sr0.83AlSiN3:0.05Eu。
The luminescent particles described in the above examples and comparative examples were respectively made into luminescent devices, and the test results obtained: the luminous intensity and the aging properties of comparative example 1 were lower than those of examples 1 to 3, see Table 1. Wherein the aging conditions are as follows: SMD-2835 type LED lamp pearl, chip size 10 x 30mil, chip wave band 452.5-455nm, electric current 150mA, power 0.5W, environmental condition: normal temperature and normal humidity.
TABLE 1
Example 4:
weighing Ca3N26.173g，AlN5.566g，Si3N46.349g，Eu2O31.911g, mixing the above raw materials in nitrogen gas for 3h, and chargingQuickly transferring the molybdenum crucible into a tubular furnace, gradually heating to 1750 ℃ under the protection of a nitrogen-argon mixed gas atmosphere, and preserving heat for 12 hours; and crushing and sieving the obtained luminescent particles, putting the sieved luminescent particles into deionized water, stirring for 30min, then carrying out suction filtration, finally washing until the conductivity is 5.22 mu s/cm, drying, then heating to 300 ℃ in an air atmosphere, and roasting for 8h to obtain the finished product of the nitrogen oxide luminescent particles. The emission spectrum is shown in FIG. 5, and the X-ray diffraction spectrum is shown in FIG. 6. The crystal nucleus layer of the nitride luminescent particles is Ca0.92AlSiN30.08Eu, the outer layer of the core is Ca0.92AlSiO1.2N2.20.08Eu, with a thickness of 480 nm.
Example 5:
weighing Ca3N26.207g，AlN5.596g，Si3N46.384g and EuN1.813g, fully mixing the raw materials in nitrogen for 3h, loading into a molybdenum crucible, rapidly transferring into a tube furnace, gradually heating to 1750 ℃ under the protection of nitrogen-argon mixed gas atmosphere, and keeping the temperature for 12 h; and crushing and sieving the obtained luminescent particles, putting the sieved luminescent particles into deionized water, stirring for 30min, then carrying out suction filtration, finally washing until the conductivity is 6.13 mu s/cm, drying, then heating to 300 ℃ in an air atmosphere, and roasting for 8h to obtain the finished product of the nitrogen oxide luminescent particles. The emission spectrum is shown in FIG. 5, and the X-ray diffraction spectrum is shown in FIG. 6. The crystal nucleus layer of the nitrogen oxide luminescent particles is Ca0.92AlSiN30.08Eu, the outer layer of the core is Ca0.92Al0.9Si0.85O0.9N2.10.08Eu, with a thickness of 390 nm.
Example 6:
weighing Ca3N25.909g，AlN5.327g，Si3N46.078g，EuCl32.686g, fully mixing the raw materials in nitrogen for 3h, loading into a molybdenum crucible, quickly transferring into a tubular furnace, gradually heating to 1750 ℃ under the protection of nitrogen-argon mixed gas atmosphere, and keeping the temperature for 12 h; pulverizing the obtained luminescent particles, sieving, adding the sieved luminescent particles into deionized water, stirring for 30min, vacuum filtering, and washing to obtain the final productThe conductivity is 6.98 mus/cm, the temperature is raised to 300 ℃ in the air atmosphere after drying, and the roasting time is 8 hours, thus obtaining the finished product of the nitrogen oxide luminescent particles. The emission spectrum is shown in FIG. 5, and the X-ray diffraction spectrum is shown in FIG. 6. The crystal nucleus layer of the nitrogen oxide luminescent particles is Ca0.92AlSiN30.08Eu, the outer layer of the core is Ca0.92AlSiO4.50.08Eu, and the thickness is 150 nm.
Example 7:
weighing Ca3N26.064g，AlN5.468g，Si3N46.238g，EuF32.23g, fully mixing the raw materials in nitrogen for 3 hours, loading the mixture into a molybdenum crucible, quickly transferring the molybdenum crucible into a tubular furnace, gradually heating to 1750 ℃ under the protection of nitrogen-argon mixed gas atmosphere, and keeping the temperature for 12 hours; and crushing and sieving the obtained luminescent particles, putting the sieved luminescent particles into deionized water, stirring for 30min, then carrying out suction filtration, finally washing until the conductivity is 6.98 mu s/cm, drying, then heating to 300 ℃ in an air atmosphere, and roasting for 8h to obtain the finished product of the nitrogen oxide luminescent particles. The crystal nucleus layer of the nitrogen oxide luminescent particles is Ca0.92AlSiN30.08Eu, the outer layer of the core is Ca0.92AlSi0.79ON2The thickness is 300 nm.
Comparative example 2:
weighing Ca3N26.173g，AlN5.566g，Si3N46.349g，Eu2O31.911g, fully mixing the raw materials in nitrogen for 3h, loading the mixture into a molybdenum crucible, quickly moving the molybdenum crucible into a tubular furnace, gradually heating to 1750 ℃ under the protection of nitrogen-argon mixed atmosphere, and keeping the temperature for 12 h; and crushing and sieving the obtained luminescent particles, putting the sieved luminescent particles into deionized water, stirring for 30min, then performing suction filtration, finally washing until the conductivity is 5.22 mu s/cm, and drying to obtain the finished product of the luminescent particles. The emission spectrum is shown in FIG. 5, and the X-ray diffraction spectrum is shown in FIG. 6. The luminescent particles are Ca0.92AlSiN3:0.08Eu。
The luminescent particles described in the above examples and comparative examples were respectively made into luminescent devices, and the test results obtained: the luminescence intensity and the aging behavior of comparative example 2 are lower than those of examples 4 to 7, see Table 2. Wherein the aging conditions are as follows: SMD-2835 type LED lamp pearl, chip size 10 x 30mil, chip wave band 452.5-455nm, electric current 150mA, power 0.5W, environmental condition: normal temperature and normal humidity.
TABLE 2
Example 8:
weighing Ca3N21.188g，Sr3N28.544g，Li3N0.013g，AlN4.644g，Al2O30.058g，Si3N45.351g，Eu2O30.201g, fully mixing the raw materials in nitrogen for 2 hours, loading the mixture into a molybdenum crucible, quickly transferring the molybdenum crucible into a tube furnace, gradually heating to 1850 ℃ under the protection of nitrogen-argon mixed gas atmosphere, and preserving heat for 9 hours; and crushing and sieving the obtained luminescent particles, putting the sieved luminescent particles into deionized water, stirring for 30min, then carrying out suction filtration, finally washing until the conductivity is 5.41 mu s/cm, drying in a nitrogen-oxygen mixed gas atmosphere (wherein the volume percentage of oxygen is 6%), heating to 250 ℃, and roasting for 15h to obtain the finished product of the nitrogen oxide luminescent particles, wherein the scanning electron microscope picture is shown in figure 7. The crystal nucleus layer of the nitrogen oxide luminescent particles is Ca0.21Sr0.77Li0.01AlSiO0.01N2.990.01Eu, the outer layer of the core is Ca0.21Sr0.77Li0.01AlSi0.8025O0.8N2.20.01Eu, and the thickness is 420 nm.
Example 9:
weighing Ca3N21.193g，Sr3N28.473g，Li3N0.027g，AlN4.713g，Si3N45.33g，SiO20.069g，Eu2O30.202g, fully mixing the raw materials in nitrogen for 2 hours, loading the mixture into a molybdenum crucible, quickly transferring the molybdenum crucible into a tube furnace, gradually heating to 1850 ℃ under the protection of nitrogen-argon mixed gas atmosphere, and preserving heat for 9 hours; pulverizing the obtained luminescent particlesSieving, placing the sieved luminescent particles into deionized water, stirring for 30min, then carrying out suction filtration, finally washing until the conductivity is 3.55 mu s/cm, drying in a nitrogen-oxygen mixed gas atmosphere (wherein the volume percentage of oxygen is 6%), heating to 250 ℃, and roasting for 15h to obtain the finished product of the nitrogen oxide luminescent particles. The crystal nucleus layer of the nitrogen oxide luminescent particles is Ca0.21Sr0.76Li0.02AlSiO0.02N2.980.01Eu, the outer layer of the core is Ca0.21Sr0.76Li0.02AlSi1.01O0.9N2.4The thickness was 250 nm.
Example 10:
weighing Ca3N21.126g，CaO0.064g，Sr3N28.614g，AlN4.669g，Si3N45.326g，Eu2O30.2g, fully mixing the raw materials in nitrogen for 2 hours, loading the mixture into a molybdenum crucible, quickly transferring the molybdenum crucible into a tube furnace, gradually heating to 1850 ℃ under the protection of nitrogen-argon mixed gas atmosphere, and preserving heat for 9 hours; and crushing and sieving the obtained luminescent particles, putting the sieved nitride luminescent particles into deionized water, stirring for 30min, then carrying out suction filtration, finally washing until the conductivity is 4.77 mu s/cm, drying in a nitrogen-oxygen mixed gas atmosphere (wherein the volume percentage of oxygen is 6%), heating to 250 ℃, and roasting for 15h to obtain the nitride luminescent particle finished product. The crystal nucleus layer of the nitride luminescent particles is Ca0.21Sr0.78AlSiN30.01Eu, the outer layer of the core is Ca0.21Sr0.78AlSiO1.2N2.20.01Eu, and the thickness is 100 nm.
Comparative example 3:
weighing Ca3N21.183g，Sr3N28.618g，AlN4.671g，Si3N45.328g，Eu2O30.201g, fully mixing the raw materials in nitrogen for 2h, loading into a molybdenum crucible, quickly transferring into a tube furnace, gradually heating to 1850 ℃ under the protection of nitrogen-argon mixed gas atmosphere, preserving heat for 9h, crushing the obtained luminescent particles, sieving, and placing the sieved luminescent particles into deionized waterStirring for 30min, filtering, and washing to conductivity of 5.63 μ s/cm to obtain final product. The scanning electron microscope picture is shown in FIG. 8. The luminescent particles are Ca0.21Sr0.78AlSiN3:0.01Eu。
The luminescent particles described in the above examples and comparative examples were respectively made into luminescent devices, and the test results obtained: the luminescence intensity and the aging behavior of comparative example 3 are lower than those of examples 8 to 10, see Table 3. Wherein the aging conditions are as follows: SMD-2835 type LED lamp pearl, chip size 10 x 30mil, chip wave band 452.5-455nm, electric current 150mA, power 0.5W, environmental condition: normal temperature and normal humidity.
TABLE 3
Example 11:
weighing Ca3N21.079g，Sr3N27.414g，AlN4.477g，Si3N45.108g，Eu2O31.922g, fully mixing the raw materials in a nitrogen atmosphere for 1h, loading the mixture into a molybdenum crucible, quickly transferring the molybdenum crucible into a tubular furnace, gradually heating to 1840 ℃ under the protection of a nitrogen-argon mixed gas atmosphere, and preserving heat for 10 h; and cooling to 200 ℃, introducing air at a speed of 4L/min for roasting for 18h, crushing the obtained luminescent particles, sieving, putting the sieved luminescent particles into deionized water, stirring for 30min, performing suction filtration, finally washing until the conductivity is 6.23 mu s/cm, and drying to obtain the finished product of the nitrogen oxide luminescent particles. The crystal nucleus layer of the nitrogen oxide luminescent particles is Ca0.2Sr0.7AlSiN30.1Eu, the outer layer of the core is Ca0.2Sr0.7AlSiO3N is 0.1Eu, and the thickness is 470 nm.
Example 12:
weighing Ca3N20.921g，Ba3N29.262g，AlN3.819g，Si3N44.357g，Eu2O31.64g, fully mixing the raw materials in a nitrogen atmosphere for 1h, loading the mixture into a molybdenum crucible, quickly transferring the molybdenum crucible into a tubular furnace, gradually heating to 1840 ℃ under the protection of a nitrogen-argon mixed gas atmosphere, and preserving heat for 10 h; and cooling to 200 ℃, introducing air at a speed of 4L/min for roasting for 18h, crushing the obtained luminescent particles, sieving, putting the sieved luminescent particles into deionized water, stirring for 30min, performing suction filtration, finally washing until the conductivity is 5.79 mu s/cm, and drying to obtain the finished product of the nitrogen oxide luminescent particles. The crystal nucleus layer of the nitrogen oxide luminescent particles is Ca0.2Ba0.7AlSiN30.1Eu, the outer layer of the core is Ca0.2Ba0.7AlSi0.975O4.3N0.10.1Eu, and the thickness is 420 nm.
Example 13:
weighing Ca3N21.078g，Sr3N27.395g，AlN4.466g，Si3N45.044g，Ge3N40.099g，Eu2O31.917g, fully mixing the raw materials in a nitrogen atmosphere for 1h, loading the mixture into a molybdenum crucible, quickly transferring the molybdenum crucible into a tubular furnace, gradually heating to 1840 ℃ under the protection of a nitrogen-argon mixed gas atmosphere, and preserving heat for 10 h; and cooling to 200 ℃, introducing air at a speed of 4L/min for roasting for 18h, crushing the obtained luminescent particles, sieving, putting the sieved luminescent particles into deionized water, stirring for 30min, performing suction filtration, finally washing until the conductivity is 5.63 mu s/cm, and drying to obtain the finished product of the nitrogen oxide luminescent particles. The crystal nucleus layer of the nitrogen oxide luminescent particles is Ca0.2Sr0.7AlSi0.99Ge0.01N30.1Eu, the outer layer of the core is Ca0.2Sr0.7AlSi0.99Ge0.01O0.9N2.40.1Eu, and the thickness is 270 nm.
Example 14
Weighing Ca3N21.085g，Sr3N27.348g，Y2O30.124g，AlN4.502g，Si3N45.008g，Eu2O31.933g, fully mixing the raw materials in a nitrogen atmosphere for 1h, loading the mixture into a molybdenum crucible, quickly transferring the molybdenum crucible into a tubular furnace, gradually heating to 1840 ℃ under the protection of a nitrogen-argon mixed gas atmosphere, and preserving heat for 10 h; and cooling to 200 ℃, introducing air at a speed of 4L/min for roasting for 18h, crushing the obtained luminescent particles, sieving, putting the sieved luminescent particles into deionized water, stirring for 30min, performing suction filtration, finally washing until the conductivity is 4.88 mu s/cm, and drying to obtain the finished product of the nitrogen oxide luminescent particles. The crystal nucleus layer of the nitrogen oxide luminescent particles is Ca0.2Sr0.69Y0.01AlSi0.975O0.1N2 .90.1Eu, the outer layer of the core is Ca0.2Sr0.69Y0.01AlSi0.7O1.2N1.80.1Eu, its thickness is 240 nm.
Example 15
Weighing Ca3N21.083g，Sr3N27.224g，Sc2O30.151g，AlN4.491g，Si3N45.123g，Eu2O31.927g, fully mixing the raw materials in a nitrogen atmosphere for 1h, loading the mixture into a molybdenum crucible, quickly transferring the molybdenum crucible into a tubular furnace, gradually heating to 1840 ℃ under the protection of a nitrogen-argon mixed gas atmosphere, and preserving heat for 10 h; cooling to 200 ℃, introducing air at the speed of 4L/min for roasting for 18h, crushing the obtained luminescent particles, sieving, putting the sieved luminescent particles into deionized water, stirring for 30min, then carrying out suction filtration, finally washing until the conductivity is 6.02 mu s/cm, and drying to obtain the finished product of the nitrogen oxide luminescent particles. The crystal nucleus layer of the nitrogen oxide luminescent particles is Ca0.2Sr0.68Sc0.02AlSiN30.1Eu, the outer layer of the core is Ca0.2Sr0.68Sc0.02AlSiO4.50.1Eu, and the thickness is 370 nm.
Comparative example 4
Weighing Ca3N21.079g，Sr3N27.414g，AlN4.477g，Si3N45.108g，Eu2O31.922g, fully mixing the raw materials in a nitrogen atmosphere for 1h, loading the mixture into a molybdenum crucible, quickly moving the molybdenum crucible into a tube furnace, gradually heating to 1840 ℃ under the protection of a nitrogen-argon mixed gas atmosphere, preserving heat for 10h, crushing the obtained luminescent particles, sieving, putting the sieved luminescent particles into deionized water, stirring for 30min, carrying out suction filtration, and finally washing until the conductivity is 6.08 mus/cm, thus obtaining the finished product of the luminescent particles. The luminescent particles are Ca0.2Sr0.7AlSiN3:0.1Eu。
The luminescent particles described in the above examples and comparative examples were respectively made into luminescent devices, and the test results obtained: the luminescence intensity and the aging behavior of comparative example 4 are lower than those of examples 11 to 15, see Table 4. Wherein the aging conditions are as follows: SMD-2835 type LED lamp pearl, chip size 10 x 30mil, chip wave band 452.5-455nm, electric current 150mA, power 0.5W, environmental condition: normal temperature and normal humidity.
TABLE 4
Example 16:
weighing Ca3N25.125g，AlN5.185g，Si3N45.619g，Eu2O33.339g，Tm2O30.732g, fully mixing the raw materials in nitrogen atmosphere for 2h, loading into a molybdenum crucible, rapidly transferring into a tube furnace, gradually heating to 1790 ℃ under the protection of nitrogen atmosphere, and keeping the temperature for 12 h; and crushing and sieving the obtained luminescent particles, putting the sieved luminescent particles into deionized water, stirring for 30min, then carrying out suction filtration, finally washing until the conductivity is 6.54 mu s/cm, drying, then heating to 270 ℃ in an air atmosphere, and roasting for 12h to obtain the finished product of the nitrogen oxide luminescent particles. The excitation spectrum is shown in figure 9, and the thermal quenching spectrum is shown in figureFig. 10. The crystal nucleus layer of the nitrogen oxide luminescent particles is Ca0.82AlSi0.95O0.2N2.80.15Eu,0.03Tm, the outer layer of the core is Ca0.82AlSiO4.50.15Eu,0.03Tm, and the thickness is 420 nm.
Example 17:
weighing Ca3N24.938g，AlN5.056g，Si3N45.768g，Eu2O33.256g，Lu2O30.982g, fully mixing the raw materials in nitrogen atmosphere for 2h, loading into a molybdenum crucible, rapidly transferring into a tubular furnace, gradually heating to 1790 ℃ under the protection of nitrogen atmosphere, and keeping the temperature for 12 h; and crushing and sieving the obtained luminescent particles, putting the sieved luminescent particles into deionized water, stirring for 30min, then carrying out suction filtration, finally washing until the conductivity is 4.58 mu s/cm, drying, then heating to 270 ℃ in an air atmosphere, and roasting for 12h to obtain the finished product of the nitrogen oxide luminescent particles. The excitation spectrum is shown in FIG. 9, and the thermal quenching spectrum is shown in FIG. 10. The crystal nucleus layer of the luminescent particles of the oxygen nitride is Ca0.81AlSiN30.15Eu,0.04Lu, the outer layer of the core is Ca0.81AlSi0.5O2N is 0.15Eu and 0.04Lu, and the thickness is 290 nm.
Example 18:
weighing Ca3N25.011g，AlN5.131g，Si3N45.854g，Eu2O33.304g，Dy2O30.7g, fully mixing the raw materials in nitrogen atmosphere for 2h, loading into a molybdenum crucible, quickly transferring into a tubular furnace, gradually heating to 1790 ℃ under the protection of nitrogen atmosphere, and keeping the temperature for 12 h; and crushing and sieving the obtained luminescent particles, putting the sieved luminescent particles into deionized water, stirring for 30min, then carrying out suction filtration, finally washing until the conductivity is 6.31 mu s/cm, drying, then heating to 270 ℃ in an air atmosphere, and roasting for 12h to obtain the finished product of the nitrogen oxide luminescent particles. The excitation spectrum is shown in FIG. 9, and the thermal quenching spectrum is shown in FIG. 10. The crystal nucleus layer of the nitrogen oxide luminescent particles is Ca0.82AlSiN30.15Eu,0.03Dy, the core outer layer being Ca0.82AlSiO2.1N1.60.15Eu and 0.03Dy, and the thickness is 400 nm.
Comparative example 5:
weighing Ca3N25.38g，AlN5.25g，Si3N45.989g，Eu2O33.381g, fully mixing the raw materials in nitrogen atmosphere for 2h, loading into a molybdenum crucible, rapidly transferring into a tube furnace, gradually heating to 1790 ℃ under the protection of nitrogen atmosphere, and keeping the temperature for 12 h; and crushing and sieving the obtained luminescent particles, putting the sieved luminescent particles into deionized water, stirring for 30min, then performing suction filtration, and finally washing until the conductivity is 2.15 mu s/cm, thus obtaining the finished product of the luminescent particles. The excitation spectrum is shown in FIG. 9, and the thermal quenching spectrum is shown in FIG. 10. The luminescent particles are Ca0.85AlSiN3:0.15Eu。
The luminescent particles described in the above examples and comparative examples were respectively made into luminescent devices, and the test results obtained: the luminescence intensity and the aging behavior of comparative example 5 are lower than those of examples 16 to 18, see Table 5. Wherein the aging conditions are as follows: SMD-2835 type LED lamp pearl, chip size 10 x 30mil, chip wave band 452.5-455nm, electric current 150mA, power 0.5W, environmental condition: normal temperature and normal humidity.
TABLE 5
The embodiments of the present invention are described in detail with reference to the prior art, and the description thereof is not limited thereto.
The invention obtains satisfactory trial effect through repeated test verification.
The above embodiments and examples are specific supports for the technical ideas of the oxynitride luminescent particle and the preparation method thereof, the oxynitride luminescent body and the luminescent device provided by the present invention, and the protection scope of the present invention cannot be limited thereby.
Claims (10)
1. The oxynitride luminescent particle is characterized in that the structure of the oxynitride luminescent particle comprises a crystal nucleus layer and a crystal nucleus outer layer, the main body of the crystal nucleus layer is a nitride luminescent crystal or an oxygen-containing solid solution thereof, and the main body of the crystal nucleus outer layer is an oxide material;
the chemical general formula of the nitride luminescent crystal or the oxygen-containing solid solution thereof is Mm-m1Aa1Bb1Oo1Nn1：Rm1；
The chemical general formula of the oxide material is Mm-m2Aa2Bb2Oo2：Rm2；
Wherein, the M element is at least one of Mg, Ca, Sr, Ba, Zn, Li, Na, K, Y and Sc;
the element A is at least one of B, Al, Ca and In;
the B element is at least one of C, Si, Ge and Sn;
the R element is at least one of Ce, Rr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu;
0.5≤m≤1.5；
0.001≤m1≤0.2，0.5≤a1≤1.5，0.5≤b1≤1.5，0≤o1≤0.5，2.5≤n1≤3.5；
0＜m2≤0.2，0.5≤a2≤1.5，0.5≤b2≤1.5，0.1≤o2≤5；
the thickness range of the outer layer of the core is within 500nm, and the inner side of the outer layer of the core of the nitrogen oxide luminescent particle is a crystal core layer.
2. The oxynitride luminescent particle of claim 1 wherein the core has a tunable distribution of the amount of oxygen in the outer layer from the outer surface to the inner surface.
3. The oxynitride luminescent particle of claim 1 wherein the oxygen content in the outer layer of the core is distributed in a structure that gradually increases from the inner surface to the outer surface.
4. The oxynitride luminescent particle according to claim 1, wherein the content of the nitride luminescent crystal or the oxygen-containing solid solution thereof in the core layer is not less than 90%, and the content of the oxide material in the core outer layer is not less than 50%.
5. The oxynitride luminescent particle of claim 1, wherein the core outer layer has a thickness in the range of 150 to 500 nm.
6. The oxynitride luminescent particle of claim 1, wherein the nitride luminescent crystal is (Sr)xCa1-x-y1)AlSiN3:y1Eu；
The oxide material is (Sr)xCa1-x-y1)AlSiO4.5:y1Eu；
Wherein x is more than or equal to 0 and less than or equal to 0.99, y1 is more than or equal to 0.001 and less than or equal to 0.2, and z1 is more than 0 and less than or equal to 3.
7. An oxynitride luminescent body comprising a mixture of the oxynitride luminescent particles according to any one of claims 1 to 6 with other crystalline grains or amorphous particles;
in the mixture, the proportion of the oxynitride luminescent particles is not less than 50 wt%.
8. A method for producing the nitrogen oxide luminescent particle as claimed in claim 1, characterized by comprising the following sequential basic steps in this order:
step 1: m, A, B, R nitride, oxide or halide is used as raw material and has the chemical formula Mm-m1Aa1Bb1Nn1：Rm1Weighing the required raw materials according to the stoichiometric ratio of cations in the composition;
step 2: uniformly mixing the raw materials weighed in the step 1 in a nitrogen atmosphere to form a mixture; the mixing time of the raw materials is 1-5 h;
and step 3: carrying out primary high-temperature roasting on the mixture obtained in the step 2 in a roasting atmosphere, then cooling to a preset temperature, and introducing nitrogen-oxygen mixed gas or air for primary low-temperature roasting to obtain a nitrogen oxide luminescent particle semi-finished product;
the primary high-temperature roasting temperature is 1400-2000 ℃, and the roasting time is 6-18 h; the roasting atmosphere is nitrogen atmosphere, nitrogen-argon mixed gas atmosphere, other inert gas atmosphere, nitrogen-hydrogen mixed gas atmosphere or other reducing gas atmosphere; the pressure of the roasting atmosphere is 1-100 atmospheric pressures;
the primary low-temperature roasting temperature is 200-450 ℃, and the low-temperature roasting time is 1-24 h; the speed of introducing nitrogen-oxygen mixed gas or air in the primary low-temperature roasting is 0.1-10L/min; the volume percentage of oxygen in the nitrogen-oxygen mixed gas atmosphere is within 20 percent;
and 4, step 4: carrying out post-treatment on the semi-finished product of the nitrogen oxide luminescent particles obtained in the step (3) to obtain a finished product of the nitrogen oxide luminescent particles;
and the post-treatment comprises grinding, sieving, washing and drying, wherein the washing is carried out until the conductivity of the finished product of the nitrogen oxide luminescent particles is less than 10 mu s/cm.
9. The method for preparing an oxynitride luminescent particle as claimed in claim 1, which comprises the following successive basic steps:
step 1: m, A, B, R nitride, oxide or halide is used as raw material and has the chemical formula Mm-m1Aa1Bb1Nn1：Rm1Weighing the required raw materials according to the stoichiometric ratio of cations in the composition;
step 2: uniformly mixing the raw materials weighed in the step 1 in a nitrogen atmosphere to form a mixture; the mixing time of the raw materials is 1-5 h;
and step 3: carrying out primary high-temperature roasting on the mixture obtained in the step 2 in roasting atmosphere to obtain a nitrogen oxide luminescent particle semi-finished product;
the primary high-temperature roasting temperature is 1400-2000 ℃, and the roasting time is 6-18 h; the roasting atmosphere is nitrogen atmosphere, nitrogen-argon mixed gas atmosphere, other inert gas atmosphere, nitrogen-hydrogen mixed gas atmosphere or other reducing gas atmosphere; the pressure of the roasting atmosphere is 1-100 atmospheric pressures;
and 4, step 4: carrying out post-treatment on the nitrogen oxide luminescent particle semi-finished product obtained in the step (3);
the post-treatment comprises grinding, sieving, washing and drying, wherein the washing is carried out until the conductivity of the finished product of the nitrogen oxide luminescent particles is less than 10 mu s/cm;
and 5: carrying out primary low-temperature roasting on the nitrogen oxide luminescent particles obtained after the post-treatment in the step 4 in a nitrogen-oxygen mixed gas or air atmosphere to obtain nitrogen oxide luminescent particle finished products; the primary low-temperature roasting temperature is 200-450 ℃, the low-temperature roasting time is 1-24h, and the volume percentage of oxygen in the nitrogen-oxygen mixed gas atmosphere is within 20 percent.
10. A light-emitting device is characterized by at least comprising an LED chip and fluorescent powder;
the LED chip is selected from any one of an ultraviolet LED chip, a purple LED chip or a blue LED chip;
wherein the phosphor comprises the oxynitride luminescent particle according to any one of claims 1 to 5;
or, the nitroxide emitter of claim 6;
or, any one of the nitrogen oxide luminescent particles obtained by the production method according to claim 7 or 8;
preferably, the method also comprises mixing other types of fluorescent powder so as to meet the illumination requirement or be applied to a high-color-rendering backlight white LED through the complementation of the luminous colors.
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