CN102504813A - Method for preparing Mn<2+>-doped AlON fluorescent powder - Google Patents
Method for preparing Mn<2+>-doped AlON fluorescent powder Download PDFInfo
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Abstract
The invention relates to a method for preparing Mn<2+>-doped AlON (aluminum oxynitride) fluorescent powder, belonging to the field of fluorescent ceramic material preparation. A method for preparing Mn<2+>-doped AlON fluorescent powder comprises the following steps: 1) mixing alpha-aluminum oxide, aluminum nitride and MnO (magnesium oxide), in which alpha-aluminum oxide is 69.00-87.91 wt%, aluminum nitride is 10.6-23.69 wt% and MnO is 1.41-8.41 wt%, to obtain mixed powder, and ball milling to obtain slurry; 2) drying to obtain a mixture; and 3) putting the dried mixture into a graphite reactor, putting the graphite reactor into a large-current reaction synthesis device, and filing nitrogen or mixed gas containing nitrogen into the large-current synthesis device; and directly applying a large current to the graphite reactor, heating to 1,650-1,850DEG C at a rate of 100-400DEG C/min, maintaining the temperature for 0-30min, and naturally cooling to obtain Mn<2+>-doped AlON fluorescent powder. The method of the invention has a high preparation speed; and the obtained Mn<2+>-doped AlON fluorescent powder has high purity.
Description
Technical field
The present invention relates to a kind of preparation Mn
2+The method of doped with Al ON phosphor powder belongs to the fluorescence ceramics field of material preparation.
Background technology
Utilize GaN base LED to realize that general white-light illuminating has become the whole world and realized one of main technical schemes of solid-state illumination.Target to realizing general illumination has blue-ray LED+YAG:Ce fluorescent material and UV-LED+ three-color phosphor two lines at present.For the scheme that adopts blue-ray LED+YAG:Ce fluorescent material synthesize white light; Because the deficiency of color developing improve color developing so need to add red fluorescence powder, and green emitting phosphor is indispensable; For the scheme of UV-LED+ three-color phosphor synthesize white light, green emitting phosphor is essential equally.Owing to need make excitaton source with UV-light or blue-light LED chip, these two kinds of schemes are all had higher requirement at aspects such as physics, chemicalstabilities to fluorescent material simultaneously.
At present, the research of green emitting phosphor mainly concentrates on following three big type.1) thiogallate salt system is like SrGa
2S
4: Eu
2+, excite emission 535nm green glow down at 470nm.(Y.Do, K.Ko, S.Na, Y.Huh.Luminescenceproperties of potential Sr such as Y.Do
1-xCa
xGa
2S
4Green and greenish-yellow-emitting phosphors forwhite LED.J.Electrochem.Soc.2006,153 (7): H142.) find, with Ca
2+Progressively replace Sr
2+After, emmission spectrum to 555nm, and uses these two kinds of fluorescent material to combine 455nm blue chips to make green light LED by the 535nm red shift.Yet this fluorescent material needs at deleterious H
2Synthetic in the S atmosphere, human body and environment all there are certain infringement.(I.Sastry, C.Bacalski, J.McKittrick.Preparation and green-emitting Sr such as I.Sastry
1-xEu
xGa
2S
4Phosphors by a solid-state rapid metathesis reaction.J.Electrochem.Soc.1999; 146:4316.) at a lower temperature, need not to use H with solid phase RMR method (Solid-state Rapid Metathesis Reaction)
2S gas has prepared Sr
1-xEu
xGa
2S
4(Y.Jiang, G.Villalobos, J.Souriau, H.Paris, C.Summers, Z.Wang.Synthesis and properties of green phosphor SrGa such as Y.Jiang
2S
4: Eu
2+For field emission displays by an environmentally clean technique.Solid StateCommunications.2000 113:475.) does not use H
2S gas has also prepared the SrGa that class is spherical, size distribution is even, luminous efficiency is high
2S
4: Eu
2+Fluorescent material.In addition, because the less stable of this system fluorescent material, in practical application, owing to be heated for a long time, this system fluorescent material is prone to decompose, and luminous efficiency and work-ing life etc. is caused adverse influence.2) silicate systems.Earth alkali metal orthosilicate matrix is one type of substrate material that is suitable for white light LEDs.Eu
2+Owing to get into lattice site easily with the alkaline earth metal ion similar radius, and mix Eu through Different Alkali earth metals ionic
2+Bigger crystal field splitting can appear in the 5d electronic configuration that energy is minimum, thereby produces the excitation band of broad.I.Chen etc. (I.Chen, C.Lin, C.Yeh, R.Liu.Light converting inorganic phosphors for white light-emitting diodes.Materials.2010 3:2172.) has reported (Ba
1.1Sr
0.7Eu
0.2) SiO
4Fluorescent material, this fluorescent material is blue-light excited by 460nm's, produces the green emission of 528nm.But the luminescent properties of this system fluorescent material receives Influence of Temperature very big, its luminous intensity when 150 ℃ and 300 ℃, 77% and 9% when having only 25 ℃ respectively.Therefore, this type of fluorescent material is faced with the problem that luminescent properties is degenerated in the white light LEDs use.3) nitrogen (oxygen) is changed objects system.The oxynitride green emitting phosphor mainly contains Eu at present
2+, Ce
3+, Yb
2+Etc. rare-earth ion activated Sialon (Sialon) and MSiO
2N
2Two big types.(R.J.Xie, N.Hirosaki, M.Mitomo such as R.J.Xie; K.Uheda; T.Suehiro, X.Xu, Y.Yamamoto; T.Sekiguchi.Strong green emission from activated by divalent ytterbium under blue light irradiation.Journal of Physicai Chemistry B.2005,109:9490.) at the N of 0.5MPa
2Prepared (M in 1700 ℃ of Synthetic 2 h in the atmosphere
1-xYb
x)
M/2Si
12-m-nAl
M+nO
nN
16-n, M=Ca
2+, Li
+, Mg
2+, Y
2+, x=0.002-0.1,0.5≤m=2n≤3.5.Sample presents the multimodal broadband excitation, and 445nm excites down emission 549nm green glow, can cooperate blue chip to use preferably.But the preparation process condition of nitric oxide fluorescent powder is comparatively harsh, consumption and energy consumption when in practical application, having increased, and the while has also increased the cost of fluorescent material.
The active ions overwhelming majority of phosphor for white light LED is a rare earth element ion at present, and this mainly has benefited from the advantages such as narrowband emission spectrum of abundant energy level of rare earth ion and type atom.But, receive the excitation band of rare earth ion narrow, the influence of unfavorable factor such as simultaneously its application cost is high, the transiting group metal elements ion has caused people's attention more and more, especially Mn
2+The research of doping fluorescent powder is more extensive.Study more Mn at present
2+Adulterated fluorescent material has the spinel system.(V.Singh, R.P.S.Chakrahdar, J.L.Rao, D.K.Kim.Synthesis, characterization, photoluminescence and EPR investigations of Mn doped MgAl such as V.Singh
2O
4Phosphors.Journal ofSolid State Chemistry.2007 180:2067.) adopts combustion synthesis method under 500 ℃, to prepare MgAl
2O
4: Mn
2+Green emitting phosphor.The synthesis condition of this fluorescent material is comparatively gentle, and has reduced cost.(K.Izumi, S.Miyazaki, S.Yoshida, T.Mizokawa, E.Hanamura.optical properties of 3d transition-metal-doped MgAl such as K.Izumi
2O
4B.2007, spinels.Physics Review 76:1.) studies the adulterated magnesium aluminate spinel fluorescent powder of a series of transition-metal ions, finds to work as doped with Mn
2+The time magnesium aluminate spinel fluorescent powder transmitting green light.
γ-AlON is the cubic spinel type crystal structure, has good thermostability and chemicalstability, is a kind of ideal fluorescent material substrate material.(R.J.Xie, N.Hirosaki, X.J.Liu, T.Takeda, H.L.Li.Crystal structure and photoluminescence of Mn such as R.J.Xie
2+-Mg
2+Codoped gamma aluminum oxynitride (γ-AlON): A promising phosphor for white light-emitting diodes.Applied PhysicsLetters.92; 201905 (2008) .) adopt Alpha-alumina, aluminium nitride AlN, Natural manganese dioxide and manganous carbonate; At synthesis temperature is 1800 ℃; Soaking time is 2h, the N of 0.5MPa
2Under the condition of atmosphere pressures, prepared the AlON:Mg of pure phase
2+, Mn
2+Phosphor powder, and its crystalline structure and photoluminescence performance studied.The result shows AlON:Mg
2+, Mn
2+Fluorescent material has peak wavelength and is positioned at the broadband green light emission of 520nm, monochromaticity is good, quantum yield is high and hot-quenching is gone out little characteristics, is a kind of fluorescent material that is applicable to general White-light LED illumination.(S.Kikkawa such as S.Kikkawa; N.Hatta; T.Takeda.Preparation of Aluminum Oxynitride by Nitridation of a Precursor Derived from Aluminum-Glycine Gel and the Effect of the Presence of the Europium.Journal of theAmerican Ceramic Society.2008 91:924.) has synthesized Eu through the method for nitride-oxide presoma
2+Adulterated AlON fluorescent material, but because Eu
2+The ionic radius is too big, can't be solidly soluted in the AlON crystal, and Eu
2+Ion is proved in the oxide compound that is present in the Magnetoplumbate-type structure.(L.J.Yin, X.Xu, L.Y.Hao, W.J.Xie, Y.F.Wang, L.X.Yang, X.F.Yang.Synthesis and photoluminescence of Eu such as L.J.Yin
2+-Mg
2+Co-doped γ-AlON phosphors.Materials Letters.2009 63:1511.) then adopts high temperature solid-state method under 1800 ℃ of high temperature, to be incubated 2h with the intensification of 300 ℃/min and rate of temperature fall and carries out Eu
2+Adulterated AlON fluorescent material, processing condition are more harsh, yet still can't obtain the Eu of pure phase
2+Doped with Al ON fluorescent material.(F.Zhang, L.Q.An, X.J.Liu, G.H.Zhou, X.Y.Yuan, S.W.Wang.Upconversion luminescence in γ-AlON:Yb such as F.Zhang
3+, Tm
3+Ceramic phosphors.Journal of the American Ceramic Society.2009 is 92:1888.) to Yb
3+And Tm
3+The up-conversion luminescence performance of codoped AlON fluorescent material is studied.From existing research, Mn
2+The research of doped with Al ON fluorescent material still is in the starting stage, does not see other relevant report.
Summary of the invention
The purpose of this invention is to provide a kind of preparation Mn
2+The method of doped with Al ON phosphor powder, it is fast that this method prepares speed, gained Mn
2+Doped with Al ON phosphor powder purity is high.
To achieve these goals, technical scheme of the present invention is: a kind of preparation Mn
2+The method of doped with Al ON phosphor powder is characterized in that it comprises the steps:
1) by the shared mass percent of Alpha-alumina, aluminium nitride AlN and MnO (maybe can be decomposed into the compound of MnO) is: Alpha-alumina 69.00-87.91wt%, aluminium nitride AlN 10.68-23.69wt%, MnO 1.41-8.14wt%; Alpha-alumina, aluminium nitride AlN and MnO (maybe can be decomposed into the compound of MnO) are mixed, obtain mixed powder; By ball (aluminum oxide) material mass ratio is 2～4: 1, and mixed powder is scattered in the absolute ethyl alcohol, and ball milling is no less than 24 hours, gets slurry;
2) slurry with step 1) places vacuum drying oven at 40-60 ℃ of following freeze-day with constant temperature 100-200min, gets mixture;
3) dried mixture is placed graphiote reactor, graphiote reactor places big current response synthesizer, is filled with nitrogen in the big current response synthesizer or contains the mixed gas of nitrogen, and the body pressure of inflating is not more than 0.1MPa; Graphiote reactor is directly applied big electric current, be heated to 1650-1850 ℃ with the heat-up rate of 100 ℃ of-400 ℃/min, soaking time is 0-30min, behind the naturally cooling, Mn
2+Doped with Al ON phosphor powder.
The purity of described Alpha-alumina is greater than 99.5wt%, and median size is less than or equal to 1 μ m, and the concentration of contained metallic impurity is lower than 500ppm (being meant mass concentration).
The purity of described aluminium nitride AlN is greater than 98wt%, and median size is less than or equal to 200nm, and the concentration of contained metallic impurity is lower than 5000ppm (being meant mass concentration).
Described MnO can be obtained by the compound decomposition that can be decomposed into MnO.The compound powder that can be decomposed into MnO is that in the powder such as manganous carbonate, manganous nitrate one or more mix arbitrarily.
The purity of said MnO (maybe can be decomposed into the compound of MnO) is 98wt%, and median size is below 5 μ m.
The described mixing of step 1) can mix the sufficiently long time in the mixing equipment of any kind of, thereby obtains uniform mixture.For example: mixing time can be 24-48 hour in ball mill.Above-mentioned mixing can be adopted to do and mix or wet mixing technology.Wet mixing can be used water-free organic solvent, for example methyl alcohol, absolute ethyl alcohol, Virahol or toluene etc.
Step 2) drying of described mixture is generally carried out in dry gas atmosphere, anyly in the drying temperature scope can not be used as dry gas with the gas of said mixture generation chemical reaction; For example: nitrogen; Argon gas, helium and air etc. are preferably selected air.Drying can be carried out under normal pressure or negative pressure.Drying temperature generally is no more than 60 ℃, and needs time enough to make described mixture complete drying.
Principle of the present invention is: be the basis with Alpha-alumina, aluminium nitride AlN, MnO (maybe can be decomposed into the compound of MnO) three-phase solid state reaction, use big electric current synthesizer synthetic powder.Fast intensification and the cooling rate and short soaking time of big electric current effectively suppressed growing up of product crystal grain in building-up process, reduced synthesis temperature, improved transformation efficiency.
The invention has the beneficial effects as follows:
1, the fluorescent material of this method preparation have high purity (>=98.2wt%) and size distribution even, building-up process speed is fast, preparation efficiency is high, energy consumption is low.
2, the Mn of preparation
2+Doped with Al ON fluorescent material has the green emission that peak wavelength is 510nm, is applicable to the application of white light LEDs.
3, this procedure is simple.
Description of drawings
Fig. 1 is Mn of the present invention
2+The XRD figure spectrum of doped with Al ON phosphor powder has 4 spectral lines, the Mn that makes among embodiment 1, embodiment 3, embodiment 5 and the embodiment 7 respectively
2+Doped with Al ON phosphor powder;
The Mn of Fig. 2 for making in the embodiment of the invention 3
2+The exciting light spectrogram of doped with Al ON phosphor powder, emission wavelength are 510nm;
The Mn of Fig. 3 for making in the embodiment of the invention 3
2+The emmission spectrum figure of doped with Al ON phosphor powder, excitation wavelength is 445nm.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with accompanying drawing, embodiment and not only be confined to following embodiment.
Following embodiment 1-8 is adopted: the purity of Alpha-alumina is greater than 99.5wt%, and median size is less than or equal to 1 μ m, and the concentration of contained metallic impurity is lower than 500ppm.The purity of aluminium nitride AlN is greater than 98wt%, and median size is less than or equal to 200nm, and the concentration of contained metallic impurity is lower than 5000ppm.The purity of MnO (maybe can be decomposed into the compound of MnO) is 98wt%, and median size is below 5 μ m.
Embodiment 1:
Take by weighing the 69.00g Alpha-alumina, 22.86g aluminium nitride AlN and 8.14g MnO put into the batch mixing bottle and mix, and obtain mixed powder; By ball (aluminum oxide) material mass ratio is 4: 1, adds the 200mL absolute ethyl alcohol, and ball milling 24 hours gets slurry; Slurry at 60 ℃ of following vacuum-drying 120min, is got mixture; The mixture that drying is good is crossed 100 mesh sieves, gets 3g and packs in the graphiote reactor, and graphiote reactor places big current response synthesizer, feeds 0.1MPa nitrogen as shielding gas in the big current response synthesizer; Graphiote reactor is directly applied big electric current, be heated to 1750 ℃ with the heat-up rate of 100 ℃/min, and under this temperature, be incubated 10min, reduce to room temperature then naturally, obtain Mn
2+Doped with Al ON phosphor powder.
Adopt XRD to this Mn
2+Doped with Al ON phosphor powder is carried out thing and is detected mutually, and the gained powder is single phase Mn
2+Doped with Al ON (as shown in Figure 1) does not find residual Alpha-alumina, aluminium nitride AlN and MnO.Can know the Mn in the powder that obtains through quantitative analysis
2+The purity of doped with Al ON thing phase is 99.6wt%.Luminescent spectrum shows, Mn
2+Doped with Al ON fluorescent material has stronger broad-band illumination (excitation wavelength is 445nm) at the 510nm place.This heat-up rate with 100 ℃/min of embodiment is heated to 1750 ℃, and under this temperature, is incubated 10min, and it is fast to explain that this method prepares speed.
Embodiment 2:
Measure the 87.91g Alpha-alumina, 10.68g aluminium nitride AlN and 1.41g MnO put into the batch mixing bottle and mix, and obtain mixed powder; By ball (aluminum oxide) material mass ratio is 4: 1, adds the 200mL absolute ethyl alcohol, and ball milling 24 hours gets slurry; Slurry at 60 ℃ of following vacuum-drying 150min, is got mixture; The mixture that drying is good is crossed 100 mesh sieves, gets 3g and packs in the graphiote reactor, and graphiote reactor places big current response synthesizer, feeds 0.1MPa nitrogen as shielding gas in the big current response synthesizer; Graphiote reactor is directly applied big electric current, be heated to 1750 ℃ with the heat-up rate of 100 ℃/min, and under this temperature, be incubated 10min, reduce to room temperature then naturally, gained is Mn
2+Doped with Al ON phosphor powder.
Adopt XRD that this powder is carried out thing and detect mutually, the gained powder is single phase Mn
2+Doped with Al ON does not find residual Alpha-alumina, aluminium nitride AlN and MnO.Can know the Mn in the powder that obtains through quantitative analysis
2+The purity of doped with Al ON thing phase is 98.7wt%.Luminescent spectrum shows, Mn
2+Doped with Al ON fluorescent material has stronger broad-band illumination (excitation wavelength is 445nm) at the 510nm place.
Embodiment 3:
Measure the 76.50g Alpha-alumina, 15.50g aluminium nitride AlN and 8.00g MnO put into the batch mixing bottle and mix, and obtain mixed powder; By ball (aluminum oxide) material mass ratio is 4: 1, adds the 200mL absolute ethyl alcohol, and ball milling 24 hours gets slurry; Slurry at 60 ℃ of following vacuum-drying 180min, is got mixture; The mixture that drying is good is crossed 100 mesh sieves, gets 3g and packs in the graphiote reactor, and graphiote reactor places big current response synthesizer, feeds 0.1MPa nitrogen as shielding gas in the big current response synthesizer; Graphiote reactor is directly applied big electric current, be heated to 1750 ℃ with the heat-up rate of 100 ℃/min, and under this temperature, be incubated 10min, reduce to room temperature then naturally, gained is Mn
2+Doped with Al ON phosphor powder.
Adopt XRD that this powder is carried out thing and detect mutually, the gained powder is single phase Mn
2+Doped with Al ON (as shown in Figure 1) does not find residual Alpha-alumina, aluminium nitride AlN and MnO.Can know the Mn in the powder that obtains through quantitative analysis
2+The purity of doped with Al ON thing phase is 99.2wt%.Luminescent spectrum shows, Mn
2+Doped with Al ON fluorescent material has stronger broad-band illumination (excitation wavelength is 445nm) (like Fig. 2, shown in Figure 3) at the 510nm place.
Embodiment 4:
Measure the 82.52g Alpha-alumina, 16.05g aluminium nitride AlN and 1.43g MnO put into the batch mixing bottle and mix, and obtain mixed powder; By ball (aluminum oxide) material mass ratio is 4: 1, adds the 200mL absolute ethyl alcohol, and ball milling 24 hours gets slurry; Slurry at 60 ℃ of following vacuum-drying 120min, is got mixture; The mixture that drying is good is crossed 100 mesh sieves, gets 3g and packs in the graphiote reactor, and graphiote reactor places big current response synthesizer, feeds 0.1MPa nitrogen as shielding gas in the big current response synthesizer; Graphiote reactor is directly applied big electric current, be heated to 1750 ℃ with the heat-up rate of 100 ℃/min, and under this temperature, be incubated 10min, reduce to room temperature then naturally, gained is Mn
2+Doped with Al ON phosphor powder.
Adopt XRD that this powder is carried out thing and detect mutually, the gained powder is single phase Mn
2+Doped with Al ON does not find residual Alpha-alumina, aluminium nitride AlN and MnO.Can know the Mn in the powder that obtains through quantitative analysis
2+The purity of doped with Al ON thing phase is 98.9wt%.Luminescent spectrum shows, Mn
2+Doped with Al ON fluorescent material has stronger broad-band illumination (excitation wavelength is 445nm) at the 510nm place.
Embodiment 5:
Measure the 80.01g Alpha-alumina, 15.82g aluminium nitride AlN and 4.17g MnO put into the batch mixing bottle and mix, and obtain mixed powder; By ball (aluminum oxide) material mass ratio is 4: 1, adds the 200mL absolute ethyl alcohol, and ball milling 24 hours gets slurry; Slurry at 60 ℃ of following vacuum-drying 180min, is got mixture; The mixture that drying is good is crossed 100 mesh sieves, gets 3g and packs in the graphiote reactor, and graphiote reactor places big current response synthesizer, feeds 0.1MPa nitrogen as shielding gas in the big current response synthesizer; Graphiote reactor is directly applied big electric current, be heated to 1650 ℃ with the heat-up rate of 100 ℃/min, and under this temperature, be incubated 10min, reduce to room temperature then naturally, gained is Mn
2+Doped with Al ON phosphor powder.
Adopt XRD that this powder is carried out thing and detect mutually, the gained powder is single phase Mn
2+Doped with Al ON does not find residual Alpha-alumina, aluminium nitride AlN and MnO.Can know the Mn in the powder that obtains through quantitative analysis
2+The purity of doped with Al ON thing phase is 99.7wt%.Luminescent spectrum shows, Mn
2+Doped with Al ON fluorescent material has stronger broad-band illumination (excitation wavelength is 445nm) at the 510nm place.
Embodiment 6:
Measure the 80.01g Alpha-alumina, 15.82g aluminium nitride AlN and 4.17g MnO put into the batch mixing bottle and mix, and obtain mixed powder; By ball (aluminum oxide) material mass ratio is 4: 1, adds the 200mL absolute ethyl alcohol, and ball milling 24 hours gets slurry; Slurry at 50 ℃ of following vacuum-drying 110min, is got mixture; The mixture that drying is good is crossed 100 mesh sieves, gets 3g and packs in the graphiote reactor, and graphiote reactor places big current response synthesizer, feeds 0.1Mpa nitrogen as shielding gas in the big current response synthesizer; Graphiote reactor is directly applied big electric current, be heated to 1850 ℃ with the heat-up rate of 400 ℃/min, and under this temperature, be incubated 10min, reduce to room temperature then naturally, gained is Mn
2+Doped with Al ON phosphor powder.
Adopt XRD that this powder is carried out thing and detect mutually, the gained powder is single phase Mn
2+Doped with Al ON does not find residual Alpha-alumina, aluminium nitride AlN and MnO.Can know the Mn in the powder that obtains through quantitative analysis
2+The purity of doped with Al ON thing phase is 98.2wt%.Luminescent spectrum shows, Mn
2+Doped with Al ON fluorescent material has stronger broad-band illumination (excitation wavelength is 445nm) at the 510nm place.
Embodiment 7:
Measure the 80.01g Alpha-alumina, 15.82g aluminium nitride AlN and 4.16g MnO put into the batch mixing bottle and mix, and obtain mixed powder; By ball (aluminum oxide) material mass ratio is 4: 1, adds the 200mL absolute ethyl alcohol, and ball milling 24 hours gets slurry; Slurry at 60 ℃ of following vacuum-drying 190min, is got mixture; The mixture that drying is good is crossed 100 mesh sieves, gets 3g and packs in the graphiote reactor, and graphiote reactor places big current response synthesizer, feeds 0.1MPa nitrogen as shielding gas in the big current response synthesizer; Graphiote reactor is directly applied big electric current, be heated to 1850 ℃ with the heat-up rate of 50 ℃/min, and under this temperature, be incubated 0min, reduce to room temperature then naturally, gained is Mn
2+Doped with Al ON phosphor powder.
Adopt XRD that this powder is carried out thing and detect mutually, the gained powder is single phase Mn
2+Doped with Al ON does not find residual Alpha-alumina, aluminium nitride AlN and MnO.Can know the Mn in the powder that obtains through quantitative analysis
2+The purity of doped with Al ON thing phase is 98.5wt%.Luminescent spectrum shows, Mn
2+Doped with Al ON fluorescent material has stronger broad-band illumination (excitation wavelength is 445nm) at the 510nm place.
Embodiment 8:
Measure the 80.01g Alpha-alumina, 15.82g aluminium nitride AlN and 4.17g MnO put into the batch mixing bottle and mix, and obtain mixed powder; By ball (aluminum oxide) material mass ratio is 4: 1, adds the 200mL absolute ethyl alcohol, and ball milling 24 hours gets slurry; Slurry at 50 ℃ of following vacuum-drying 100min, is got mixture; The mixture that drying is good is crossed 100 mesh sieves, gets 3g and packs in the graphiote reactor, and graphiote reactor places big current response synthesizer, feeds 0.051MPa nitrogen as shielding gas in the big current response synthesizer; Graphiote reactor is directly applied big electric current, be heated to 1650 ℃ with the heat-up rate of 400 ℃/min, and under this temperature, be incubated 30min, reduce to room temperature then naturally, gained is Mn
2+Doped with Al ON phosphor powder.
Adopt XRD that this powder is carried out thing and detect mutually, the gained powder is single phase Mn
2+Doped with Al ON does not find residual Alpha-alumina, aluminium nitride AlN and MnO.Can know the Mn in the powder that obtains through quantitative analysis
2+The purity of doped with Al ON thing phase is 99.0wt%.Luminescent spectrum shows, Mn
2+Doped with Al ON fluorescent material has stronger broad-band illumination (excitation wavelength is 445nm) at the 510nm place.
Embodiment 8:
Measure the 72.3g Alpha-alumina, 23.69g aluminium nitride AlN and 4.01g MnO put into the batch mixing bottle and mix, and obtain mixed powder; By ball (aluminum oxide) material mass ratio is 3: 1, adds the 200mL absolute ethyl alcohol, and ball milling 48 hours gets slurry; Slurry at 40 ℃ of following vacuum-drying 200min, is got mixture; The mixture that drying is good is crossed 100 mesh sieves, gets 3g and packs in the graphiote reactor, and graphiote reactor places big current response synthesizer, feeds 0.1MPa gas (mixed gas that promptly contains nitrogen) as shielding gas in the big current response synthesizer; Graphiote reactor is directly applied big electric current, be heated to 1650 ℃ with the heat-up rate of 400 ℃/min, and under this temperature, be incubated 2min, reduce to room temperature then naturally, gained is Mn
2+Doped with Al ON phosphor powder.
Adopt XRD that this powder is carried out thing and detect mutually, the gained powder is single phase Mn
2+Doped with Al ON does not find residual Alpha-alumina, aluminium nitride AlN and MnO.Can know the Mn in the powder that obtains through quantitative analysis
2+The purity of doped with Al ON thing phase is 99.0wt%.Luminescent spectrum shows, Mn
2+Doped with Al ON fluorescent material has stronger broad-band illumination (excitation wavelength is 445nm) at the 510nm place.
Embodiment 9:
At first, decompose, obtain MnO by manganous carbonate;
Measure the 80.01g Alpha-alumina, 15.82g aluminium nitride AlN and 4.17g MnO put into the batch mixing bottle and mix, and obtain mixed powder; By ball (aluminum oxide) material mass ratio is 2: l, add the 200mL absolute ethyl alcohol, and ball milling 36 hours gets slurry; Slurry at 50 ℃ of following vacuum-drying 160min, is got mixture; The mixture that drying is good is crossed 100 mesh sieves; Getting 3g packs in the graphiote reactor; Graphiote reactor places big current response synthesizer, and the mixed gas (nitrogen and argon gas, volume respectively account for l/2) that feeding 0.1MPa contains nitrogen in the big current response synthesizer is as shielding gas; Graphiote reactor is directly applied big electric current, be heated to 1650 ℃ with the heat-up rate of 400 ℃/min, and under this temperature, be incubated 5min, reduce to room temperature then naturally, gained is Mn
2+Doped with Al ON phosphor powder.
Adopt XRD that this powder is carried out thing and detect mutually, the gained powder is single phase Mn
2+Doped with Al ON does not find residual Alpha-alumina, aluminium nitride AlN and MnO.Can know the Mn in the powder that obtains through quantitative analysis
2+The purity of doped with Al ON thing phase is 99.0wt%.Luminescent spectrum shows, Mn
2+Doped with Al ON fluorescent material has stronger broad-band illumination (excitation wavelength is 445nm) at the 510nm place.
Embodiment 10:
Basic identical with embodiment 9, difference is: the heat-up rate with 400 ℃/min is heated to 1650 ℃, reduces to room temperature (promptly not being incubated) then naturally, and gained is Mn
2+Doped with Al ON phosphor powder.
Adopt XRD that this powder is carried out thing and detect mutually, the gained powder is single phase Mn
2+Doped with Al ON does not find residual Alpha-alumina, aluminium nitride AlN and MnO.Can know the Mn in the powder that obtains through quantitative analysis
2+The purity of doped with Al ON thing phase is 99.0wt%.Luminescent spectrum shows, Mn
2+Doped with Al ON fluorescent material has stronger broad-band illumination (excitation wavelength is 445nm) at the 510nm place.
Embodiment 11:
Basic identical with embodiment 9, difference is: decomposed by manganous nitrate manganese, obtain MnO.
Employing can be decomposed into the compound of MnO, like one or both and the above mixed powder thereof in manganous carbonate or the manganous nitrate etc., all can realize identical effect, does not enumerate embodiment one by one at this.
The bound value of each processing parameter of the present invention (like heat-up rate, temperature, time etc.), with and interval value, can both realize the present invention, do not enumerate embodiment one by one at this.
Claims (5)
1. one kind prepares Mn
2+The method of doped with Al ON phosphor powder is characterized in that it comprises the steps:
1) by the shared mass percent of Alpha-alumina, aluminium nitride AlN and MnO be: Alpha-alumina 69.00-87.91wt%, aluminium nitride AlN 10.68-23.69wt%, MnO 1.41-8.14wt%, Alpha-alumina, aluminium nitride AlN and MnO are mixed, obtain mixed powder; By ball material mass ratio is 2～4: 1, and mixed powder is scattered in the absolute ethyl alcohol, and ball milling is no less than 24 hours, gets slurry;
2) slurry with step 1) places vacuum drying oven at 40-60 ℃ of following freeze-day with constant temperature 100-200min, gets mixture;
3) dried mixture is placed graphiote reactor, graphiote reactor places big current response synthesizer, is filled with nitrogen in the big current response synthesizer or contains the mixed gas of nitrogen, and the body pressure of inflating is not more than 0.1MPa; Graphiote reactor is directly applied big electric current, be heated to 1650-1850 ℃ with the heat-up rate of 100 ℃ of-400 ℃/min, soaking time is 0-30min, behind the naturally cooling, Mn
2+Doped with Al ON phosphor powder.
2. a kind of preparation Mn according to claim 1
2+The method of doped with Al ON phosphor powder is characterized in that: the purity of described Alpha-alumina is greater than 99.5wt%, and median size is less than or equal to 1 μ m, and the concentration of contained metallic impurity is lower than 500ppm.
3. a kind of preparation Mn according to claim 1
2+The method of doped with Al ON phosphor powder is characterized in that: the purity of described aluminium nitride AlN is greater than 98wt%, and median size is less than or equal to 200nm, and the concentration of contained metallic impurity is lower than 5000ppm.
4. a kind of preparation Mn according to claim 1
2+The method of doped with Al ON phosphor powder is characterized in that: the purity of said MnO is 98wt%, and median size is below 5 μ m.
5. according to claim 1 or 4 described a kind of preparation Mn
2+The method of doped with Al ON phosphor powder is characterized in that: described MnO is obtained by the compound decomposition that can be decomposed into MnO, and the compound powder that can be decomposed into MnO is that in manganous carbonate, the manganous nitrate powder one or more mix arbitrarily.
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