CN103374347A - Aluminum oxynitride luminescent powder and preparation method thereof - Google Patents
Aluminum oxynitride luminescent powder and preparation method thereof Download PDFInfo
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- CN103374347A CN103374347A CN2012101193322A CN201210119332A CN103374347A CN 103374347 A CN103374347 A CN 103374347A CN 2012101193322 A CN2012101193322 A CN 2012101193322A CN 201210119332 A CN201210119332 A CN 201210119332A CN 103374347 A CN103374347 A CN 103374347A
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Abstract
The invention relates to an aluminum oxynitride luminescent powder and a preparation method thereof. The chemical structural general formula of the blue-light luminescent powder is M1.5yMg1.5xAl23-x-yO27N5, wherein the doping element M is a transition metal element or a rare earth element, x is greater than or equal to 0 and less than 6.0, and y is greater than or equal to 0 and less than 3.0. The blue-light luminescent powder controllable in emission wavelength can be obtained by regulating the type of the doping element; and the doping quantity of the rare earth element in the aluminum oxynitride luminescent powder is low so that the dosage of the rare earth element can be saved.
Description
Technical field
The present invention relates to Material Field, be specifically related to a kind of aluminum oxynitride luminescent powder, especially be doped with aluminum oxynitride luminescent powder of transition metal ion and/or rare earth ion and preparation method thereof.
Background technology
At present, what business-like white light LEDs usually adopted is by body fluorescence conversion technology, with the utilizing emitted light of CaN blue-ray LED or InGaN near-ultraviolet light LED with made up to produce white light by the utilizing emitted light of its fluorescent material that excites, for example the InGaN blue light cooperates Y
3Al
5O
12: Ce
3+(YAG:Ce
3+) yellow fluorescent powder realize the ejaculation of white light.The kind of luminescent material and quantity are a lot of at present, also play a significant role in fields such as industry, daily lifes, yet both at home and abroad large quantity research and the fluorescent material that uses mostly with oxide compound, sulfide or oxysulfide as body material, and mix in these body materials a small amount of transition metal ion or rare earth ion (Re) are as luminescence center.These material thermal shock resistances are relative with chemical stability relatively poor.For example, to YAG:Ce
3+Temperature profile research find that along with the LED working hour increases, the temperature of fluorescent material raises gradually, luminous efficiency obviously weakens, thereby affects the white light LEDs working life.
Nitride and oxynitride have a lot of good character, such as very high thermostability, chemical stability, wide excite with emission wavelength, have high fluorescence efficiency etc. at rare earth ion in as the activator situation.Therefore, nitride/oxynitride fluorescent material is regarded as the preferred material of white light LEDs in recent years.
As nitrogen oxide fluorescent material, the Si-O-N system is present study hotspot because it has stable physicochemical property.For example, patent CN 100336886 C of the application before the applicant unit one belongs to disclose a kind of nitrogen oxide fluorescent material and preparation method thereof, and its chemical formula is Eu
2Al
3Si
13N
19O
2, it is added with Al and forms the Si-Al-O-N system and be doped with Eu in the Si-O-N system.Report about the fluorescent material of Si-Al-O-N system also has CN 1876755 A, CN 101157854B and CN 101760190 A, although these materials have also comprised Al, yet its major metal or Si, for example clearly mention at least among CN 101157854B and CN 101760190 A and will contain Si, that is to say to comprise Si but can not comprise Al.
Al-(O, N)
4Tetrahedral network structure is given aluminum oxynitride (AlON) system and is had very high chemistry and thermostability, makes it at high temperature still can keep higher stability of photoluminescence.Therefore, the inventor recognizes that AlON may become large power white light LED one of candidate material of fluorescent material matrix.Yet, at present that AlON is also less as the fluorescent material report of luminous host, and relate to as the Yellow light emitting powder more.Yet, at present that AlON is also less as the fluorescent material report of luminous host, and relate to as the Yellow light emitting powder, for example CN 102020988 A disclose a kind of doped with cerium and terbium γ-AlON base Yellow light emitting powder. more
At present also fewer about the report of the preparation of pure phase AlON matrix, main method has two kinds: (1) is with Al
2O
3With AlN be raw material, by the preparation of direct high temperature solid state reaction; (2) be standby with aluminium glycine gels precursor legal system.The aluminum oxide that wherein easily has not nitrogenize in the former product; Latter Yi Shengcheng rare earth aluminate.The two all is difficult to obtain pure phase AlON host luminescent powder.If the AlON fluorescent material that preparation is mixed, because the complicacy of chemical ingredients and phase composition, the technical difficulty of the doping fluorescent powder of synthetic pure phase is larger.
Summary of the invention
The present invention is at this aluminum oxynitride blue light emitting powder that a kind of novelty is provided, and the chemical structure of general formula of this blue light emitting powder is M
1.5yMg
1.5xAl
23-x-yO
27N
5, wherein doped element M is transition metal or rare earth element, 0≤x＜6.0,0≤y＜3.0.Transition metal can adopt Mn, and rare earth element can adopt Eu or Ce.
Aluminum oxynitride blue light emitting powder provided by the invention has excellent fluorescence property.
Again, preferably, 0≤x≤3.0, more preferably 0＜x＜1.5.
Again, preferably, 0≤y≤2.0, more preferably 0＜y≤1.
Again, aluminum oxynitride blue light emitting powder of the present invention has emission peak in 385～458nm scope under ultraviolet excitation.
Again, aluminum oxynitride blue light emitting powder of the present invention has the cubic spinel structure.The particle size range of aluminum oxynitride blue light emitting powder of the present invention is 1～5 μ m.
On the other hand, the invention provides a kind of preparation method of aluminum oxynitride blue light emitting powder, comprise predetermined amount proportioning raw material A l
2O
3, AlN, MgO and doped element M source, ball milling is mixed to get uniform sizing material; The slurry of dry gained makes powder, powder is sieved; And the powder after will sieving is put into boron nitride crucible, under the flowing nitrogen atmosphere, place vacuum hotpressing stove, nitrogen flow is 0.4～1.2 liter of per minute, temperature rise rate is 5 ~ 20 ℃ of per minutes, calcining in 1700 ~ 1950 ℃ temperature range, soaking time is 1～6 hour, obtains the blue light emitting powder material.Should be understood that in above-mentioned preparation method MgO can be used as and helps the knot agent to use, and also can be used as the doped element source of doped element Mg is provided.Should also be understood that and in above-mentioned preparation method, can not add as required MgO and/or doped element M source to prepare unadulterated aluminum oxynitride blue light emitting powder.
Carbonate or the oxide compound of M can be adopted in doped element M source.When M is transition metal Mn, preferably adopt manganous carbonate (MnCO
3); When M is rare earth element, preferential oxidation europium (Eu
2O
3) or cerium oxide (CeO
2).
Preferably, nitrogen flow can be 0.4～0.6 liter of per minute.Temperature rise rate is preferably 7～10 ℃ of per minutes, and preferably calcining in 1800 ~ 1900 ℃ temperature range, and soaking time is preferably 2～4 hours.
Again, in ball milling, preferably adopt dehydrated alcohol as grinding medium, and use Si
3N
4Ball.Si
3N
4The mass ratio of ball, reaction mixture and dehydrated alcohol is preferably (3 ~ 10): 1:10.
Compared with prior art, the invention has the advantages that:
1, the present invention in 7 ~ 10 ℃ of scopes of per minute, can obtain pure phase AlON fluorescent material by the control temperature rise rate according to the difference of doped with rare-earth elements kind and temperature of reaction;
2, can obtain the adjustable blue colour fluorescent powder of emission wavelength by regulation and control doped element kind, the taking second place of the longest, the doped with Mn of the Eu that namely mixes, be again doped Ce or only doped with Mg, be unadulterated aluminum oxynitride at last;
3, the amount of rare earth elements doping of the present invention is that the y value can be little 10 times than existing reported values, can save the consumption of rare earth element, has low-cost advantage when large-scale production.
Description of drawings
Fig. 1 is the X-ray diffractogram of embodiment 1 corresponding aluminum oxynitride blue light emitting powder;
The emission collection of illustrative plates of Fig. 2 embodiment 1 corresponding aluminum oxynitride blue light emitting powder.
Embodiment
Below, with reference to accompanying drawing, and further specify with the following embodiments the present invention.
The present invention is with aluminum oxide (Al
2O
3, purity 99.99%) and aluminium nitride (AlN, purity 98%) prepare aluminum oxynitride blue light emitting powder as main raw material, mainly may further comprise the steps.
Get a certain amount of Al
2O
3, AlN, magnesium oxide (MgO, purity 99%) and doped element M source, ball milling is mixed to get uniform sizing material.Carbonate or the oxide compound of M can be adopted in doped element M source.When M is transition metal Mn, preferably adopt manganous carbonate (MnCO
3, purity 98%); When M is rare earth element, preferential oxidation europium (Eu
2O
3, purity 99.99%) or cerium oxide (CeO
2), purity 99.99%.In the present invention, MgO ties the agent use as helping, but also can understand conduct for the doped element source of doped element Mg is provided.Should also be understood that and not add as required MgO, MnCO
3, Eu
2O
3Or CeO
2To prepare unadulterated aluminum oxynitride blue light emitting powder.Ball milling can carry out in ball grinder, can select dehydrated alcohol as grinding medium, and uses Si
3N
4Ball.The mass ratio of the ball that adopts in the ball milling, reaction mixture and dehydrated alcohol can be (3 ~ 10): 1:10, and Ball-milling Time can be 12～36 hours.
The slurry of dry above-mentioned ball milling gained, sieve.The dry mode that can adopt oven dry is for example 60～100 ℃ of lower oven dry.Sieve and to adopt 60～100 mesh sieves, for example 80 mesh sieves commonly used.
Powder after sieving is put into boron nitride crucible, under the flowing nitrogen atmosphere, place vacuum hotpressing stove, nitrogen flow is 0.4～1.2 liter of per minute, 0.4～0.6 liter of preferred per minute, and temperature rise rate is 5 ~ 20 ℃ of per minutes, 7～10 ℃ of preferred per minutes, calcining in 1700 ~ 1950 ℃ temperature range, preferred 1800～1900 ℃ temperature range, soaking time are 1～6 hour, preferred 2～4 hours, obtain the blue light emitting powder material.Mensuration makes the X-ray diffractogram of luminescent powder, determines that it has the cubic spinel structure.By electron-microscope scanning, measuring the particle size range that makes luminescent powder is 1～5 μ m.The analysis means such as employing ultimate analysis are determined its chemical constitution.The luminescent powder emitting fluorescence that adopts ultraviolet excitation to make finds that luminescent powder of the present invention has the blue emission peak in 385～458nm scope.
Should be understood that the above-mentioned embodiment that the present invention describes in detail, and following examples only are used for explanation the present invention and are not used in and limit the scope of the invention.The raw material that adopts, reagent can marketable material or traditional chemical transform mode are synthetic to be made by buying.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, for example is " condition in the smooth organic chemistry handbook of Bel Si (Chemical Industry Press, 1996), or the condition of advising according to manufacturer.Unless stated otherwise, ratio and per-cent are based on molar mass.Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any method and material similar to described content or that be equal to all can be applicable in the inventive method in addition.Other aspects of the present invention are because the disclosure of this paper is that appearance is intelligible to those skilled in the art.
Below, by embodiment the present invention is described in more details.
Embodiment 1
Get aluminum oxide (Al
2O
3) 841.5g, aluminium nitride (AlN) 205g, magnesium oxide (MgO) 86g, cerium oxide (CeO
2) 18.93g.Place the tetrafluoroethylene ball grinder, use Si
3N
4Ball, take dehydrated alcohol as the grinding medium ball mill mixing 24 hours, the slurry that obtains mixing.Slurry is put into the baking oven that is preheated to 80～100 ℃ after dry 24 hours, sieve the dry powder that obtains mixing with 80 mesh sieves.Dry powder is placed boron nitride crucible, and put into vacuum hotpressing stove, at flowing nitrogen (N
2) reacting by heating in the atmosphere; Nitrogen flow is 0.4～0.6 liter of per minute, from room temperature to 1000 a ℃ heating-up time be 60 minutes, from 1000 to 1800 ℃ of heating-up times are 90 minutes, obtain the luminescent powders of AlON:Ce pure phase of doped Ce in 2 hours in 1800 ℃ of insulations.Its X-ray diffractogram is referring to Fig. 1 (X-coordinate is 2 times of diffraction angle, and ordinate zou is intensity), and it is the cubic spinel structure that its structure is shown.Adopt ultimate analysis to determine that the accurate chemical expression of this luminescent powder is: Ce
0.11Mg
2.15Al
21.5O
27N
5Electron microscopic observation, the particle diameter that makes luminescent powder are 1.0～3.0 μ m.The strong blue light of emission under the ultraviolet excitation of wavelength 305nm, its emission collection of illustrative plates has emission peak referring to Fig. 2 at the 392nm place.
Embodiment 2
Get aluminum oxide (Al
2O
3) 795.6g, aluminium nitride (AlN) 205g, magnesium oxide (MgO) 86g, europium sesquioxide (Eu
2O
3) 0.4g.Place the tetrafluoroethylene ball grinder, use Si
3N
4Ball, take dehydrated alcohol as the grinding medium ball mill mixing 24 hours, the slurry that obtains mixing.Slurry is put into the baking oven that is preheated to 80～100 ℃ after dry 24 hours, sieve the dry powder that obtains mixing with 80 mesh sieves.Dry powder is placed boron nitride crucible, and put into vacuum hotpressing stove, at flowing nitrogen (N
2) reacting by heating in the atmosphere; Nitrogen flow is 0.4～0.6 liter of per minute, from room temperature to 1000 a ℃ heating-up time be 60 minutes, from 1000 to 1800 ℃ of heating-up times are 90 minutes, in 1800 ℃ of insulations obtained in 4 hours mixing luminescent powder of AlON:Eu pure phase of Eu.The luminescent powder that makes has the cubic spinel structure, and particle diameter is 1.0～4.5 μ m.Adopt ultimate analysis to determine that the accurate chemical expression of this luminescent powder is: Eu
0.0022Mg
2.15Al
21.6O
27N
5The strong blue light of emission under the ultraviolet excitation of wavelength 275nm, emission peak positions is at the 401nm place.
Embodiment 3
Adopt 1.06g g Eu
2O
3Replace 0.4 g Eu among the embodiment
2O
3, all the other conditions make the luminescent powder of the AlON:Eu pure phase of doping Eu with embodiment 2.The luminescent powder that makes has the cubic spinel structure, and particle diameter is 1.0～4.5 μ m.Adopt ultimate analysis to determine that the accurate chemical expression of this luminescent powder is: Eu
0.006Mg
2.15Al
21.5O
27N
5The strong blue light of emission under the ultraviolet excitation of wavelength 275nm, emission peak positions is at the 448nm place.
Embodiment 4
Adopt 1.94g Eu
2O
3Replace 0.4 g Eu among the embodiment
2O
3, all the other conditions make the luminescent powder of the AlON:Eu pure phase of doping Eu with embodiment 2.The luminescent powder that makes has the cubic spinel structure, and particle diameter is 1.0～4.5 μ m.Adopt ultimate analysis to determine that the accurate chemical expression of this luminescent powder is: Eu
0.011Mg
2.15Al
21.5O
27N
5The strong blue light of emission under the ultraviolet excitation of wavelength 275nm, emission peak positions is at the 454nm place.
Embodiment 5
Adopt 3.17g Eu
2O
3Replace 0.4 g Eu among the embodiment
2O
3, all the other conditions make the luminescent powder of the AlON:Eu pure phase of doping Eu with embodiment 2.The luminescent powder that makes has the cubic spinel structure, and particle diameter is 1.0～4.5 μ m.Adopt ultimate analysis to determine that the accurate chemical expression of this luminescent powder is: Eu
0.018Mg
2.15Al
21.5O
27N
5The strong blue light of emission under the ultraviolet excitation of wavelength 275nm, emission peak positions is at the 455nm place.
Embodiment 6
Get aluminum oxide (Al
2O
3) 797.13g, aluminium nitride (AlN) 205g, magnesium oxide (MgO) 82.4g, europium sesquioxide (Eu
2O
3) 263.94g.Place the tetrafluoroethylene ball grinder, use Si
3N
4Ball, take dehydrated alcohol as the grinding medium ball mill mixing 24 hours, the slurry that obtains mixing.Slurry is put into the baking oven that is preheated to 80～100 ℃ after dry 24 hours, sieve the dry powder that obtains mixing with 80 mesh sieves.Dry powder is placed boron nitride crucible, and put into vacuum hotpressing stove, at flowing nitrogen (N
2) reacting by heating in the atmosphere; Nitrogen flow is 0.4～0.6 liter of per minute, from room temperature to 1000 a ℃ heating-up time be 60 minutes, from 1000 to 1800 ℃ of heating-up times are 90 minutes, in 1800 ℃ of insulations obtained in 4 hours mixing luminescent powder of AlON:Eu pure phase of Eu.The luminescent powder that makes has the cubic spinel structure, and particle diameter is 1.0～4.5 μ m.Adopt ultimate analysis to determine that the accurate chemical expression of this luminescent powder is: Eu
1.5Mg
2.06Al
20.63O
27N
5The strong blue light of emission under the ultraviolet excitation of wavelength 275nm, emission peak positions is at the 456nm place.
Embodiment 7
Get aluminum oxide (Al
2O
3) 748.68g, aluminium nitride (AlN) 205g, magnesium oxide (MgO) 78.8g, europium sesquioxide (Eu
2O
3) 527.88g.Place the tetrafluoroethylene ball grinder, use Si
3N
4Ball, take dehydrated alcohol as the grinding medium ball mill mixing 24 hours, the slurry that obtains mixing.Slurry is put into the baking oven that is preheated to 80～100 ℃ after dry 24 hours, sieve the dry powder that obtains mixing with 80 mesh sieves.Dry powder is placed boron nitride crucible, and put into vacuum hotpressing stove, at flowing nitrogen (N
2) reacting by heating in the atmosphere; Nitrogen flow is 0.4～0.6 liter of per minute, from room temperature to 1000 a ℃ heating-up time be 60 minutes, from 1000 to 1800 ℃ of heating-up times are 90 minutes, in 1800 ℃ of insulations obtained in 4 hours mixing luminescent powder of AlON:Eu pure phase of Eu.Make luminescent powder and have the cubic spinel structure, particle diameter is 1.0～4.5 μ m.Adopt ultimate analysis to determine that the accurate chemical expression of this luminescent powder is: Eu
3.0Mg
1.97Al
19.68O
27N
5The strong blue light of emission under the ultraviolet excitation of wavelength 275nm, emission peak positions is at the 458nm place.
Embodiment 8
Get aluminum oxide (Al
2O
3) 464.1g, aluminium nitride (AlN) 205g, magnesium oxide (MgO) 357.2g, europium sesquioxide (Eu
2O
3) 779.5g.Place the tetrafluoroethylene ball grinder, use Si
3N
4Ball, take dehydrated alcohol as the grinding medium ball mill mixing 24 hours, the slurry that obtains mixing.Slurry is put into the baking oven that is preheated to 80～100 ℃ after dry 24 hours, sieve the dry powder that obtains mixing with 80 mesh sieves.Dry powder is placed boron nitride crucible, and put into vacuum hotpressing stove, at flowing nitrogen (N
2) reacting by heating in the atmosphere; Nitrogen flow is 0.4～0.6 liter of per minute, from room temperature to 1000 a ℃ heating-up time be 60 minutes, from 1000 to 1800 ℃ of heating-up times are 90 minutes, in 1800 ℃ of insulations obtained in 4 hours mixing luminescent powder of AlON:Eu pure phase of Eu.Make luminescent powder and have the cubic spinel structure, particle diameter is 1.0～4.5 μ m.Adopt ultimate analysis to determine that the accurate chemical expression of this luminescent powder is: Eu
4.43Mg
8.93Al
14.1O
27N
5The strong blue light of emission under the ultraviolet excitation of wavelength 275nm, emission peak positions is at the 465nm place.
Embodiment 9
Get aluminum oxide (Al
2O
3) 800.19g, aluminium nitride (AlN) 205g, magnesium oxide (MgO) 82g, manganous carbonate (MnCO
3) 161g.Place the tetrafluoroethylene ball grinder, use Si
3N
4Ball, take dehydrated alcohol as the grinding medium ball mill mixing 24 hours, the slurry that obtains mixing.Slurry is put into the baking oven that is preheated to 80～100 ℃ after dry 24 hours, sieve the dry powder that obtains mixing with 80 mesh sieves.Dry powder is placed boron nitride crucible, and put into vacuum hotpressing stove, at flowing nitrogen (N
2) reacting by heating in the atmosphere; Nitrogen flow is 0.4～0.6 liter of per minute, from room temperature to 1000 a ℃ heating-up time be 60 minutes, from 1000 to 1850 ℃ of heating-up times are 90 minutes, obtain the luminescent powders of AlON:Mn pure phase of doped with Mn in 2 hours in 1850 ℃ of insulations.The luminescent powder that makes has the cubic spinel structure, and particle diameter is 1.0～5.0 μ m.Adopt ultimate analysis to determine that the accurate chemical expression of this luminescent powder is: Mn
1.4Mg
2.05Al
20.69O
27N
5The strong blue light of emission under the ultraviolet excitation of wavelength 275nm, emission peak positions is at the 398nm place.
Get aluminum oxide (Al
2O
3) 867g, aluminium nitride (AlN) 205g, magnesium oxide (MgO) 60g.Place the tetrafluoroethylene ball grinder, use Si
3N
4Ball, take dehydrated alcohol as the grinding medium ball mill mixing 24 hours, the slurry that obtains mixing.Slurry is put into the baking oven that is preheated to 80～100 ℃ after dry 24 hours, sieve the dry powder that obtains mixing with 80 mesh sieves.Dry powder is placed boron nitride crucible, and put into vacuum hotpressing stove, at flowing nitrogen (N
2) reacting by heating in the atmosphere; Nitrogen flow is 0.4～0.6 liter of per minute, from room temperature to 1000 a ℃ heating-up time be 60 minutes, from 1000 to 1850 ℃ of heating-up times are 90 minutes, obtain the luminescent powder of AlON pure phase in 2 hours in 1850 ℃ of insulations.The luminescent powder that makes has the cubic spinel structure, and particle diameter is 1.0～2.5 μ m.Adopt ultimate analysis to determine that the accurate chemical expression of this luminescent powder is: Mg
1.5Al
22O
27N
5The strong blue light of emission under the ultraviolet excitation of wavelength 275nm, emission peak positions is at the 390nm place.
Embodiment 11
Get aluminum oxide (Al
2O
3) 845.07g, aluminium nitride (AlN) 205g, magnesium oxide (MgO) 86g.Place the tetrafluoroethylene ball grinder, use Si
3N
4Ball, take dehydrated alcohol as the grinding medium ball mill mixing 24 hours, the slurry that obtains mixing.Slurry is put into the baking oven that is preheated to 80～100 ℃ after dry 24 hours, sieve the dry powder that obtains mixing with 80 mesh sieves.Dry powder is placed boron nitride crucible, and put into vacuum hotpressing stove, at flowing nitrogen (N
2) reacting by heating in the atmosphere; Nitrogen flow is 0.4～0.6 liter of per minute, from room temperature to 1000 a ℃ heating-up time be 60 minutes, from 1000 to 1850 ℃ of heating-up times are 90 minutes, obtain the luminescent powder of AlON pure phase in 2 hours in 1850 ℃ of insulations.Make luminescent powder and have the cubic spinel structure, particle diameter is 1.0～2.5 μ m.Adopt ultimate analysis to determine that the accurate chemical expression of this luminescent powder is: Mg
2.15Al
21.57O
27N
5The strong blue light of emission under the ultraviolet excitation of wavelength 275nm, emission peak positions is at the 390nm place.
Embodiment 12
Get aluminum oxide (Al
2O
3) 765g, aluminium nitride (AlN) 205g, magnesium oxide (MgO) 180g.Place the tetrafluoroethylene ball grinder, use Si
3N
4Ball, take dehydrated alcohol as the grinding medium ball mill mixing 24 hours, the slurry that obtains mixing.Slurry is put into the baking oven that is preheated to 80～100 ℃ after dry 24 hours, sieve the dry powder that obtains mixing with 80 mesh sieves.Dry powder is placed boron nitride crucible, and put into vacuum hotpressing stove, at flowing nitrogen (N
2) reacting by heating in the atmosphere; Nitrogen flow is 0.4～0.6 liter of per minute, from room temperature to 1000 a ℃ heating-up time be 60 minutes, from 1000 to 1850 ℃ of heating-up times are 90 minutes, obtain the luminescent powder of AlON pure phase in 2 hours in 1850 ℃ of insulations.The luminescent powder that makes has the cubic spinel structure, and particle diameter is 1.0～2.5 μ m.Adopt ultimate analysis to determine that the accurate chemical expression of this luminescent powder is: Mg
4.5Al
20O
27N
5The strong blue light of emission under the ultraviolet excitation of wavelength 275nm, emission peak positions is at the 391nm place.
Embodiment 13
Get aluminum oxide (Al
2O
3) 918g, aluminium nitride (AlN) 205g.Place the tetrafluoroethylene ball grinder, use Si
3N
4Ball, take dehydrated alcohol as the grinding medium ball mill mixing 24 hours, the slurry that obtains mixing.Slurry is put into the baking oven that is preheated to 80～100 ℃ after dry 24 hours, sieve the dry powder that obtains mixing with 80 mesh sieves.Dry powder is placed boron nitride crucible, and put into vacuum hotpressing stove, at flowing nitrogen (N
2) reacting by heating in the atmosphere; Nitrogen flow is 0.4～0.6 liter of per minute, from room temperature to 1000 a ℃ heating-up time be 60 minutes, from 1000 to 1900 ℃ of heating-up times are 120 minutes, obtain the luminescent powder of AlON pure phase in 2 hours in 1900 ℃ of insulations.The luminescent powder that makes has the cubic spinel structure, and particle diameter is 1.0～5.0 μ m.Adopt ultimate analysis to determine that the accurate chemical expression of this luminescent powder is: Al
23O
27N
5The strong blue light of emission under the ultraviolet excitation of wavelength 275nm, emission peak positions is at the 385nm place.
Each important parameter of above-mentioned each embodiment is shown in following table 1:
Table 1
Ginseng sees the above table 1, comparative example 1,4,9,11 and 13 as can be known, for calcining temperature, doped with rare-earth elements Ce, Eu can relatively low temperature carry out in the calcination temperature range that allows, containing transition metal element M n the or only calcining temperature of doped with Mg is then slightly high, the calcining temperature of plain aluminum oxynitride is then relatively high; For the emission wavelength of the luminescent powder that makes, the taking second place of the longest, the doped with Mn of doping Eu, be again doped Ce or only doped with Mg, be unadulterated aluminum oxynitride at last.
The embodiment 2～8 of contrast doping Eu, along with the increase of the doping of Eu, the wavelength of emission peak also has a small increase.
Industrial applicability
:Method of the present invention prepares gained aluminum oxynitride luminescent powder can send blue light under the exciting of UV-light, be expected to become large power white light LED one of candidate material of fluorescent material matrix.Preparation method of the present invention, technique is simple, cost is low, yield is high, is fit to scale production.
Claims (17)
1. an aluminum oxynitride blue light emitting powder is characterized in that, the chemical structure of general formula of described blue light emitting powder is M
1.5yMg
1.5xAl
23-x-yO
27N
5, wherein doped element M is transition metal or rare earth element, 0≤x＜6.0,0≤y＜3.0.
2. aluminum oxynitride blue light emitting powder according to claim 1 is characterized in that, described doped element M is transition metal Mn.
3. aluminum oxynitride blue light emitting powder according to claim 1 is characterized in that, described doped element M is rare earth element Eu or Ce.
4. each described aluminum oxynitride blue light emitting powder is characterized in that 0≤x≤3.0 according to claim 1～3.
5. aluminum oxynitride blue light emitting powder according to claim 4 is characterized in that 0＜x＜1.5.
6. each described aluminum oxynitride blue light emitting powder is characterized in that 0≤y≤2.0 according to claim 1～3.
7. aluminum oxynitride blue light emitting powder according to claim 6 is characterized in that 0＜y≤1.
8. each described aluminum oxynitride blue light emitting powder is characterized in that according to claim 1～3, and described aluminum oxynitride blue light emitting powder has emission peak in 385～458nm scope under ultraviolet excitation.
9. each described aluminum oxynitride blue light emitting powder is characterized in that according to claim 1～3, and described aluminum oxynitride blue light emitting powder has the cubic spinel structure.
10. each described aluminum oxynitride blue light emitting powder is characterized in that according to claim 1～3, and the particle size range of described aluminum oxynitride blue light emitting powder is 1～5 μ m.
11. one kind according to claim 1～10 in the preparation method of each described aluminum oxynitride blue light emitting powder, it is characterized in that, comprising:
By predetermined amount proportioning raw material A l
2O
3, AlN, MgO and doped element M source, the slurry that ball milling must mix;
The slurry of dry gained makes powder, powder is sieved; And
Powder after sieving is put into boron nitride crucible, under the flowing nitrogen atmosphere, place vacuum hotpressing stove, nitrogen flow is 0.4～1.2 liter of per minute, temperature rise rate is 5～20 ℃ of per minutes, in 1700～1950 ℃ temperature range, calcine, soaking time is 1～6 hour, obtains the blue light emitting powder material.
12. preparation method according to claim 11 is characterized in that, described doped element M source is carbonate or the oxide compound of M.
13. preparation method according to claim 12 is characterized in that, described doped element M source is MnCO
3, Eu
2O
3Or CeO
2
14. preparation method according to claim 11 is characterized in that, described nitrogen flow is 0.4～0.6 liter of per minute.
15. preparation method according to claim 11 is characterized in that, temperature rise rate is 7～10 ℃ of per minutes, and calcining in 1800 ~ 1900 ℃ temperature range, and soaking time is 2～4 hours.
16. preparation method according to claim 11 is characterized in that, in ball milling, adopts dehydrated alcohol as grinding medium, and uses Si
3N
4Ball.
17. preparation method according to claim 16 is characterized in that, Si
3N
4The mass ratio of ball, reaction mixture and dehydrated alcohol is (3 ~ 10): 1:10.
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| CN103555324A (en) * | 2013-10-31 | 2014-02-05 | 电子科技大学 | Blue fluorescent powder and preparation method thereof |
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| LIANGJUN YIN等: "Synthesis and photoluminescence of Eu2+–Mg2+ co-doped γ-AlON phosphors", 《MATERIALS LETTERS》 * |
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