CN101117576B - Oxynitrides luminescent material and illuminating or exhibiting light source produced thereby - Google Patents
Oxynitrides luminescent material and illuminating or exhibiting light source produced thereby Download PDFInfo
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- CN101117576B CN101117576B CN2006100890189A CN200610089018A CN101117576B CN 101117576 B CN101117576 B CN 101117576B CN 2006100890189 A CN2006100890189 A CN 2006100890189A CN 200610089018 A CN200610089018 A CN 200610089018A CN 101117576 B CN101117576 B CN 101117576B
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- 239000000463 material Substances 0.000 title claims abstract description 77
- 230000001747 exhibiting effect Effects 0.000 title 1
- 238000005286 illumination Methods 0.000 claims abstract description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 75
- 241001025261 Neoraja caerulea Species 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 abstract description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 3
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 abstract 1
- 230000008450 motivation Effects 0.000 abstract 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 150000004767 nitrides Chemical class 0.000 description 11
- 238000000695 excitation spectrum Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012423 maintenance 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Luminescent Compositions (AREA)
Abstract
The present invention relates to oxy-nitride luminescent material and its manufactured illumination and display light source. The molecular formula of oxy-nitride luminescent material is A2B5-xOxN8-x to Euy, wherein, A is alkali metal, one or a plurality of alkaline-earth metal; B is one or a plurality of 3-5 family elements contains at least Si; 0 is less than or equal to x and x is less than or equal to 1; 0.005 is less than or equal to y, and y is less than or equal to 1.0. The luminescent material is motivated by motivation light sources such as ultraviolet ray, near ultraviolet ray or blue light as LED, the high light red color light with wave length at 600 to 680 nm can be motivated. The present invention also relates to the preparation method of the oxy-nitride luminescent material. The present invention of luminescent material can make novel white light LED light source cooperated with ultraviolet ray, near ultraviolet ray or blue light LED as well as other luminescent material such as yttrium aluminum garnet type luminescent material, or can make red LED light source matched with ultraviolet ray and near ultraviolet ray.
Description
Technical field
The present invention relates to semiconductor applications, particularly relate to a kind of nitrogen oxides luminescent material and preparation method thereof and by its illumination of making or display light source.
Background technology
GaN based light-emitting diode LED (Light-Emitting Diode) is a kind of novel light-emitting device that is described as the 21 century solid-state illumination, have that volume is little, power saving, life-span be long, do not contain advantages such as the mercury, high-level efficiency of contaminate environment, low maintenance, can be widely used on the various lighting installations, comprise interior lighting, traffic signals/pilot lamp, automobile tail light/headlamp, outdoor ultra-large type screen, display screen and advertisement screen etc., have to replace the present various bulb that uses and the trend of luminescent lamp.This novel green light source will become lighting system of new generation, and energy-saving and environmental protection, the aspects such as quality of life that improve people are had extensively and profound significance.The manufacturing technology of white light LEDs mainly comprises: the combination of (1) three kind of monochromatic LED (blue, green, red); (2) blue-ray LED+yellow fluorescent powder; (3) ultraviolet LED+redgreenblue fluorescent material.But the phosphor that can effectively be excited by blue-ray LED seldom.At present, mainly with yttrium aluminium garnet YAG: the Ce fluorescent material combines by the complementary color principle with blue-ray LED and obtains white light.But, since YAG send photochromic yellowish green partially, can only obtain the higher cool tone white light of colour temperature, and its colour rendering index awaits further raising.For white light (being transferred to warm tones) and the higher colour rendering index that obtains different-colour, need to add red fluorescence powder from cool colour.
At present, the red fluorescence powder that can be excited by blue light (420-480nm) is mainly based on the sulfide of the two valency europiums that mix.As (Ca, Sr, Ba) S:Eu
2+But the chemical and the thermostability of sulphide fluorescent material are very poor, easily react with airborne moisture content, are heated and easily decompose, and have waste gas to discharge contaminate environment in process of production.Recently, by SiN
4The nitride that elementary cell constitutes has been subjected to paying close attention to widely as the base material of fluorescent material.Because stronger covalent linkage and bigger crystal field splitting, this compounds can be luminous at long wavelength under the doping of rare earth element such as divalent europium, as yellow, orange and red.European patent (PCT/EP2000/012047) has been reported M
2Si
5N
8: Eu
2+(M=Ca, Sr, Ba) red fluorescence powder and preparation method thereof.This fluorescent material can be by blue-light excited, and chemistry and thermally-stabilised good.But the luminous intensity of this fluorescent material remains further to be improved.Particularly, this luminescent material can only adopt metal and the nitride metal raw material that is difficult for depositing when synthetic in air, and adopts horizontal pipe furnace synthetic, therefore, the synthesis technique complexity of this patent report, wayward, and can not realize volume production.
Summary of the invention:
The present invention is directed to the defective in above-mentioned field, provide that a kind of chemical property is stable, luminescent properties is excellent, the white light LEDs that can be excited by ultraviolet LED or blue-ray LED is with nitrogen oxygen joint compound red illuminating material; Its excitation wavelength is between 300-500nm, and emission wavelength is between 600-680nm.
Another object of the present invention provides a kind of method of making this luminescent material, this manufacture method is simple, easy handling, be easy to volume production, pollution-free, cost is low.
A further object of the present invention provides a kind of by this luminescent material made White-light LED illumination or display light source.
A kind of nitrogen oxides luminescent material, its chemical formula is: A
2B
5-xO
xN
8-x: Eu
y,
Wherein, A is one or more in basic metal, the alkaline-earth metal;
B be in the III-V family element one or more and contain Si at least;
0≤x≤1；0.005≤y≤1.0。
Wherein, A is preferably Li, Na, Mg, Ca, Sr or Ba;
B is preferably Si, Ge, B, Al, Ga or In.
The preparation method of above-mentioned nitrogen oxides luminescent material comprises the steps:
(1) with containing oxide compound, nitride, nitrate or the carbonate of A, contain nitride or the oxide compound of B, and the nitride of Eu, oxide compound or nitrate is raw material, ground and mixed is even;
(2) mixture that step (1) is obtained carries out high-temperature roasting with gas pressure sintering method or solid reaction process under protection of inert gas, perhaps carries out high temperature with the method for carbothermal reduction-nitridation and synthesizes.
(3) product of roasting that step (2) is obtained promptly makes nitrogen oxides luminescent material of the present invention again through pulverizing, removal of impurities, oven dry, classification.
Can also add solvent dehydrated alcohol or normal hexane during described grinding.
Rare gas element is a nitrogen in the described gas pressure sintering method, and nitrogen pressure is a 1-200 normal atmosphere.
Rare gas element in the described solid reaction process is the mixed gas of normal pressure nitrogen and hydrogen, and the volume ratio of nitrogen and hydrogen is 95: 5.
The temperature of described high-temperature roasting is 1200-1800 ℃, and roasting time is 0.5-30 hour, and roasting can repeatedly be carried out.
The temperature of described carbothermal reduction-nitridation is 1200-1600 ℃, and the time is 0.5-30 hour.
Also be added with reaction flux in the described raw material, described fusing assistant is to contain the halogenide of A or in the boric acid one or more.
The addition of described reaction flux is the 0.01-10% of raw material gross weight.
Described removal of impurities comprises pickling or washing.
A kind of White-light LED illumination light source is characterized in that: contain ultraviolet, near ultraviolet or blue-ray LED and above-mentioned nitrogen oxides luminescent material.
A kind of red LED light source is characterized in that: contain ultraviolet or near ultraviolet LED and above-mentioned nitrogen oxides luminescent material.
Nitrogen oxides luminescent material of the present invention can excite orange red, the red or wine-colored light that sends 600-680nm down at 300-500nm light, and its chemical formula is: A
2B
5-xO
xN
8-x: Eu
y,
Wherein, A is preferably and can be more active Li in the basic metal, Na, in the alkaline-earth metal than neutral Mg, Ca, one or more among Sr or the Ba;
B is an III-V family element, preferred Si, Ge, B, Al, Ga, one or more among the In and contain Si at least; 0≤x≤1; 0.005≤y≤1.0.
Synthetic method of the present invention, its raw material adopts A nitride metal beyond the region of objective existence, also can adopt oxide compound, carbonate, nitrate etc., these salts have enriched the range of choice of its raw material as long as can resolve into the raw material that metal oxide then can become the above-mentioned luminescent material of preparation under high-temperature roasting, have also reduced synthetic cost when being both, and the character of salt is more stable, in building-up process, do not need raw material is handled especially, make reaction be easy to control, realize mass production easily.A metal nitride, oxide compound, carbonate, nitrate etc. synthesize luminescent material of the present invention with nitride or the oxide compound of oxide compound, nitride and the Eu of B under high-temperature roasting; feed inert protective gas in the process of high-temperature roasting, the purpose that feeds protection gas is that (1) protects some nitride raw material and reaction product that the effect of playing reducing atmosphere with (2) at high temperature takes place to decompose.Rare gas element often adopts N
2, or adopt N
2With H
2Mixed gas, can adopt high pressure, also can adopt normal pressure.Before high-temperature roasting, can add etoh solvent or normal hexane during the raw material ground and mixed makes the raw material mixing more even, the halogenide or the boric acid that can add fusing assistant A before the roasting, need in the last handling process of reaction unnecessary reaction impurities is removed, above-mentioned raw materials is through after the high-temperature roasting, impurity be generally A or/and B or/and the oxide compound of Eu can adopt pickling or washing to remove, remaining impurity has then turned to gaseous volatilization.
Synthetic nitrogen oxides luminescent material of the present invention can excite orange red, the red or wine-colored light that send down 600-680nm at 300-500nm light, therefore can be coated in other luminescent material such as green luminescent material and prepare novel white light LEDs on the blue-light LED chip; Also can be coated on ultraviolet or the near ultraviolet LED chip and prepare novel white light LEDs, the energy transformation height as blue, green luminescent material with other luminescent material; Can also be complementary with blue-ray LED, ultraviolet LED or near ultraviolet LED, or mix other luminescent materials, the preparation color LED.
The present invention unstable alkaline earth nitride or metal by using oxide compound but not in air are realized the simplification of synthesis technique; Realize the purpose of volume production by the method that adopts gas pressure sintering; Realize the improvement of wavelength-tunable and luminous intensity by the method for part substitutional element.Luminescent material synthetic method provided by the present invention has that method is simple, easy handling, easily realize volume production, pollution-free, low cost and other advantages.
Characteristics of the present invention are:
(1) luminescent material of the present invention is an oxynitride, and performance is highly stable, good temp characteristic.
(2) the non-constant width of excitation spectrum scope of luminescent material of the present invention is all good especially from the stimulation effect of 300-500nm.
(3) simple and practical, pollution-free, the easy volume production of the preparation method of luminescent material provided by the present invention, easy to operate.
(4) the prepared white light LEDs colour rendering index height of the present invention, reference color temperature is wide.
(5) the prepared red-light LED brightness height of the present invention.
Description of drawings:
Fig. 1 is the XRD figure spectrum of embodiment 1.
Fig. 2 a is the emmission spectrum of embodiment 1.
Fig. 2 b is the excitation spectrum of embodiment 1.
Fig. 3 is the XRD figure spectrum of embodiment 8.
Fig. 4 a is the emmission spectrum of embodiment 8.
Fig. 4 b is the excitation spectrum of embodiment 8.
Fig. 5 a is the emmission spectrum of embodiment 14.
Fig. 5 b is the excitation spectrum of embodiment 14.
Fig. 6 is the XRD figure spectrum of embodiment 14.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Sr
1.96Si
5N
8: Eu
0.04Be the disclosed compound of European patent (PCT/EP2000/012047). synthetic according to its disclosed method, as the reference examples of this experiment.
Embodiment 1:Sr
1.90Mg
0.06Si
4.80Al
0.20O
0.20N
7.80: Eu
0.04The preparation example (solid reaction process) of luminescent material
Take by weighing Sr by above-mentioned composition
3N
2(43.1932 gram), Mg
3N
2(0.4671 gram), Si
3N
4(52.3152 gram), Al
2O
3(2.3822 gram) and Eu
2O
3(1.6442 gram), in glove box mix grinding evenly after, the boron nitride crucible of packing into is at the tubular type kiln roasting, normal pressure feeds N down
2/ H
2(95%/5%), flow is 2 liters/minute, with 0.1gSrF
2Be fusing assistant, 1400 ℃ of insulations 4 hours, the gained powder after grinding again with same condition again high-temperature roasting once promote the growth of crystal grain.The gained luminescent material promptly obtains red illuminating material 100g of the present invention through pulverizing, hydrochloric acid washing impurity-removing, oven dry.Its X diffracting spectrum as shown in Figure 1, as can be seen from the figure this powder is single phase, shows Mg
2+, Al
3+And O
2-Enter Sr
2Si
5N
8Lattice form sosoloid.Its emmission spectrum is seen Fig. 2 a, and excitation spectrum is seen Fig. 2 b.Can find the emmission spectrum broad of this luminescent material from Fig. 2 a, the spectrographic halfwidth is about 30nm, and the emission main peak is positioned at the ruddiness zone of 625nm; The excitation spectrum that can see this luminescent material from Fig. 2 b is very wide, extends to visible region from the ultraviolet region always, and particularly this luminescent material can effectively be excited by UV-light (300-420nm) and blue light (420-490nm) simultaneously. and its luminous intensity sees Table 1.Can find out the luminescent material that the present invention makes from table 1, its luminous intensity all is higher than comparative example.
Embodiment 2-7:
Take by weighing corresponding raw material by chemical formula composition and stoichiometry listed among each embodiment in the table 1, preparation process is identical with embodiment 1, and wherein employed reaction flux is the muriate of A, and the luminescent material luminous intensity that obtains sees Table 1.
The chemical formula of table 1 embodiment 1-7 and the characteristics of luminescence thereof (excitation wavelength is 450nm)
| Embodiment | Chemical formula | Emission main peak nm | Relative intensity % |
| 1 | Sr 1.90Mg 0.06Si 4.80Al 0.20O 0.20N 7.80:Eu 0.04 | 625 | 124 |
| 2 | Sr 1.90Li 0.12Si 4.90Al 0.10O 0.10N 7.90:Eu 0.04 | 623 | 135 |
| 3 | Sr 1.90Zn 0.06Si 4.80Al 0.20O 0.20N 7.80:Eu 0.04 | 618 | 113 |
| 4 | Sr 1.4Ba 0.5Mg 0.06Si 4.80Al 0.20O 0.20N 7.80:Eu 0.04 | 612 | 102 |
| 5 | Sr 1.96Si 4.70Ge 0.1Al 0.20O 0.20N 7.80:Eu 0.04 | 627 | 109 |
| 6 | Sr 1.96Si 4.80B 0.1Al 0.10O 0.20N 7.80:Eu 0.04 | 624 | 128 |
| 7 | Sr 1.96Si 4.7Al 0.20Ga 0.1O 0.30N 7.70:Eu 0.04 | 621 | 104 |
| Comparative example | Sr 1.96Si 5N 8:Eu 0.04 | 632 | 100 |
Embodiment 8:Sr
1.90Mg
0.06Si
4.80Al
0.20O
0.20N
7.80: Eu
0.04The preparation example of luminescent material (gas pressure sintering method)
Take by weighing SrCO by above-mentioned composition
3(53.5782 gram), MgO (0.573 gram), Si
3N
4(42.6797 gram), Al
2O
3(1.9434 gram) and Eu
2O
3(1.3413 gram), after adding normal hexane mix grinding was even, the boron nitride crucible of packing into was carried out roasting in the air pressure stove, feed the N of 10 barometric points
2, 1500 ℃ of insulations 6 hours, the gained luminescent material promptly obtained red illuminating material 100g of the present invention through pulverizing, pickling impurity removal, oven dry.From preparation process, this synthetic method is simple, and raw materials cost is low and chemical stability good, needn't carry out the batch mixing operation in glove box, thereby can realize low-cost and large batch of production.Its X diffracting spectrum as shown in Figure 3, as can be seen from the figure this powder comprises principal crystalline phase Sr
2Si
5N
8(greater than 80wt%) and paracrystalline phase Sr
2SiO
4(less than 20wt%).Its emmission spectrum sees that Fig. 4 a and excitation spectrum see Fig. 4 b.From Fig. 4 a, can find the emmission spectrum broad of this luminescent material, the spectrographic halfwidth is about 30nm, the emission main peak is positioned at the ruddiness zone of 618nm, the excitation spectrum that can see this luminescent material from Fig. 4 b is very wide, extend to visible region from the ultraviolet region always, particularly this luminescent material can effectively be excited by UV-light (300-420nm) and blue light (420-490nm) simultaneously, and its luminous intensity sees Table 2.Can find out the luminescent material that the present invention makes from table 2, its luminous intensity is higher than comparative example.
Embodiment 9-13:
Take by weighing corresponding raw material by chemical formula composition and stoichiometry listed among each embodiment in the table 2, preparation process is identical with embodiment 8, and the luminescent material luminous intensity that obtains sees Table 2.
The chemical formula of table 2 embodiment 8-13 and the characteristics of luminescence thereof (excitation wavelength is 450nm)
| Embodiment | Chemical formula | Emission main peak nm | Relative intensity % |
| 8 | Sr
1.90Mg
0.06Si
4.80Al
0.20O
0.20N
7.80: |
618 | 119 |
| 9 | Sr 1.90Li 0.12Si 4.80Al 0.20O 0.20N 7.80:Eu 0.04 | 620 | 125 |
| 10 | Sr 1.4Ba 0.5Mg 0.06Si 4.80Al 0.20O 0.20N 7.80:Eu 0.04 | 614 | 110 |
| 11 | Sr 1.96Si 4.70Ge 0.1Al 0.20O 0.20N 7.80:Eu 0.04 | 616 | 105 |
| 12 | Sr
1.96Si
4.70B
0.1Al
0.20O
0.20N
7.80: |
622 | 102 |
| 13 | Sr
1.96Si
4.7Al
0.20Ga
0.1O
0.30N
7.70: |
625 | 120 |
| Comparative example | Sr 1.96Si 5N 8:Eu 0.04 | 632 | 100 |
Embodiment 14:Sr
1.92Mg
0.04Si
4.90Al
0.10O
0.10N
7.90: Eu
0.04The preparation example (carbothermal reduction-nitridation) of luminescent material
Take by weighing Sr (NO by above-mentioned composition
3)
2(76.5568 gram), MgO (0.2931 gram), Al
2O
3(0.9343 gram), Si
3N
4(41.8921 gram), Eu
2N
3(2.5107 gram) and carbon dust (2.2424 gram), after adding ethanol mix grinding was even, the boron nitride crucible of packing into was carried out carbothermal reduction-nitridation in tube furnace, feed normal pressure N
2, be fusing assistant with 10g boric acid, 1600 ℃ of insulations 10 hours, the gained powder carried out the processing that removes of residual carbon again with same roasting condition after grinding.The gained luminescent material promptly obtains red illuminating material 100g of the present invention through pulverizing, pickling impurity removal, oven dry.From preparation process, this synthetic method is simple, needn't carry out the batch mixing operation in glove box, thereby can realize large batch of production.Its emmission spectrum and excitation spectrum are seen Fig. 5.From Fig. 5 a, can find the emmission spectrum broad of this luminescent material, the spectrographic halfwidth is about 30nm, the emission main peak is positioned at the ruddiness zone of 622nm, the excitation spectrum that can see this luminescent material from Fig. 5 b is very wide, extend to visible region from the ultraviolet region always, particularly this luminescent material can effectively be excited by UV-light (300-420nm) and blue light (420-490nm) simultaneously, and its luminous intensity sees Table 3.
The chemical formula of table 3 embodiment 14 and the characteristics of luminescence thereof (excitation wavelength is 450nm)
| Embodiment | Chemical formula | Emission main peak nm | Relative intensity % |
| 14 | Sr
1.92Mg
0.04Si
4.90Al
0.10O
0.10N
7.90: |
622 | 92 |
| Comparative example | Sr 1.96Si 5N 8:Eu 0.04 | 632 | 100 |
Claims (16)
1. nitrogen oxides luminescent material, its structural formula is Sr
1.90Mg
0.06Si
4.80Al
0.20O
0.20N
7.80: Eu
0.04
2. nitrogen oxides luminescent material, its structural formula is Sr
1.90Li
0.12Si
4.90Al
0.10O
0.10N
7.90: Eu
0.04
3. nitrogen oxides luminescent material, its structural formula is Sr
1.90Zn
0.06Si
4.80Al
0.20O
0.20N
7.80: Eu
0.04
4. nitrogen oxides luminescent material, its structural formula is Sr
1.4Ba
0.5Mg
0.06Si
4.80Al
0.20O
0.20N
7.80: Eu
0.04
5. nitrogen oxides luminescent material, its structural formula is Sr
1.96Si
4.70Ge
0.1Al
0.20O
0.20N
7.80: Eu
0.04
6. nitrogen oxides luminescent material, its structural formula is Sr
1.96Si
4.80B
0.1Al
0.10O
0.20N
7.80: Eu
0.04
7. nitrogen oxides luminescent material, its structural formula is Sr
1.96Si
4.7Al
0.20Ga
0.1O
0.30N
7.70: Eu
0.04
8. nitrogen oxides luminescent material, its structural formula is Sr
1.90Mg
0.06Si
4.80Al
0.20O
0.20N
7.80: Eu
0.04
9. nitrogen oxides luminescent material, its structural formula is Sr
1.90Li
0.12Si
4.80Al
0.20O
0.20N
7.80: Eu
0.04
10. nitrogen oxides luminescent material, its structural formula is Sr
1.4Ba
0.5Mg
0.06Si
4.80Al
0.20O
0.20N
7.80: Eu
0.04
11. a nitrogen oxides luminescent material, its structural formula are Sr
1.96Si
4.70Ge
0.1Al
0.20O
0.20N
7.80: Eu
0.04
12. a nitrogen oxides luminescent material, its structural formula are Sr
1.96Si
4.70B
0.1Al
0.20O
0.20N
7.80: Eu
0.04
13. a nitrogen oxides luminescent material, its structural formula are Sr
1.96Si
4.7Al
0.20Ga
0.1O
0.30N
7.70: Eu
0.04
14. a nitrogen oxides luminescent material, its structural formula are Sr
1.92Mg
0.04Si
4.90Al
0.10O
0.10N
7.90: Eu
0.08
15. a White-light LED illumination light source is characterized in that: contain the arbitrary described nitrogen oxides luminescent material of ultraviolet, near ultraviolet or blue-ray LED and claim 1-14.
16. a red LED light source is characterized in that: contain the arbitrary described nitrogen oxides luminescent material of ultraviolet or near ultraviolet LED and claim 1-14.
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| CN101671562B (en) * | 2007-07-02 | 2013-08-14 | 北京宇极科技发展有限公司 | Nitrogen oxides luminescent material and preparation method and application thereof |
| CN102559177B (en) * | 2010-12-28 | 2014-09-03 | 北京宇极科技发展有限公司 | Nitrogen oxides luminescent material and preparation method thereof and lighting source made of same |
| KR101786093B1 (en) | 2011-06-16 | 2017-10-18 | 엘지이노텍 주식회사 | Phosphor, phosphor manufacturing method, and light emitting device |
| CN103045257B (en) * | 2011-10-17 | 2015-09-23 | 有研稀土新材料股份有限公司 | A kind of nitride luminescent material and the luminescent device adopting this luminescent material to make |
| WO2014094975A1 (en) * | 2012-12-21 | 2014-06-26 | Merck Patent Gmbh | Luminescent substances |
| WO2014094974A1 (en) * | 2012-12-21 | 2014-06-26 | Merck Patent Gmbh | Phosphors |
| CN104109536B (en) * | 2013-04-19 | 2016-03-02 | 四川新力光源股份有限公司 | Oxynitride luminescent material, preparation method and the LED light source be made up of it |
| CN103305214A (en) * | 2013-06-16 | 2013-09-18 | 桂林理工大学 | Preparation method of color-regulatable Eu-doped fluorescent powder |
| CN103820107A (en) * | 2014-03-24 | 2014-05-28 | 中国科学院上海硅酸盐研究所 | Method for removing carbon powder from fluorescent powder prepared by carbothermal reduction reaction |
| WO2018021201A1 (en) * | 2016-07-26 | 2018-02-01 | デクセリアルズ株式会社 | Red phosphor and production method therefor, and white light source, illumination device, and display device using same |
| JP2018021167A (en) * | 2016-07-26 | 2018-02-08 | デクセリアルズ株式会社 | Red phosphor and method for producing the same, and white light source, illumination device and display device prepared therewith |
| CN111218280A (en) * | 2020-01-15 | 2020-06-02 | 厦门科煜光电有限公司 | Novel silicon nitrogen compound luminescent material and preparation method thereof |
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