CN102888218A - Preparation method of M3Si6O12N2: xRe system green fluorescent powder - Google Patents
Preparation method of M3Si6O12N2: xRe system green fluorescent powder Download PDFInfo
- Publication number
- CN102888218A CN102888218A CN2012103517129A CN201210351712A CN102888218A CN 102888218 A CN102888218 A CN 102888218A CN 2012103517129 A CN2012103517129 A CN 2012103517129A CN 201210351712 A CN201210351712 A CN 201210351712A CN 102888218 A CN102888218 A CN 102888218A
- Authority
- CN
- China
- Prior art keywords
- xre
- preparation
- emitting phosphor
- green emitting
- system green
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention discloses a preparation method of M3Si6O12N2: xRe system green fluorescent powder. According to the preparation method, M is one or the mixture of more than two of Ca, Sr and Ba; Re means a rare-earth element; and x is more than or equal to 0.2 mol% and less than or equal to 20mol%. The method comprises the steps as follows: weighing raw materials based on the stoichiometric ratio of various elements in the chemical formula of fluorescent powder; fully and uniformly mixing the raw materials; then placing the mixture into a sagger manufactured by a wave-transmitting material; positioning the sagger into a special microwave oven; adjusting the microwave power to control the temperature raise rate under a certain gas atmosphere; heating to reach the synthesizing temperature; and finally, cooling and simply grinding to obtain the system green fluorescent powder. Compared with traditional high-temperature solid phase method, the preparation method disclosed by the invention adopts microwave heating, therefore, the synthesizing temperature is reduced to 1000 to 1500 DEG C, moreover, the reaction time is reduced, and the production efficiency is improved; and the prepared green fluorescent powder has the advantages of fine grain size, high crystallizing performance, narrow range of size distribution, regular appearance and shape, high particle dispersing performance, and the like, and is specifically applied to white light and backlight LEDs (Light Emitting Diodes).
Description
Technical field
The invention belongs to the luminescent material technical field, particularly a kind of M
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor is particularly useful for white light and backlight LED.
Background technology
White light LEDs (or claim semiconductor lighting) have environmental protection, overlong service life, energy-efficient, anti-adverse environment, simple in structure, volume is little, lightweight, response is fast, operating voltage is low and the good characteristics of security, therefore be described as after incandescent light, fluorescent lamp and electricity-saving lamp the 4th generation lighting electric light source, or be called the 21 century green light source.
White light LEDs can pass through accomplished in many ways, wherein the combination of (1) blue-light LED chip and yellow fluorescent powder is that to study also be the most ripe method the earliest, the white light LEDs luminous efficiency of preparation is considerably beyond incandescent light, yet the method is on the one hand owing to the low colorrendering quality that causes of intensity of green glow is poor, colour rendering index is low owing to lack ruddiness on the other hand, colour temperature is high, can not use as interior lighting.Therefore, in order to improve the color developing of white light LEDs, researchers have been researched and developed other two kinds of methods that realize white light LEDs: (2) blue-ray LED chip and red, green emitting phosphor combination, and and (3) purple LED chip and the combination of red, green, blue three primary colors fluorescent powder.The white light LEDs color developing that the third mode obtains significantly improves, but fluorescent dye in high efficiency also relatively lacks, exist color to absorb again and proportioning regulation and control problem between the fluorescent material, and that is that all right is ripe for purple LED chip technology of preparing, and these factors cause near ultraviolet conversion hysteria white light LEDs to be difficult in a short time obtain large-scale application; And the second way has the advantage of other dual modes, the blue-light LED chip that adopts, research and comparison is ripe both at home and abroad, obtain large-scale application, the blue light that is sent by chip mixes with ruddiness and the green glow that fluorescent material is changed out, generates white light, has good color reducibility, meet the human vision requirement, so high-performance is red, green emitting phosphor is a key factor.
At present sulfide system, silicate systems, tungsten silicate system and nitride system etc. can be arranged by blue-light excited red, green emitting phosphor.The sulfide system is unstable, and high temperature easily decomposes, and produces toxicant, does not meet environmental requirement; The silicate systems maturing temperature is than characteristics such as aluminates system are low, but luminous efficiency is also lower; Tungsten silicate system luminous efficiency is on the low side, and powder density is excessive, excite and emmission spectrum narrower; Nitride phosphor has good fluorescent characteristic, but easy and air and steam reaction of alkaline-earth nitride in the raw material, complicated process of preparation, the powder purity that makes is low, is difficult at present realize industrialization.
Nitric oxide fluorescent powder is because its unique excitation spectrum, as excites scope to contain ultraviolet, near ultraviolet, blue light even green glow, and the excellent characteristics of luminescence, as launches green, yellow, ruddiness; Little, the advantages such as luminous efficiency is high, material itself is nontoxic, good stability that hot-quenching is gone out are very suitable for being applied in white light and the backlight LED, the particularly application of the white light LEDs of blue chip, thereby received the very big concern of scientific circles and industrial community.
Chemical formula is M
3Si
6O
12N
2: the oxynitride fluorescent powder of xRe is a kind of green emitting phosphor commonly used at present, is particularly useful for white light and backlight LED.Wherein, M is the mixing of a kind of or two or more elements in Ca, Sr, the Ba element, and Re represents rare earth element.But the preparation method of this system green emitting phosphor still adopts other oxynitride fluorescent powders preparation method commonly used, i.e. traditional high temperature solid-state method at present.
High temperature solid-state method adopts Si usually
3N
4With AlN be initial feed because oxynitride fluorescent powder has very strong covalent linkage, spread coefficient is low, reactive behavior is poor, therefore needs higher sintering temperature (1600～2000 ℃), even needs higher reaction pressure (5～10atm).The reaction principle of high temperature solid-state method is self-diffusion and the mutual diffusion that starting material at high temperature passes through interface ion, makes original chemical bond fracture and forms new key, and this variation is to solid material inside or deep diffusion, thus the generation cenotype.At present; high temperature solid-state method generally adopts traditional combustion gas or heating by electric cooker; its principle be thermal source by the mode of thermal conduction, radiation or convection current, it is temperature required that material from outward appearance to inner essence progressively is heated to, synthesis temperature is high, the time is long; the particle diameter ratio of particle is larger; and it is serious to reunite, and usually also needs to carry out aftertreatment such as techniques such as pulverizing, and pulverizing will inevitably cause the destruction of particle surface; cause the generation of exhibiting high surface defective, reduce its luminous efficiency and stability.These composite factors cause the preparation process of nitric oxide fluorescent powder complicated, and energy consumption is larger, and production cost is high.
In addition, some documents have reported that also the employing softening method prepares oxynitride fluorescent powder both at home and abroad, method synthesize white light and backlight LED oxynitride fluorescent powders such as sol-gel method, homogeneous precipitation method, low-temperature combustion synthesis, hydrothermal synthesis method.The advantages such as synthesis temperature is low although these class methods have, reaction is even, the particle diameter preparation powder is less, efficient and the output of its synthetic powder are lower, and synthesis cycle is long, is not suitable for the large-scale industrial production needs.For example Chinese patent CN102191045A has announced two-step approach and has made a kind of nitrogen oxide green fluorescent powder, at first is to add the solubility promoter sintering to obtain presoma, then the synthetic target product of doped element in above-mentioned gained presoma matrix; Chinese patent CN101914379A has announced first and has obtained presoma by obtaining suspension after the three-step approach through low-temperature sintering, and then obtains final fluorescent material through high temperature sintering.Although they obtain certain progress, complex process.
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 the advantages such as rate of heating is fast, heat utilization rate is high, environmental protection.At present, existing bibliographical information the application of microwave heating method in some fluorescent material systems, for example Chinese patent CN101486905A discloses the method with preparing blue fluorescent powder for PDP by high temperature microwave method, Chinese patent CN101775283A discloses the method for preparing silicate yellow fluorescent powder with microwave method, Chinese patent CN101591539A discloses the method for preparing the RE phosphate green emitting phosphor with microwave method, Chinese patent CN1702143A discloses the method for preparing sulphide fluorescent material with microwave method, US Patent No. 2003/0230740A1 discloses the method for preparing borate fluorescent powder with microwave method, and Korean Patent KR2005088793A discloses with microwave method and prepared vacuum ultraviolet-excited green emitting phosphor.In addition, application number is that 201110152682.4 Chinese patent application discloses with microwave heating method and prepares white light LEDs with the method for nitride/oxynitride fluorescent material, still, and for this white light and backlight LED M
3Si
6O
12N
2: the green emitting phosphor of xRe system, the correlated performance when wherein specifically openly not using microwave heating method to prepare etc.
Summary of the invention
Technology of the present invention and purpose are to be M for adopting existing high temperature solid-state method to prepare chemical formula
3Si
6O
12N
2: the state of the art of the green emitting phosphor of xRe system, a kind of novel method for preparing this system green emitting phosphor is provided, the method specifically adopts microwave heating method, can reduce its synthesis temperature and pressure, obtain having the green emitting phosphor of the advantages such as particle diameter is thin, brightness is high, good crystallinity, pattern rule, be particularly useful for white light and backlight LED.
The present invention realizes that the technical scheme that above-mentioned technical purpose adopts is: a kind of M
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor, wherein, M is the mixing of a kind of or two or more elements in Ca, Sr, the Ba element, Re represents rare earth element, 0.2mol%≤x≤20mol%; The method is specially: the stoichiometric ratio according to each element in the described green emitting phosphor chemical formula takes by weighing raw material, fully pack into behind the mixing in the saggar of being made 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, finally by cooling, the simple grinding obtains M
3Si
6O
12N
2: xRe system green emitting phosphor.
Rare earth element Re can be selected from but be not limited to 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.
Raw material can be simple substance, nitride, oxide compound, fluorochemical, muriate, bromide, phosphoric acid salt, the nitrate of respective element in the described green emitting phosphor chemical formula, and the one or more kinds of mixtures in the precursor of respective element.Raw material can carry out thermal pretreatment, also can disposablely be heated rapidly to temperature required.
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 2.45GHz, 5.8GHz, 0.915GHz, 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, then passes into gas 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 passes into gas in the furnace chamber of professional microwave oven is 0～10L/min, and preferable flow rate is 0.1L/min～0.5L/min.In reaction process, can in furnace chamber, be filled with nitrogenous gas, such 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
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 Nitrogen element ammonium salts 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 described green emitting phosphor chemical formula rare earth elements Re needs reduction, its reduction can be adopted the reduction powders such as carbon dust, organic carbon, also can adopt N
2/ H
2, CH
4, NH
3, CO, H
2Mixing reducing atmosphere Deng one or several reduces.
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～50h, 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 for the bad raw material of absorbing property, preferably add auxiliary hot material at the saggar outer wall, this auxiliary hot material directly contacts placement with the saggar outer wall, perhaps places apart from certain intervals with the saggar outer wall; For the auxiliary hot material that does not react with raw material, preferably directly it is added in raw material, through after the microwave heating, applied chemistry method and/or physical method are removed synthetic M again
3Si
6O
12N
2: contained this auxiliary hot material in the xRe system green emitting phosphor.Auxiliary hot material includes but not limited to SiC, ferrite, Co
2O
3, CuO, decolorizing carbon, graphite, WO
3, MoS
2, PbS, CuFeS
2, BaTiO
3, FeTiO
3, WC and ZrO
2Deng in one or several mixture.The applied chemistry method is removed this M
3Si
6O
12N
2: contained auxiliary hot material can pass through acidity/alkalescence/organic solvent processing removal in the xRe system green emitting phosphor, 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 auxiliary hot material mainly is to remove by methods such as electric field, magnetic field, gravity field in the Applied Physics method removal oxynitride fluorescent powder.
In order to increase heat insulation effect, preferably saggar is put into attemperator, then carry out microwave heating.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.
It is worth mentioning that preparation method of the present invention not only can prepare M under the atmosphere of elevated pressures
3Si
6O
12N
2: xRe system green emitting phosphor can also prepare this system green emitting phosphor under normal pressure.Therefore, the present invention has overcome generally needs restriction synthetic under high-temperature and high-pressure conditions 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 1000 ℃～1500 ℃, more preferably 1100 ℃～1450 ℃.The M that utilizes preparation method of the present invention to obtain
3Si
6O
12N
2: the grain-size of xRe system green emitting phosphor is 0.1 μ m～30 μ m, and excitation wavelength is 200nm～500nm, and emission wavelength is 450nm～650nm.
The M that utilizes preparation method provided by the invention to obtain
3Si
6O
12N
2: xRe system green emitting phosphor is at present multiplex in white light and backlight LED; but the development along with science and technology; the application of this system green emitting phosphor has more than and is defined in white light and backlight LED; 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.
The present invention utilizes microwave method to synthesize M
3Si
6O
12N
2: xRe system green emitting phosphor, compared with prior art, its beneficial effect is:
(1) starting raw material and microwave direct-coupling make the inside and outside simultaneously thermally equivalent of material monolithic, and the field distribution of reactant internal temperature is even, and thermograde is little; Meanwhile be in the microwave electromagnetic field owing to reactant, inner particles is subject to the effect of electromagnetic field, and the particle activity is larger, thereby promotes the ion diffusion, reduces temperature of reaction, Reaction time shorten.
(2) sintering temperature of the present invention is lower than the solid phase method reaction of prior art, but save energy also can be avoided introducing dephasign from reactor, phase purity height owing to the sintering temperature height.
(3) can under normal pressure, synthesize M
3Si
6O
12N
2: xRe system green emitting phosphor, direct heating synthesizes and does not need insulation to process, and perhaps soaking time shortens greatly, has shortened the production cycle, has improved production efficiency; Reduced the gas usage that consumes in the sintering process, reduced unnecessary consumption, energy-conserving and environment-protective are pollution-free;
(4) M for preparing
3Si
6O
12N
2: xRe system green emitting phosphor has the advantages such as particle diameter is thin, good crystallinity, particle size distribution is narrow, pattern is regular, particle dispersion is good; This synthetic system green emitting phosphor only needs simple grinding, does not need the high strength break process through the later stage;
(5) the method can not only improve M
3Si
6O
12N
2: the brightness of xRe system green emitting phosphor, simultaneously can modulate its emission wavelength, make it can pass through to regulate the doping of each element, the product emission peak is regulated between 520～550nm, widened the colour gamut of this system green emitting phosphor, be particularly useful in the white light and backlight LED of high color rendering index (CRI).
Therefore, preparation method of the present invention be a kind of fast, efficient, energy-saving and environmental protection, the M that is easy to again realize suitability for industrialized production with low cost
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor.
Description of drawings
Fig. 1 is 1250 ℃ of synthetic Ba among the embodiment 1
3Si
6O
12N
2: Eu
2+The fluorescence spectrum spectrogram of fluorescent material;
Fig. 2 is 1250 ℃ of synthetic Ba among the embodiment 1
3Si
6O
12N
2: Eu
2+The particle size distribution figure of fluorescent material.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described in further detail.It is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and it is not played any restriction effect.
Embodiment 1:
M
3Si
6O
12N
2: xEu
2+Fluorescent material, M=Ba wherein, the synthetic method of x=0.2 is as follows:
With chemical formula Ba
3Si
6O
12N
2: xEu
2+(x=0.2) stoichiometric ratio in takes by weighing an amount of BaCO
3, SiO
2, Si
3N
4And Eu
2O
3As raw material, then raw material is placed on and mixes in the agate mortar and grinding; 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 auxiliary hot material of SiC at the saggar outer wall simultaneously; Then insulated tank is put into microwave oven; By Modulating Power, with the temperature rise rate of 20 ℃/min, under the gas flow rate of 0.3L/min, normal heating to 1250 ℃, and insulation 2h; React and turn off microwave source after complete, reactant naturally cools to room temperature with stove, synthetic fluorescent material is simply ground through agate mortar, products therefrom be particle diameter thin, without the green powder of sintering phenomenon.
Use XRD, fluorescence spectrum and sreen analysis and characterize the powder for preparing, Fig. 1 is the fluorescence spectrum spectrogram of this powder, and Fig. 2 is the particle size distribution figure of this powder.Powder is by pure phase Ba
3Si
6O
12N
2Form, and crystallinity is better; Under the 460nm wavelength excited, this fluorescent material transmitted wave peak position was in the green light of 527nm; Diameter of particle is 3 μ m～5 μ m, and particle size distribution is narrow, pattern is regular, particle dispersion is good.
Embodiment 2～7:
Identical with embodiment 1, embodiment 2～7 also is M
3Si
6O
12N
2: xEu
2+The synthetic method of fluorescent phosphor powder, the method is basic identical with embodiment 1, and difference is chemical formula M
3Si
6O
12N
2: xEu
2+In M, x value, M raw material, and synthesis temperature, soaking time adopts different values, and is as shown in table 1 below.
Table 1: embodiment 2～6 synthetic M
3i
6O
12N
2: xEu
2+Component content during fluorescent material and processing condition
Use fluorescence spectrum and sreen analysis and characterize the powder for preparing.From the test the material phase analysis result as can be known: powder is by pure phase M
3Si
6O
12N
2Form, and crystallinity is better; The powder granularity narrow distribution range, pattern is regular, particle dispersion good; The characteristics of luminescence and particle size are as shown in table 2 below.
The M that table 2: embodiment 2～7 synthesizes
3Si
6O
12N
2: xEu
2+The characteristics of luminescence of fluorescent material and particle size
| Embodiment | Excitation wavelength | Emission wavelength | Luminous intensity | Particle diameter |
| 2 | 450nm | 525nm | 2800 | 3～5μｍ |
| 3 | 450nm | 523nm | 2300 | 3～5μｍ |
| 4 | 450nm | 528nm | 2200 | 3～5μｍ |
| 5 | 450nm | 536nm | 2500 | 3～5μｍ |
| 6 | 450nm | 545nm | 2400 | 3～5μｍ |
| 7 | 450nm | 550nm | 2300 | 3～5μｍ |
Above-described embodiment has been described in detail technical scheme of the present invention and beneficial effect; be understood that the above only is specific embodiments of the invention; be not limited to the present invention; all any modifications of in principle scope of the present invention, making, replenish and be equal to replacement etc., all should be included within protection scope of the present invention.
Claims (15)
1. M
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor, wherein, M is the mixing of a kind of or two or more elements in Ca, Sr, the Ba element, Re represents rare earth element, 0.2mol%≤x≤20mol%, it is characterized in that: the stoichiometric ratio according to each element in the described green emitting phosphor chemical formula takes by weighing raw material, fully pack into behind the mixing in the saggar of being made 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, finally by cooling, the simple grinding obtains M
3Si
6O
12N
2: xRe system green emitting phosphor.
2. M according to claim 1
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor is characterized in that: described Re 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.
3. M according to claim 1
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor, it is characterized in that: described raw material is simple substance, nitride, oxide compound, fluorochemical, muriate, bromide, phosphoric acid salt, the nitrate of respective element in the described green emitting phosphor chemical formula, and the one or more kinds of mixtures in the precursor of respective element.
4. M according to claim 1
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor is characterized in that: 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.
5. M according to claim 1
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor is characterized in that: the microwave frequency of described professional microwave oven is 300MHz～300GHz.
6. M according to claim 5
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor is characterized in that: the microwave frequency of described professional microwave oven is 2.45GHz, 5.8GHz, 0.915GHz or 24.15GHz.
7. M according to claim 1
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor is characterized in that: add NH in the described raw material
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.
8. M according to claim 1
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor 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.
9. M according to claim 1
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor is characterized in that: be incubated processing after being heated to synthesis temperature, soaking time is 0.1h～50h.
10. M according to claim 1
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor is characterized in that: described temperature rise rate is 5 ℃/min～200 ℃/min.
11. the described M of arbitrary claim in 10 according to claim 1
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor is characterized in that: described synthesis temperature is 1000 ℃～1500 ℃.
12. M according to claim 11
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor is characterized in that: described synthesis temperature is 1100 ℃～1450 ℃.
13. the described M of arbitrary claim in 10 according to claim 1
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor is characterized in that: the grain-size of described oxynitride fluorescent powder is 0.1 μ m～30 μ m.
14. the described M of arbitrary claim in 10 according to claim 1
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor is characterized in that: synthesize under normal pressure and finish.
15. the described M of arbitrary claim in 10 according to claim 1
3Si
6O
12N
2: the preparation method of xRe system green emitting phosphor is characterized in that: the M that obtains
3Si
6O
12N
2: the excitation wavelength of xRe system green emitting phosphor is 200nm～500nm, and emission wavelength is 450nm～650nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103517129A CN102888218A (en) | 2012-09-20 | 2012-09-20 | Preparation method of M3Si6O12N2: xRe system green fluorescent powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103517129A CN102888218A (en) | 2012-09-20 | 2012-09-20 | Preparation method of M3Si6O12N2: xRe system green fluorescent powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102888218A true CN102888218A (en) | 2013-01-23 |
Family
ID=47531903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103517129A Pending CN102888218A (en) | 2012-09-20 | 2012-09-20 | Preparation method of M3Si6O12N2: xRe system green fluorescent powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102888218A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103589425A (en) * | 2013-09-24 | 2014-02-19 | 厦门通士达新材料有限公司 | Silicon-based nitric oxide green luminescent material for LEDs (Light Emitting Diode) and preparation method thereof |
| TWI577782B (en) * | 2013-06-24 | 2017-04-11 | Gen Res Inst Nonferrous Metals | A phosphor and a light-emitting device containing the same |
| CN109765206A (en) * | 2019-01-31 | 2019-05-17 | 清华大学 | Characterize the method and its application of two-dimensional material defect |
| CN114426847A (en) * | 2022-01-07 | 2022-05-03 | 云南大学 | Boron tellurate base red fluorescent material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864300A (en) * | 2010-06-30 | 2010-10-20 | 彩虹集团公司 | Rare-earth doped nitrogen oxide fluorescent powder and preparation method thereof |
| CN102260500A (en) * | 2011-06-08 | 2011-11-30 | 中国科学院宁波材料技术与工程研究所 | Method for making nitride/nitrogen oxide fluorescent powder for white light LED (Light Emitting Diode) |
-
2012
- 2012-09-20 CN CN2012103517129A patent/CN102888218A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864300A (en) * | 2010-06-30 | 2010-10-20 | 彩虹集团公司 | Rare-earth doped nitrogen oxide fluorescent powder and preparation method thereof |
| CN102260500A (en) * | 2011-06-08 | 2011-11-30 | 中国科学院宁波材料技术与工程研究所 | Method for making nitride/nitrogen oxide fluorescent powder for white light LED (Light Emitting Diode) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI577782B (en) * | 2013-06-24 | 2017-04-11 | Gen Res Inst Nonferrous Metals | A phosphor and a light-emitting device containing the same |
| CN103589425A (en) * | 2013-09-24 | 2014-02-19 | 厦门通士达新材料有限公司 | Silicon-based nitric oxide green luminescent material for LEDs (Light Emitting Diode) and preparation method thereof |
| CN103589425B (en) * | 2013-09-24 | 2015-09-09 | 厦门通士达新材料有限公司 | A kind of LED silica-based oxynitride green luminescent material and preparation method thereof |
| CN109765206A (en) * | 2019-01-31 | 2019-05-17 | 清华大学 | Characterize the method and its application of two-dimensional material defect |
| CN109765206B (en) * | 2019-01-31 | 2020-11-24 | 清华大学 | Method for characterizing two-dimensional material defects and application thereof |
| CN114426847A (en) * | 2022-01-07 | 2022-05-03 | 云南大学 | Boron tellurate base red fluorescent material and preparation method and application thereof |
| CN114426847B (en) * | 2022-01-07 | 2022-11-11 | 云南大学 | Boron tellurate base red fluorescent material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Enhanced luminescence of novel Ca3B2O6: Dy3+ phosphors by Li+-codoping for LED applications | |
| CN102260500A (en) | Method for making nitride/nitrogen oxide fluorescent powder for white light LED (Light Emitting Diode) | |
| Wang et al. | Potential tunable white-emitting phosphor LiSr4 (BO3) 3: Ce3+, Eu2+ for ultraviolet light-emitting diodes | |
| CN104087293B (en) | Red-emitting phosphors and carbothermal reduction-nitridation preparation method thereof and application | |
| CN102391861B (en) | Nitrogen compound luminescent material, preparation method thereof and lighting source made therefrom | |
| Li et al. | Sol–gel synthesis, structure and luminescence properties of Ba2ZnMoO6: Eu3+ phosphors | |
| CN103484112B (en) | Rare-earth europium-activated single-component white-light fluorescent powder and preparation method thereof | |
| CN106221695A (en) | The preparation method of aluminum-nitride-based fluorescent material | |
| CN103980900B (en) | Silicate blue light fluorescent powder and preparation method thereof | |
| Li et al. | Warm-white-light emission from Eu2+/Mn2+-coactivated NaSrPO4 phosphor through energy transfer | |
| CN103725285B (en) | Single-substrate white-light fluorescent powder for white-light LEDs (light-emitting diodes) and preparation method thereof | |
| CN102888218A (en) | Preparation method of M3Si6O12N2: xRe system green fluorescent powder | |
| CN103320124A (en) | Rapid preparation method for MSi2O2N2:Eu<2+> phosphor | |
| Hu et al. | Preparation and characterization of Gd3 (ScAl) 2Al3O12: Ce3+ garnet phosphors towards high-color-rendering white-light illumination | |
| CN101805607A (en) | Low-temperature synthetic method of silicate green-light fluorescent powder | |
| CN101760191B (en) | High-brightness barium-silicate-based blue-green fluorescent powder for LED and high-temperature reducing preparation method thereof | |
| CN103525407A (en) | Method for preparing silicon-based nitride or nitric oxide fluorescent powder for LED | |
| CN103740367B (en) | Single-matrix white fluorescent powder for warm white LED (Light Emitting Diode) and preparation method thereof | |
| CN103436262B (en) | Silicate red nano fluorescent powder and preparation method thereof | |
| CN107418575B (en) | A kind of europkium-activated silicate blue-green fluorescent powder and preparation method thereof | |
| CN102559175B (en) | Sr2SiO4:XEu<2+> fluorescent powder and preparation method thereof | |
| CN101914379A (en) | Method for preparing nitrogen oxide phosphor powder | |
| Yin et al. | Realization of high-quality white light emission in single-phased α-Sr2P2O7: Dy3+, Tm3+ phosphor | |
| CN101747892A (en) | Red phosphor powder for white light LED and preparation method thereof | |
| CN104277827B (en) | A kind of preparation method of silicon nitrogen base Blue-green phosphor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130123 |