CN102260500A - Method for making nitride/nitrogen oxide fluorescent powder for white light LED (Light Emitting Diode) - Google Patents
Method for making nitride/nitrogen oxide fluorescent powder for white light LED (Light Emitting Diode) Download PDFInfo
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- CN102260500A CN102260500A CN2011101526824A CN201110152682A CN102260500A CN 102260500 A CN102260500 A CN 102260500A CN 2011101526824 A CN2011101526824 A CN 2011101526824A CN 201110152682 A CN201110152682 A CN 201110152682A CN 102260500 A CN102260500 A CN 102260500A
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- 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
- C09K11/77347—Silicon Nitrides or Silicon Oxynitrides
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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
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Abstract
The invention discloses a method for making nitride/nitrogen oxide fluorescent powder for a white light LED (Light Emitting Diode). Raw materials are weighed according to the stoichiometric ratio of all elements in the chemical formula of the nitride/nitrogen oxide fluorescent powder and put in a saggar made of wave transparent materials after being fully mixed. The saggar is put in a professional microwave oven, a heating rate is controlled through regulating microwave power in a certain gas atmosphere, the raw materials are heated to a synthesis temperature, and the nitride/nitrogen oxide fluorescent powder for a white light LED is finally obtained through cooling and simple grinding. Compared with the prior art, the invention has the advantages that the synthesis temperature is lowered, the production period is shortened, so that the production cost is greatly reduced; meanwhile, the nitride/nitrogen oxide fluorescent powder for a white light LED can be synthesized under normal pressure, and the defects that the traditional method has a limitation on the condition of synthesis which always requires high pressure are overcome; and the prepared nitride/nitrogen oxide fluorescent powder has the advantages of good crystallinity, fine grain size, small grain distribution range, good grain disperstiveness, tidy form and the like.
Description
Technical field
The invention belongs to the luminescent material technical field, relate in particular to the preparation method of a kind of white light LEDs with nitride/oxynitride fluorescent material.
Background technology
At present, illumination total electricity consumption in the whole world accounts for 40 percent of global total electricity consumption, and the new lighting source of seeking to have concurrently power saving and environmental protection notion becomes the problem that solution is needed in national governments and scientific research circle badly.Compare with traditional incandescent light, luminescent lamp and high-intensity gas discharge lamp, realize that by semiconductor light-emitting-diode the white light LEDs of opto-electronic conversion not only has characteristics such as luminous efficiency height, life-span length, less energy-consumption and environmentally safe, also have the brightness height, volume is little, response is fast, the heating less with the reliability advantages of higher, be acknowledged as 21 century tool development potentiality and one of the new high-tech product of market outlook, be expected to replace tengsten lamp and mercuryvapour lamp becomes the new lighting source that has power saving and environmental protection concurrently.
Fluorescent material plays decisive role in the white light LEDs technology, its performance has determined the critical technical parameters such as luminescent spectrum, luminous efficiency, colour rendering index, colour temperature and work-ing life of white light LEDs.Tradition LED mainly comprises aluminate, silicate and sulfide with phosphor material powder, but the defective that these materials all exist some to overcome in application process.The aluminates system material is fit to be applied in the white light LEDs of high colour temperature, but its thermostability is relatively poor; Though the silicate systems material can increase the luminous intensity in ruddiness zone, improve colour rendering index and reduce colour temperature, thermostability remains one of its difficult problem that need solve; The easy deliquescence of sulfide system material, thereby cause in the product use affected by environment bigger.At present, the nitride/oxynitride fluorescent material progressively becomes the preferred of phosphor for white light LED material owing to features such as chemical stability with heat resistanceheat resistant cancellation, excellence and high-quantum efficiencies.
At present, traditional high temperature solid-state method is still adopted in the preparation of nitride/oxynitride fluorescent material, its reaction principle is self-diffusion and the mutual diffusion that reactant at high temperature passes through interface ion, make original chemical bond take place to rupture and form new key, this variation is to solid material inside or deep diffusion, thereby generates new material.High temperature solid-state method generally adopts traditional combustion gas or electric furnace heating, and its principle is the mode of thermal source by thermal conduction, radiation or convection current, and it is temperature required that material from outward appearance to inner essence progressively is heated to.The required synthesis temperature height of this heating means, time are long, and it is inhomogeneous to be heated, and the fluorescent material ratio that makes is easier to caking, and particle grain size is bigger.Especially when synthesizing nitride/oxynitride fluorescent material, because employed nitride raw material has very strong covalent linkage, spread coefficient is low, therefore need react synthetic under higher synthesis temperature and pressure, with the reactive behavior of raising raw material.The reaction conditions that this is harsh, the special device of needs design high temperature high voltage resistant, and synthetic required energy consumption is bigger, has increased production cost.On the other hand; just because of the synthesis condition that uses High Temperature High Pressure; make the powder reuniting of preparation serious; usually also need to carry out aftertreatment as technologies such as pulverizing; and for the hardness height, the serious fluorescent material of reuniting, pulverizing will inevitably cause the destruction of particle surface; cause the exhibiting high surface generation of defects, directly influence luminescent properties.In addition, the distribution of granular size is also inhomogeneous, makes that the tap density of powder is little, and scattering coefficient increases and reduced luminous efficiency.
In order to reduce synthesis temperature, publication number is that the method that the Chinese invention patent application " method for preparing silicon-based oxynitride fluorescent powder " of CN101818063A discloses a kind of second-heating has prepared silicon-based oxynitride fluorescent powder, reduce synthesis temperature, thereby reduced production cost, reduction powder reuniting degree.But this method is a second-heating, and technology is complicated.
In addition, some documents have also been reported the employing softening method both at home and abroad, method synthesize white light LED nitride/oxynitride fluorescent material such as colloidal sol～gel method, homogeneous precipitation method, low-temperature combustion synthesis, hydrothermal synthesis method for example, advantages such as synthesis temperature is low though these class methods have, reaction is even, the particle diameter preparation powder is less, but the efficient of its synthetic powder and output are lower, are not suitable for the large-scale industrial production needs.
Microwave heating is the coupling by material and microwave electric field or magnetic field, changes micro-wave energy a kind of heating means of heat energy into, has advantages such as rate of heating is fast, heat energy utilization rate height, environmental protection.At present, existing bibliographical information the application of microwave heating method in some fluorescent material systems, for example application number is that 200810120381.1 Chinese patent application discloses the method with preparing blue fluorescent powder for PDP by high temperature microwave method, application number is that 201010030805.2 Chinese patent application discloses the method for preparing silicate yellow fluorescent powder with microwave method, application number is that the Chinese patent application of 200910100430.x discloses the method for preparing the RE phosphate green emitting phosphor with microwave method, publication number is that the Chinese patent application of CN1702143A discloses the method for preparing sulphide fluorescent material with microwave method, publication number be US2003/0230740A1 U.S. Patent Application Publication prepare the method for borate fluorescent powder with microwave method, publication number is that the korean patent application of KR2005088793A discloses with microwave method and prepares vacuum ultraviolet-excited green emitting phosphor.
But, for nitride/oxynitride fluorescent material,, still adopt traditional High Temperature Gas pressing established law at present owing to be subjected to the synthesis condition restriction of High Temperature High Pressure, also do not use the relevant report of microwave heating method preparation.
Summary of the invention
The objective of the invention is deficiency at preparation method's existence of existing nitride/oxynitride fluorescent material, the preparation method of a kind of white light LEDs with nitride/oxynitride fluorescent material is provided, this method can reduce the synthesis temperature and the synthesis pressure of nitride/oxynitride fluorescent material, obtains having that particle diameter is thin, particle size distribution is narrow, the nitride/oxynitride fluorescent material of advantage such as good crystallinity, pattern are regular.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of white light LEDs preparation method of nitride/oxynitride fluorescent material, be specially: the stoichiometric ratio according to each element in the described nitride/oxynitride fluorescent material chemical formula takes by weighing raw material, fully pack into behind the mixing in the saggar of making by electromagnetic wave transparent material, then saggar is put into professional microwave oven, under certain atmosphere, by adjusting microwave power control temperature rise rate, be heated to synthesis temperature, after cooling, the simple grinding obtains white light LEDs nitride/oxynitride fluorescent material.
Raw material can be simple substance, nitride, oxide compound, fluorochemical, muriate, bromide or the phosphoric acid salt of respective element in the described nitride/oxynitride fluorescent material chemical formula, also can be the precursor that contains the desired raw material element.Raw material can carry out thermal pretreatment, also can disposablely be heated rapidly to temperature required.
Nitride/oxynitride fluorescent material includes but not limited to that chemical formula is M～alpha～Si
12～(m+n)Al
M+nO
nN
16～ n: xR, M
2Si
5N
8: xR, MSi
2O
2N
2: xR, beta～Si
6～zAl
zO
zN
8～z: xR, MAlSiN
3: xR, MAlSi
4N
7: xR, MYSi
4N
7: the nitride/oxynitride fluorescent material of systems such as xR.Wherein, rare-earth element R can be selected from a kind of element in Eu, Ce, Tb, Sm, Pr, Dy, Yb, Tm, Nd, the Gd element or the mixing of two or more elements.The source of rare-earth element R includes but not limited to the one or more kinds of mixtures in rare earth oxide, rare earth fluorine, rare earth chloride, rare earth bromide, rare earth nitrate, rare earth nitride, the rare earth metal.
The specialty microwave oven is selected from a kind of in net belt type microwave oven/kiln, push-plate type microwave oven/kiln, roller bed type microwave oven/kiln, shuttle-type microwave oven/kiln, box microwave oven/kiln and the bell-jar microwave oven/kiln.The microwave frequency of described professional microwave oven is 300MHz～300GHz, and preferred frequency is 2.45,5.8,0.915,24.15GHz.
Saggar is made by the good material of wave penetrate capability, preferably by Al
2O
3, one or more the matrix material in the material such as BN, mullite makes.
The establishment of gas atmosphere generally is after the saggar that raw material is housed is put into professional microwave oven, at first professional microwave oven to be vacuumized processing in the furnace chamber of specialty microwave oven, feeds gas then to normal pressure or higher pressure, and gas includes but not limited to N
2, H
2, NH
3, Ar, He, CH
4, one or several the mixed gas in the gas such as CO.The flow velocity that feeds gas in the furnace chamber of professional microwave oven is 0～10L/min, and preferable flow rate is 0.1L/min～0.5L/min.
For synthetic some purity nitrogen matter fluorescent powder, for avoiding using in the building-up process purity nitrogen raw material of easy decomposing oxidation in air, the corresponding oxide compound of preferred employing is a raw material, and applied microwave is synthesized target product in conjunction with methods such as carbothermal reduction-nitridation or gas reduction nitrogenize.In reaction process, can in furnace chamber, charge into nitrogenous gas, as N
2, NH
3Deng gas, or in raw material, be added on to decompose in the reaction process and generate N
2And H
2NH
4HCO
3, NH
4Cl, NH
4NO
3, NH
4HSO
4, (NH
4)
2CO
3, NH
4HCO
3, NH
4F, NH
4Br, NH
4A kind of or two or more mixture in the nitrogenous element ammonium salt such as I.The purpose of above method all is that the reduction nitridation for oxide compound in the reaction process provides nitrogenous source, to guarantee the complete reduction nitridation of raw material.
In the building-up process, if nitride/oxynitride fluorescent material chemical formula middle-weight rare earths element R needs reduction, its reduction can be adopted reduction powders such as carbon dust, organic carbon, also can adopt N
2/ H
2, CH
4, NH
3, CO, H
2Wait one or several mixing reducing atmosphere to reduce.
In order reacting fully fully, and to improve the crystallinity of prepared powder, preferably to be incubated processing after being heated to synthesis temperature, soaking time is preferably 0.1h～100h, more preferably 0.1h～10h.
In order further to reduce synthesis temperature, improve the crystallinity of prepared powder, preferably in raw material, add various solubility promoters, solubility promoter includes but not limited to NH
4Cl, SrCl
2, SrF
2, H
3BO
3And AlF
3Deng in one or several mixing.
In order to improve the temperature rise rate of raw material, when especially participating in reaction, preferably add auxilliary hot material at the saggar outer wall for the bad raw material of absorbing property, this auxilliary hot material directly contacts placement with the saggar outer wall, perhaps places apart from certain intervals with the saggar outer wall; For the auxilliary hot material that does not react with raw material, preferably directly it is added in raw material, through after the microwave heating, again applied chemistry method and/or physical method remove contained in the synthetic nitride/oxynitride fluorescent material should auxilliary hot material.
Auxilliary hot material includes but not limited to SiC, ferrite, Co
2O
3, CuO, decolorizing carbon, graphite, WO
3, MoS
2, PbS, CuFeS
2, WC and ZrO
2Deng in one or several mixture.
Contained auxilliary hot material can pass through acidity/alkalescence/organic solvent processing removal in the applied chemistry method removal nitride/oxynitride fluorescent material, and wherein acid solvent includes but not limited to H
2SO
4, HCl, HNO
3, HF, H
2CO
3Deng in one or several mixing, basic solvent includes but not limited to NaOH, KOH, NH
3H
2The mixing of one or several among the O etc., organic solvent include but not limited to one or several the mixing in ethanol, acetone, the hexane etc.
Contained auxilliary hot material mainly is to remove by methods such as electric field, magnetic field, gravity field in the Applied Physics method removal nitride/oxynitride fluorescent material.
In order to increase heat insulation effect, preferably saggar is put into attemperator, carry out microwave heating then.Insert lagging material between saggar and the attemperator inwall.Attemperator can be insulated tank, incubation chamber or insulation casket etc.Attemperator is to be made by the good material of wave penetrate capability, preferably by Al
2O
3, one or more the matrix material in the material such as BN, mullite makes.Equally, the lagging material of inserting between saggar and insulated tank inwall also is the good material of wave penetrate capability, is preferably Al
2O
3, one or more the matrix material in the material such as BN, mullite.
Process of cooling adopts and cools to room temperature with the furnace, perhaps adopts by adjusting microwave power and is cooled to room temperature with certain rate of temperature fall.
What deserves to be mentioned is that preparation method of the present invention not only can prepare white light LEDs nitride/oxynitride fluorescent material under the atmosphere of elevated pressures, can also under normal pressure, prepare white light LEDs nitride/oxynitride fluorescent material.Therefore, the present invention has overcome generally needs synthetic restriction under condition of high voltage in the traditional method.
Temperature rise rate among the preparation method of the present invention is preferably 5 ℃/min～200 ℃/min, more preferably 20 ℃/min～50 ℃/min.Synthesis temperature is generally 900 ℃～3000 ℃, more preferably 1000 ℃～2000 ℃.Utilizing white light LEDs that preparation method of the present invention obtains is 0.1 μ m～20 μ m with the grain-size of nitride/oxynitride fluorescent material.
When the chemical formula of nitride/oxynitride fluorescent material is M～alpha～Si
12～(m+n)Al
M+nO
nN
16～n: xR, wherein M is Ca, Sr, Ba, Lu, Li, Mg, one or more kinds of mixtures in the elements such as Y, R is Mn, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Tm, one or more kinds of mixtures in the elements such as Yb, 0.5≤m≤2.0,1≤n≤1.8, during 0.1mol%≤x≤15mol%, required synthesis condition is when using preparation method's synthetizing phosphor powder of the present invention: normal pressure, 1300 ℃～1550 ℃ of synthesis temperatures, required synthesis condition during with traditional air pressure synthetic method synthetizing phosphor powder: 1750 ℃ of synthesis temperatures, pressure 0.5MPa compares, synthesis temperature has reduced by 200 ℃～450 ℃, and synthetic only the need finished under normal pressure.The excitation wavelength of synthetic fluorescent material is 200nm～500nm, and emission wavelength is 450nm～750nm.
When the chemical formula of nitride/oxynitride fluorescent material is M
2Si
5N
8: xR, wherein M is Ca, Sr, Ba, one or more kinds of mixtures in the elements such as Mg, R is Mn, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Tm, one or more kinds of mixtures in the elements such as Yb, during 0.1mol%≤x≤15mol%, required synthesis condition is when using preparation method's synthetizing phosphor powder of the present invention: normal pressure, 1300 ℃～1550 ℃ of synthesis temperatures, required synthesis condition during with traditional air pressure synthetic method synthetizing phosphor powder: 1600 ℃ of synthesis temperatures, pressure 0.5MPa compares, synthesis temperature has reduced by 50 ℃～300 ℃, and synthetic only the need finished under normal pressure.The excitation wavelength of synthetic fluorescent material is 200nm～500nm, and emission wavelength is 500nm～800nm.
When the chemical formula of nitride/oxynitride fluorescent material is MSi
2O
2N
2: xR, wherein M is Ca, Sr, Ba, the mixture of one or more in the elements such as Mg, R is Mn, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Tm, the mixture of one or more in the elements such as Yb, during 0.1mol%≤x≤15mol%, required synthesis condition is when using preparation method's synthetizing phosphor powder of the present invention: normal pressure, 1300 ℃～1500 ℃ of synthesis temperatures, required synthesis condition during with traditional air pressure synthetic method synthetizing phosphor powder: 1550 ℃ of synthesis temperatures, 0.5MPa compare, synthesis temperature has reduced by 50 ℃～250 ℃, and synthetic only the need finished under normal pressure.The excitation wavelength of synthetic fluorescent material is 200nm～500nm, and emission wavelength is 500nm～750nm.
When the chemical formula of nitride/oxynitride fluorescent material is beta～Si
6～zAl
zO
zN
8～z: xR, wherein R is the one or more kinds of mixtures in the elements such as Mn, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Tm, Yb, 0.3≤z≤2.5 o'clock, required synthesis condition is during with preparation method's synthetizing phosphor powder of the present invention: 1650 ℃～1750 ℃ of normal pressure, synthesis temperatures, required synthesis condition during with traditional air pressure synthetic method synthetizing phosphor powder: 1900 ℃ of synthesis temperatures, 1MPa compare, synthesis temperature has reduced by 150 ℃～250 ℃, and synthetic only the need finished under normal pressure.The excitation wavelength of synthetic fluorescent material is 200nm～500nm, and emission wavelength is 500nm～750nm.
When the chemical formula of nitride/oxynitride fluorescent material is MAlSiN
3: xR, wherein M is Ca, Sr, Ba, Li, Mg, the mixture of one or more in the elements such as Y, R is Mn, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Tm, one or more kinds of mixtures in the elements such as Yb, during 0.1mol%≤x≤15mol%, required synthesis condition is during with preparation method's synthetizing phosphor powder of the present invention: normal pressure, 1350 ℃～1550 ℃ of synthesis temperatures, required synthesis condition during with traditional air pressure synthetic method synthetizing phosphor powder: 1600 ℃ of synthesis temperatures, 1MPa compares, synthesis temperature has reduced by 50 ℃～250 ℃, and synthetic only the need finished under normal pressure.The excitation wavelength of synthetic fluorescent material is 200nm～500nm, and emission wavelength is 500nm～750nm.
When the chemical formula of nitride/oxynitride fluorescent material is MAlSi
4N
7: xR, wherein M is Ca, Sr, Ba, Li, Mg, one or more kinds of mixtures in the elements such as Y, R is Mn, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Tm, one or more kinds of mixtures in the elements such as Yb, during 0.1mol%≤x≤15mol%, required synthesis condition is when using preparation method's synthetizing phosphor powder of the present invention: normal pressure, 1500 ℃～1700 ℃ of synthesis temperatures, required synthesis condition during with traditional air pressure synthetic method synthetizing phosphor powder: 1750 ℃ of synthesis temperatures, 0.48Mpa compare, synthesis temperature has reduced by 50 ℃～250 ℃, and synthetic only the need finished under normal pressure.The excitation wavelength of synthetic fluorescent material is 200nm～500nm, and emission wavelength is 500nm～750nm.
When the chemical formula of nitride/oxynitride fluorescent material is MYSi
4N
7: xR, wherein M is Ca, Sr, Ba, one or more kinds of mixtures in the elements such as Mg, R is Mn, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Tm, one or more kinds of mixtures in the elements such as Yb, during 0.1mol%≤x≤15mol%, required synthesis condition is when using preparation method's synthetizing phosphor powder of the present invention: normal pressure, 1300 ℃～1550 ℃ of synthesis temperatures, required synthesis condition during with traditional air pressure synthetic method synthetizing phosphor powder: 1600 ℃ of synthesis temperatures, 0.5Mpa compare, synthesis temperature has reduced by 50 ℃～300 ℃, and synthetic only the need finished under normal pressure.The excitation wavelength of synthetic fluorescent material is 200nm～500nm, and emission wavelength is 500nm～750nm.
The nitride/oxynitride fluorescent material that utilizes preparation method provided by the invention to obtain is used for white light LEDs at present more; but along with development of science and technology; the application of this nitride/oxynitride fluorescent material has more than and is defined in white light LEDs; any technological improvement or purposes change; only otherwise break away from technical spirit of the present invention, all should drop within protection scope of the present invention.
Compared with prior art, the present invention utilizes microwave method synthesize white light LED nitride/oxynitride fluorescent material, and microwave and reactant directly are coupled, with the whole heating of reactant, make the inside and outside thermally equivalent simultaneously of material monolithic on the one hand, the field distribution of reactant internal temperature is even, and thermograde is little; Be in the microwave electromagnetic field owing to reactant on the other hand, inner particles is subjected to the effect of electromagnetic field, and the particle activity is bigger, thereby promotes ion diffusion, improves the probability of collision mutually, helps reducing temperature of reaction, the shortening reaction times.Concrete beneficial effect is embodied in:
1, greatly reduces the required temperature of synthesizing nitride/oxynitride fluorescent powder, reduced energy consumption, thereby reduced production cost significantly;
2, can be at synthesize white light LED nitride/oxynitride fluorescent material under the normal pressure, having overcome must be in synthetic restriction under the condition of high voltage in the traditional method;
3, direct heating synthesizes and does not need insulation to handle, and perhaps soaking time shortens greatly, has shortened the production cycle on the one hand, has improved production efficiency; Reduce the gas usage that consumes in the sintering process on the other hand, reduced unnecessary pollution;
4, the nitride/oxynitride fluorescent material for preparing has advantages such as particle diameter is thin, good crystallinity, particle size distribution is narrow, pattern is regular, particles dispersed is good;
5, synthetic nitride/oxynitride fluorescent material only needs simple grinding, does not need the high strength break process through the later stage;
The characteristics of luminescence of the nitride/oxynitride fluorescent material that 6, prepares is after optimizing, and luminous efficiency can be suitable with the luminous efficiency of commercially available fluorescent material, but production cost is significantly less than commercially available fluorescent material;
Therefore, preparation method of the present invention be a kind of fast, efficient, energy-saving and environmental protection, with low costly be easy to realize the preparation method of the white light LEDs of scale operation again with nitride/oxynitride fluorescent material.
Description of drawings
Fig. 1 is the preparation technology schema of white light LEDs with nitride/oxynitride fluorescent material;
Fig. 2 is 1550 ℃ of synthetic alpha～SiAlON:Eu among the embodiment 1
2+The XRD spectra of fluorescent material;
Fig. 3 is 1550 ℃ of synthetic alpha～SiAlON:Eu among the embodiment 1
2+The fluorescence spectrum spectrogram of fluorescent material;
Fig. 4 is 1550 ℃ of synthetic alpha～SiAlON:Eu among the embodiment 1
2+The particle size distribution figure of fluorescent material;
Fig. 5 is 1550 ℃ of synthetic alpha～SiAlON:Eu among the embodiment 1
2+The SEM shape appearance figure of fluorescent material.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described in further detail.
Embodiment 1:
Ca～alpha～Si
12～(m+n)Al
M+nO
nN
16～n: xEu
2+The synthetic method of fluorescent material is as follows:
With chemical formula M
Val+ M/val+Si
12～(m+n)Al
M+nO
nN
16～n: xEu
2+(M=Ca wherein, m=2, n=1, x=0.07) stoichiometric ratio in takes by weighing an amount of Si
3N
4, AlN, Eu
2O
3, CaCO
3As raw material, then raw material is placed on Si
3N
4Mix in the mortar and grinding; With the BN saggar of packing into of the raw material after grinding, put into microwave oven then, and feed N
2With H
2Mixed gas, H in the mixed gas
2The quality percentage composition be 5%; By adjusting power,, under the gas flow rate of 0.3L/min, be heated to 1550 ℃, and under normal pressure, be incubated 2h with the temperature rise rate of 40 ℃/min; Turn off microwave source after reaction finishes, reactant naturally cools to room temperature, after the taking-up, through Si
3N
4Mortar simply grinds, and obtains the yellow powder product.
Use XRD, fluorescence spectrum, sreen analysis and scanning electron microscope and characterize the powder for preparing.Material phase analysis the results are shown in Figure 2, from the test the material phase analysis result as can be known, powder is made up of the alpha～SiAlON of single phase, and by the XRD diffraction peak as can be known, prepared powder crystallinity is better.The fluorescence spectrum spectrogram is seen Fig. 3, excites down at the 450nm wavelength, and this fluorescent material transmitted wave peak position is in the sodium yellow of 590nm, with YAG:Ce
3+Fluorescent material has relatively strengthened the luminous of red area.Fig. 4 and Fig. 5 are respectively the size-grade distribution and the patterns of this powder, and particle diameter is 3 μ m～5 μ m, have powder granularity narrow distribution range, pattern is regular, particles dispersed is good characteristics.
In addition, excite down at the 450nm wavelength, the external quantum efficiency of the powder of test is 43%, and that its quantum yield can be with commercial powder through optimizing after is suitable for powder.
Identical with embodiment 1, embodiment 2～10 also is Ca～alpha～Si
12～(m+n)Al
M+nO
nN
16～n: xEu
2+The synthetic method of fluorescent material, this method is basic identical with embodiment 1, and that different is chemical formula M
Val+ M/val+Si
12～ (m+n)Al
M+nO
nN
16～n: xEu
2+In M, m, n, x value, and synthesis temperature, soaking time adopts different values, and is as shown in table 1 below.
Table 1: embodiment 2～10 synthetic alpha～SiAlON:Eu
2Component content and processing condition during fluorescent material
Use XRD, fluorescence spectrum, size-grade distribution and quantum yield and characterize the powder that the foregoing description 2～10 prepares.The similar Fig. 2 of material phase analysis result, from the test the material phase analysis result as can be known, powder is made up of the alpha～SiAlON of single phase, and by the XRD diffraction peak as can be known, prepared powder crystallinity is better.The similar Fig. 4 of the size-grade distribution of powder and pattern and Fig. 5, the powder granularity narrow distribution range, pattern is regular, particles dispersed is good.The characteristics of luminescence and particle size are as shown in table 2 below.
Table 2: embodiment 2～10 synthetic alpha～SiAlON:Eu
2The characteristics of luminescence of fluorescent material and particle size
| Embodiment | Excitation wavelength | Emission wavelength | Luminous intensity | External quantum | Particle diameter | |
| 2 | 450nm | 590nm | 3800 | 40％ | 5～7μm | |
| 3 | 450nm | 593nm | 3820 | 38％ | 3～5μm | |
| 4 | 450nm | 603nm | 3700 | 35％ | 5～7μm | |
| 5 | 450nm | 590nm | 3850 | 40％ | 3～5μm | |
| 6 | 450nm | 593nm | 3562 | 37％ | 3μm | |
| 7 | 450nm | 525nm | 3100 | 28％ | 3～5μm | |
| 8 | 450nm | 598nm | 3256 | 32％ | 3～5μm | |
| 9 | 450nm | 596nm | 3150 | 31％ | 3～5μm | |
| 10 | 450nm | 580nm | 3900 | 42％ | 3～5μm |
Embodiment 11:
MSi
2O
2N
2: xEu
2+The synthetic method of (M=Sr, Ca, Ba, Mg) fluorescent material is as follows:
With chemical formula MSi
2O
2N
2: xEu
2+(M=Sr, x=0.05) stoichiometric ratio in takes by weighing an amount of SrCO
3, SiO
2, Si
3N
4And Eu
2O
3As raw material, raw material is placed on mixes in the agate mortar and grinding then; With the Al that packs into of the raw material after grinding
2O
3Saggar places Al with saggar
2O
3In the insulated tank, and between saggar and insulated tank, fill insulating cotton, place the auxilliary hot material of SiC at the saggar outer wall simultaneously; Then insulated tank is put into microwave oven; By adjusting power, with the temperature rise rate of 20 ℃/min, under the gas flow rate of 0.3L/min, normal pressure is heated to 1500 ℃, and insulation 2h; Turn off microwave source after reaction finishes, reactant naturally cools to room temperature with stove, and synthetic fluorescent material is simply ground through agate mortar, and products therefrom is that particle diameter is thin, the yellow-green colour powder of no sintering phenomenon.
Use XRD, fluorescence spectrum, sreen analysis and quantum yield and characterize the powder for preparing.From the test the material phase analysis result as can be known: powder is by pure phase SrSi
2O
2N
2Form, and crystallinity is better; Excite down at the 450nm wavelength, this fluorescent material transmitted wave peak position is in the yellow-green light of 544nm; Diameter of particle is 3 μ m～5 μ m, and particle size distribution is narrow, pattern is regular, particles dispersed is good; Excite down at the 450nm wavelength, the external quantum efficiency of this powder is 37%, and that its quantum yield can be with commercial powder through optimizing after is suitable for powder.
Embodiment 12～17:
Identical with embodiment 11, embodiment 12～17 also is MSi
2O
2N
2: xEu
2+The synthetic method of (M=Sr, Ca, Ba, Mg) fluorescent phosphor powder, this method is basic identical with embodiment 11, and that different is chemical formula MSi
2O
2N
2: xEu
2+In M, x value, and synthesis temperature, soaking time adopts different values, and is as shown in table 3 below.
Table 3: embodiment 2～10 synthetic MSi
2O
2N
2: Eu
2+Component content and processing condition during fluorescent material
Use XRD, fluorescence spectrum, sreen analysis and quantum yield and characterize the powder for preparing.From the test the material phase analysis result as can be known: powder is by pure phase MSi
2O
2N
2Form, and crystallinity is better; The powder granularity narrow distribution range, pattern is regular, particles dispersed is good; The characteristics of luminescence and particle size are as shown in table 4 below.
Table 4: embodiment 12～17 synthetic MSi
2O
2N
2: Eu
2+The characteristics of luminescence of fluorescent material and particle size
| Embodiment | Excitation wavelength | Emission wavelength | Luminous intensity | Quantum yield | Particle diameter |
| 12 | 450nm | 550nm | 4100 | 35％ | 3～5μm |
| 13 | 450nm | 495nm | 3900 | 32％ | 3～5μm |
| 14 | 450nm | 560nm | 4100 | 35％ | 3～5μm |
| 15 | 450nm | 544nm | 4200 | 36％ | 3～5μm |
| 16 | 450nm | 553nm | 3750 | 30％ | 3～5μm |
| 17 | 450nm | 550nm | 3580 | 28％ | 3～5μm |
Embodiment 18:
Beta～sialon:Eu
2+The synthetic method of fluorescent material is as follows:
With chemical formula beta～Si
6～zAl
zO
zN
8～z: (x=0.005) stoichiometric ratio in takes by weighing an amount of Si to xR for R=Eu, z=0.5
3N
4, Al
2O
3, AlN, Eu
2O
3As raw material, raw material is placed on mixes in the agate mortar and grinding then; With the BN saggar of packing into of the raw material after grinding, put into microwave oven then; By adjusting power, with the temperature rise rate of 20 ℃/min, under the gas flow rate of 0.3L/min, normal pressure is heated to 1750 ℃, and insulation 2h; Turn off microwave source after reaction finishes, reactant naturally cools to room temperature with stove, and synthetic fluorescent material is simply ground through agate mortar, and products therefrom is that particle diameter is thin, the light green powder of no sintering phenomenon.
Use XRD, fluorescence spectrum, size-grade distribution, grain morphology and quantum yield and characterize the powder for preparing.From the test the material phase analysis result as can be known: powder is by the beta～sialon:Eu of pure phase
2+Form, and crystallinity is better; Excite down at the 450nm wavelength, this fluorescent material transmitted wave peak position is in the yellow-green light of 540nm; Diameter of particle is 3 μ m～5 μ m, and particle size distribution is narrow, pattern is regular, particles dispersed is good; Excite down at the 450nm wavelength, the external quantum efficiency of this powder is 38%, and that its quantum yield can be with commercial powder through optimizing after is suitable for powder.
Embodiment 19～23:
Identical with embodiment 18, embodiment 19～23 also is beta～sialon:Eu
2+The synthetic method of fluorescent material, this method is basic identical with embodiment 18, and that different is chemical formula beta～Si
6～zAl
zO
zN
8～z: the z among the xR, x value, and synthesis temperature, soaking time adopts different values, and is as shown in table 5 below.
Table 5: embodiment 19～23 synthetic Beta～sialon:Eu
2+Component content and processing condition during fluorescent material
Use XRD, fluorescence spectrum, size-grade distribution, grain morphology and quantum yield and characterize the powder for preparing.From the test the material phase analysis result as can be known: powder is by the beta～sialon:Eu of pure phase
2+Form, and crystallinity is better; The powder granularity narrow distribution range, pattern is regular, particles dispersed is good; The characteristics of luminescence and particle size are as shown in table 6 below.
Table 6: embodiment 19～23 synthetic beta～sialon:Eu
2+The characteristics of luminescence of fluorescent material and particle size
| Embodiment | Excitation wavelength | Emission wavelength | Luminous intensity | Quantum yield | Particle diameter |
| 19 | 450 | 540 | 1800 | 23％ | 3～ |
| 20 | 450 | 545 | 3200 | 33％ | 3～5μm |
| 21 | 450 | 547 | 2000 | 27％ | 3～5μm |
| 22 | 450 | 545 | 1500 | 20％ | 3～5μm |
| 23 | 450 | 544 | 2200 | 29％ | 3～5μm |
Claims (33)
1. a white light LEDs is with the preparation method of nitride/oxynitride fluorescent material, it is characterized in that: the stoichiometric ratio according to each element in the described nitride/oxynitride fluorescent material chemical formula takes by weighing raw material, fully pack into behind the mixing in the saggar of making by electromagnetic wave transparent material, then saggar is put into professional microwave oven, under certain atmosphere, by adjusting microwave power control temperature rise rate, be heated to synthesis temperature, after cooling, the simple grinding obtains white light LEDs nitride/oxynitride fluorescent material.
2. the white light LEDs according to claim 1 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: described raw material is a kind of in the simple substance, nitride, oxide compound, fluorochemical, muriate, bromide, phosphoric acid salt of respective element in the nitride/oxynitride fluorescent material chemical formula, or contains the precursor of desired raw material element.
3. the white light LEDs according to claim 1 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: described nitride/oxynitride fluorescent material is that the system chemical formula is M～alpha～Si
12～(m+n)Al
M+nO
nN
16～ n: xR, M
2Si
5N
8: xR, MSi
2O
2N
2: xR, beta～SiAlON:xR, MAlSiN
3: xR, MAlSi
4N
7: xR, MYSi
4N
7: the nitride/oxynitride fluorescent material of xR, wherein rare-earth element R is selected from a kind of element in Eu, Ce, Tb, Sm, Pr, Dy, Yb, Tm, Nd, the Gd element or the mixing of two or more elements.
4. the white light LEDs according to claim 3 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: described rare-earth element R is from the one or more kinds of mixtures in rare earth oxide, rare earth fluorine, rare earth chloride, rare earth bromide, rare earth nitrate, rare earth nitride, the rare earth metal.
5. white light LEDs according to claim 1 is characterized in that with the preparation method of nitride/oxynitride fluorescent material: described professional microwave oven is selected from a kind of in net belt type microwave oven/kiln, push-plate type microwave oven/kiln, roller bed type microwave oven/kiln, shuttle-type microwave oven/kiln, box microwave oven/kiln and the bell-jar microwave oven/kiln.
6. the white light LEDs according to claim 1 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: the microwave frequency of described professional microwave oven is 300MHz～300GHz.
7. the white light LEDs according to claim 6 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: the microwave frequency of described professional microwave oven is 2.45GHz, 5.8GHz, 0.915GHz or 24.15GHz.
8. the white light LEDs according to claim 1 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: described saggar is by Al
2O
3, one or several the matrix material among the BN, mullite material makes.
9. the white light LEDs according to claim 1 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: described gas comprises N
2, H
2, NH
3, Ar, He, CH
4, one or several the mixed gas in the CO gas.
10. according to the preparation method of claim 1 or 9 described white light LEDs usefulness nitride/oxynitride fluorescent material, it is characterized in that: the interior gas flow rate of furnace chamber that described gas enters professional microwave oven is 0.1L/min～10L/min.
11. the white light LEDs according to claim 10 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: described gas flow rate is 0.1L/min～0.5L/min.
12. white light LEDs according to claim 1 is characterized in that: add NH in the described raw material with the preparation method of nitride/oxynitride fluorescent material
4HCO
3, NH
4Cl, NH
4NO
3, NH
4HSO
4, (NH
4)
2CO
3, NH
4HCO
3, NH
4F, NH
4Br, NH
4A kind of or two or more mixture in the I ammonium salt is used for decomposing generation N in reaction process
2And H
2, for reaction provides N
2Source and H
2The source.
13. the white light LEDs according to claim 1 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: add solubility promoter in the described raw material, described solubility promoter comprises NH
4Cl, SrCl
2, SrF
2, H
3BO
3And AlF
3In one or several mixture.
14. the white light LEDs according to claim 1 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: before professional microwave oven internal heating, described raw material carries out thermal pretreatment.
15. the white light LEDs according to claim 1 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: described saggar outer wall is provided with auxilliary hot material.
16. the white light LEDs according to claim 15 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: described auxilliary hot material comprises SiC, ferrite, Co
2O
3, CuO, decolorizing carbon, graphite, WO
3, MoS
2, PbS, CuFeS
2, WC and ZrO
2In one or several mixture.
17. the white light LEDs according to claim 1 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: described saggar is at first put into the attemperator of being made by the good material of wave penetrate capability, insert lagging material between saggar and the attemperator inwall, carry out microwave heating then.
18. the white light LEDs according to claim 17 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: described attemperator is by Al
2O
3, one or more the matrix material among the BN, mullite material makes.
19. the white light LEDs according to claim 1 preparation method of nitride/oxynitride fluorescent material is characterized in that: described process of cooling is to cool to room temperature with the furnace, or is cooled to room temperature by adjusting microwave power with certain rate of temperature fall.
20. the white light LEDs according to claim 1 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: be incubated processing after being heated to synthesis temperature, soaking time is 0.1h～100h.
21. the white light LEDs according to claim 20 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: described soaking time is 0.1h～10h.
22. white light LEDs according to claim 1 with the preparation method of nitride/oxynitride fluorescent material, is characterized in that: described temperature rise rate is 5 ℃/min～200 ℃/min.
23. white light LEDs according to claim 22 with the preparation method of nitride/oxynitride fluorescent material, is characterized in that: described temperature rise rate is 20 ℃/min～50 ℃/min.
24. the white light LEDs according to claim 1 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: described synthesis temperature is 900 ℃～3000 ℃.
25. the white light LEDs according to claim 1 preparation method of nitride/oxynitride fluorescent material, it is characterized in that: the grain-size of described nitride/oxynitride fluorescent material is 0.1 μ m～20 μ m.
26. white light LEDs according to claim 3 with the preparation method of nitride/oxynitride fluorescent material, is characterized in that: when the chemical formula of nitride/oxynitride fluorescent material is M～alpha～Si
12～(m+n)Al
M+nO
nN
16～n: xR, wherein M is one or more kinds of mixtures in the elements such as Ca, Sr, Ba, Lu, Li, Mg, Y, 0.5≤m≤2.0,1≤n≤1.8, during 0.1mol%≤x≤15mol%, synthesis temperature is 1300 ℃～1550 ℃.
27. white light LEDs according to claim 3 with the preparation method of nitride/oxynitride fluorescent material, is characterized in that: when the chemical formula of nitride/oxynitride fluorescent material is M
2Si
5N
8: xR, wherein M is the one or more kinds of mixtures in the elements such as Ca, Sr, Ba, Mg, R is the one or more kinds of mixtures in Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Tm, the Yb element, during 0.1mol%≤x≤15mol%, synthesis temperature is 1300 ℃～1550 ℃.
28. white light LEDs according to claim 3 with the preparation method of nitride/oxynitride fluorescent material, is characterized in that: when the chemical formula of nitride/oxynitride fluorescent material is MSi
2O
2N
2: xR, wherein M is one or more the mixture in Ca, Sr, Ba, the Mg element, during 0.1mol%≤x≤15mol%, synthesis temperature is 1300 ℃～1500 ℃.
29. white light LEDs according to claim 3 with the preparation method of nitride/oxynitride fluorescent material, is characterized in that: when the chemical formula of nitride/oxynitride fluorescent material is beta～Si
6～zAl
zO
zN
8～z: xR, 0.3≤z≤2.5 o'clock wherein, synthesis temperature is 1650 ℃～1750 ℃.
30. white light LEDs according to claim 3 with the preparation method of nitride/oxynitride fluorescent material, is characterized in that: when the chemical formula of nitride/oxynitride fluorescent material is MAlSiN
3: xR, wherein M is one or more the mixture in Ca, Sr, Ba, Li, Mg, the Y element, during 0.1mol%≤x≤15mol%, synthesis temperature is 1350 ℃～1550 ℃.
31. white light LEDs according to claim 3 with the preparation method of nitride/oxynitride fluorescent material, is characterized in that: when the chemical formula of nitride/oxynitride fluorescent material is MAlSi
4N
7: xR, wherein M is the one or more kinds of mixtures in Ca, Sr, Ba, Li, Mg, the Y element, during 0.1mol%≤x≤15mol%, synthesis temperature is 1500 ℃～1700 ℃.
32. white light LEDs according to claim 3 with the preparation method of nitride/oxynitride fluorescent material, is characterized in that: when the chemical formula of nitride/oxynitride fluorescent material is MYSi
4N
7: xR, wherein M is the one or more kinds of mixtures of elements such as Ca, Sr, Ba, Mg, synthesis temperature is 1300 ℃～1550 ℃.
33. according to the preparation method of the described white light LEDs of arbitrary claim in the claim 27 to 32 with nitride/oxynitride fluorescent material, it is characterized in that: synthesize under normal pressure and finish, the excitation wavelength of synthetic fluorescent material is 200nm～500nm, and emission wavelength is 450nm～800nm.
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| PCT/CN2011/079431 WO2012167517A1 (en) | 2011-06-08 | 2011-09-07 | Method for preparing nitride/oxynitride fluorescent powder used by white led |
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| Publication number | Priority date | Publication date | Assignee | Title |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6763387B2 (en) * | 2015-08-19 | 2020-09-30 | 宇部興産株式会社 | Fluorescent material, its manufacturing method, and light emitting device |
| US10845762B2 (en) * | 2015-11-27 | 2020-11-24 | Nemoto & Co., Ltd. | Reddish light emitting phosphorescent phosphor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101313048A (en) * | 2005-11-24 | 2008-11-26 | 皇家飞利浦电子股份有限公司 | Display device with solid state fluorescent material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775283B (en) * | 2010-01-06 | 2013-01-09 | 长春理工大学 | Method for preparing silicate yellow fluorescent powder for white-light light-emitting diode (LED) |
| CN101818063B (en) * | 2010-05-14 | 2013-03-06 | 中国科学技术大学 | Method for preparing silicon-based oxynitride fluorescent powder |
-
2011
- 2011-06-08 CN CN2011101526824A patent/CN102260500A/en active Pending
- 2011-09-07 WO PCT/CN2011/079431 patent/WO2012167517A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101313048A (en) * | 2005-11-24 | 2008-11-26 | 皇家飞利浦电子股份有限公司 | Display device with solid state fluorescent material |
Non-Patent Citations (3)
| Title |
|---|
| 《Materials Research Bulletin》 20031231 M. Panneerselvam et al. A microwave method for the preparation and sintering of beta'-SiAlON 第663-674页 1-32 , * |
| M. PANNEERSELVAM ET AL.: "A microwave method for the preparation and sintering of β’-SiAlON", 《MATERIALS RESEARCH BULLETIN》 * |
| 徐叙瑢: "《发光学与发光材料》", 31 October 2004, 化学工业出版社 * |
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