CN102477299B - Lanthanum aluminate luminescent material and preparation method thereof - Google Patents
Lanthanum aluminate luminescent material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to field of luminescent materials, and discloses a lanthanum aluminate luminescent material and a preparation method thereof. The lanthanum aluminate luminescent material has a chemical general formula of La(1-x-y)ReyLnxAlO3, wherein Ln is one selected from Tm, Tb, Sm and Eu, Re is Y, Gd or Lu, the value range of x is 0.001-0.2, and the value range of y is 0-0.2 times (1-x).According to the present invention, compared to the traditional lanthanum aluminate luminescent material, the luminescence efficiency of the lanthanum aluminate luminescent material of the present invention is increased by 40%, and the lanthanum aluminate luminescent material of the present invention can be applicable for field emission devices; the lanthanum aluminate luminescent material prepared by the method of the present invention has high luminescence brightness under the cathode ray excitation.
Description
Technical field
The present invention relates to field of photovoltaic materials, relate in particular to a kind of luminescent material of lanthanum aluminate doped with rare-earth elements.The invention still further relates to the preparation method of lanthanum aluminate light-emitting material.
Background technology
Feds is because its running voltage is low in recent years, power consumption is little, do not need deflector coil, without X-radiation, the advantage such as radioprotective and magneticinterference and receiving much concern, field-transmitting cathode and luminescent material can be used and the fields such as demonstration, various indication, general lighting in conjunction with the field emission light source that can obtain high brightness, high colour developing.One of key factor of preparation premium properties feds is the preparation of high-performance fluorescent powder.The fluorescent material that present feds adopts mainly is some sulfide series that are used for conventional cathode ray tube and projection TV teletron, oxide compound is serial and the oxysulfide series phosphor powder.In display application, narrowband emission spectrum has proposed less strict demand to the optical system of projection TV etc.Therefore the arrowband luminescent material of doping with rare-earth ions has larger advantage.
Summary of the invention
In order to address the above problem, the invention provides a kind of lanthanum aluminate light-emitting material, have following chemical general formula: La
1-x-yRe
yLn
xAlO
3Wherein, Ln is at least a among Tm, Tb, Sm or the Eu, and Re is at least a among Y, Gd or the Lu, and the span of x is 0.001～0.2; The span of x preferred 0.001～0.15; The span of y is 0～0.2 times of 1-x.
The present invention also provides the preparation method of above-mentioned lanthanum aluminate light-emitting material, and preparation flow is as follows:
According to chemical general formula La
1-x-yRe
yLn
xAlO
3The stoichiometric ratio of middle Al provides the source compound of Al and is configured to the Al deionized water solution; Wherein, Ln is at least a among Tm (thulium), Tb (terbium), Sm (samarium) or the Eu (europium), Re is at least a among Y (yttrium), Gd (gadolinium) or the Lu (lutetium), and the span of x is that the span of 0.001～0.2, y is 0～0.2 times of 1-x;
In above-mentioned Al deionized water solution, add alkaline solution, such as ammoniacal liquor, regulate the pH value to 8 of Al deionized water solution, make nano aluminium oxide colloidal sol;
In above-mentioned nano aluminium oxide colloidal sol, add sinking agent (its mole dosage is 1～1.5 times of Al ion molar weight), such as ammonium oxalate, drip respectively subsequently the aqueous solution that contains La ion and Ln ion, then add alkaline solution, such as ammoniacal liquor, regulate the pH value to 9 of whole mixing solutions, stir, filter, dry throw out;
Successively in 600～900 ℃ of lower thermal pretreatment 0.5～2h, and 1200～1500 ℃ of lower sintering processes 0.5～5h, grind at cooling, make described lanthanum aluminate light-emitting material to above-mentioned throw out; Wherein, thermal pretreatment is carried out under air atmosphere, and sintering processes can be carried out under air atmosphere or reduction atmosphere.
Compared with prior art, the present invention has the following advantages:
The invention provides a kind of lanthanum aluminate light-emitting material and preparation method thereof for preparing, wherein, the lanthanum aluminate light-emitting material that uses the method to prepare has higher luminosity under cathode-ray exciting, luminous efficiency than traditional lanthanum aluminate light-emitting material has 40% raising, and can be applicable in the feds.
Description of drawings
Fig. 1 is preparation technology's schema of lanthanum aluminate light-emitting material of the present invention;
Fig. 2 is the cathodoluminescence spectrum comparison diagram of the lanthanum aluminate light-emitting material of the lanthanum aluminate light-emitting material for preparing of additive method and embodiment 3 preparations; Wherein, curve 11 refers to the lanthanum aluminate light-emitting material of embodiment 3 preparations, and curve 12 is that the lanthanum aluminate that the Philips patent method prepares is mixed the Tm luminescent material;
Fig. 3 is Zn
1.992SiO
4: Mn
0.008The cathodoluminescence spectrum comparison diagram of the lanthanum aluminate light-emitting material of fluorescent material and embodiment 3 preparations; Wherein, curve 10 refers to commercial rainbow CRT blue powder ZnS:Ag (Cl) fluorescent material, and curve 11 refers to the lanthanum aluminate light-emitting material of embodiment 3 preparations;
Fig. 4 is the cathodoluminescence spectrogram of the lanthanum aluminate light-emitting material of embodiment 5 preparations.
Embodiment
The invention provides a kind of lanthanum aluminate light-emitting material, it is characterized in that, this lanthanum aluminate light-emitting material has following chemical general formula: La
1-x-yRe
yLn
xAlO
3Wherein, Ln is a kind of among Tm, Tb, Sm or the Eu, and Re is Y, Gd or Lu, and the span of x is 0.001～0.2; The span of x preferred 0.001～0.15; The span of y is 0～0.2 times of 1-x; Simultaneously, La
1-x-yRe
yLn
xAlO
3In the luminescent material, the molar weight of Al is La
1-x-yRe
yLn
xAlO
31～1.1 times of integral molar quantity.
Make the method for above-mentioned lanthanum aluminate light-emitting material, as shown in Figure 1, preparation flow is as follows:
Step S1, according to chemical general formula La
1-x-yRe
yLn
xAlO
3In the stoichiometric ratio of each element, the source compound of Al element is provided, adopt aluminum nitrate among the present invention; Wherein, Ln is at least a among Tm, Tb, Sm or the Eu, and Re is at least a among Y, Gd or the Lu, the span of y be 0～0.2 times of 1-x (be that La can partly be replaced by Y, Gd or Lu, maximum replacement amount be no more than the La molar weight 20%); The span of x is 0.001～0.2 (preferred 0.001～0.15);
Step S2, according to the above-mentioned source compound that Al is provided, it is dissolved in the deionized water, be configured to the Al deionized water solution, and the mole dosage of aluminium salt excessive 0～10% (molar weight that is Al is La
1-x-yRe
yLn
xAlO
31～1.1 times of integral molar quantity);
Under step S3,35～45 ℃ of heating conditions, add fast alkaline solution toward above-mentioned Al deionized water solution, such as ammoniacal liquor, stir, make the pH value of Al deionized water solution transfer to 8, then continue to be heated to 70 ℃ of lower stirring 1h, make nano aluminium oxide colloidal sol;
Step S4, add 1～1.5 times sinking agent of Al ion molar weight in the above-mentioned nano aluminium oxide colloidal sol, such as ammonium oxalate, drip respectively subsequently the aqueous solution that contains La ion and Ln ion, then add alkaline solution, such as ammoniacal liquor, stir 1～2h, the pH value to 9 of regulating whole mixing solutions stirs, filters, dries throw out;
Under step S5, the air atmosphere, above-mentioned throw out in 600～900 ℃ (preferred 800 ℃) lower thermal pretreatment 0.5～2h, is warming up to 1200～1500 ℃ of lower sintering processes 0.5～5h subsequently, cooling, grinding make described lanthanum aluminate light-emitting material; Wherein, thermal pretreatment is carried out under air atmosphere, and sintering processes can be carried out under air atmosphere or reduction atmosphere.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1La
0.999Tm
0.001AlO
3
At first take by weighing nine water aluminum nitrate 1.8756g (5mmol), be dissolved in the 10ml deionized water, be stirred and heated to 35 degree, add fast ammoniacal liquor, regulator solution pH to 8 continues to stir 0.5h, and then is heated to 70 degree, continue to stir 1h, add the ammonium oxalate solution that 25ml concentration is 0.3mol/L, dripping 4.995ml concentration is the lanthanum nitrate hexahydrate of 1mol/L and the thulium nitrate solution that 0.05ml concentration is 0.1mol/L, rear dropping ammoniacal liquor again, regulator solution pH to 9 continues to stir 1h.Last filtration washing oven dry throw out, pre-treatment 0.5h under air atmosphere 900 degree in the lower 1500 ℃ of heat preservation sintering 0.5h of air atmosphere, is cooled to room temperature again, grinds and namely obtains La
0.999Tm
0.001AlO
3Luminescent material.This material can be launched blue light, good luminous performance under cathode-ray exciting.
Embodiment 2La
0.9Y
0.05Sm
0.05AlO
3
At first take by weighing nine water aluminum nitrate 1.9507g (5.2mmol), be dissolved in the 10ml deionized water, be stirred and heated to 40 degree, add fast ammoniacal liquor, regulator solution pH to 8 continues to stir 0.5h, and then is heated to 70 degree, continue to stir 1h, drip the lanthanum nitrate hexahydrate that 4.5ml concentration is 1mol/L, 0.25ml concentration is that yttrium nitrate solution and the 2.5ml concentration of 1mol/L is the samarium nitrate solution of 0.1mol/L, rear dropping ammoniacal liquor again, regulator solution pH to 9 continues to stir 2h.Last filtration washing oven dry throw out, pre-treatment 1h under air atmosphere 800 degree in the lower 1200 ℃ of heat preservation sintering 5h of air atmosphere, is cooled to room temperature again, grinds and namely obtains La
0.9Y
0.05Sm
0.05AlO
3Luminescent material.This material can be launched orange red light under cathode-ray exciting, good luminous performance, and purity of color is high.
Embodiment 3La
0.99Tm
0.01AlO
3
At first take by weighing nine water aluminum nitrate 2.0632g (5.5mmol), be dissolved in the 20ml deionized water, be stirred and heated to 45 degree, add fast ammoniacal liquor, regulator solution pH to 8 continues to stir 0.5h, and then is heated to 70 degree, continue to stir 1h, add the ammonium oxalate solution that 10ml concentration is 0.3mol/L, dripping 4.95ml concentration is the lanthanum nitrate hexahydrate of 1mol/L and the thulium nitrate solution that 0.5ml concentration is 0.1mol/L, rear dropping ammoniacal liquor again, regulator solution pH to 9 continues to stir 2h.Last filtration washing oven dry throw out, pre-treatment 2h under air atmosphere 600 degree in the lower 1400 ℃ of heat preservation sintering 1h of air atmosphere, is cooled to room temperature again, grinds and namely obtains La
0.99Tm
0.01AlO
3Luminescent material.This material can be launched blue light, good luminous performance under cathode-ray exciting.
Fig. 2 is the cathodoluminescence spectrum comparison diagram of the aluminate luminescent material of the aluminate luminescent material for preparing of additive method and embodiment 3 preparations; Wherein, curve 11 refers to the aluminate luminescent material of embodiment 3 preparations, and curve 12 is that the lanthanum aluminate that the Philips patent method prepares is mixed the Tm luminescent material.
Fig. 3 is the cathodoluminescence spectrum comparison diagram of the aluminate luminescent material of commercial rainbow CRT blue powder ZnS:Ag (Cl) fluorescent material and present embodiment preparation, wherein, curve 11 refers to the aluminate luminescent material of present embodiment preparation, and curve 10 refers to commercial rainbow CRT blue powder ZnS:Ag (Cl) fluorescent material.
As shown in Figure 3, the blue-light-emitting peak strength of the luminescent material that present embodiment prepares is 430% of ZnS:Ag (Cl) fluorescent material, and the luminescent material of present embodiment has good stability, characteristics that luminous efficiency is high.
Embodiment 4La
0.7Gd
0.1Eu
0.2AlO
3
At first take by weighing nine water aluminum nitrate 2.0257g (5.4mmol), be dissolved in the 15ml deionized water, be stirred and heated to 45 degree, add fast ammoniacal liquor, regulator solution pH to 8, continue to stir 0.5h, and then be heated to 70 the degree, continue to stir 1h, add the ammonium oxalate solution that 5ml concentration is 0.3mol/L again, dripping 3.5ml concentration is the lanthanum nitrate hexahydrate of 1mol/L, 0.5ml concentration is that Gadolinium trinitrate solution and the 1ml concentration of 1mol/L is the europium nitrate solution of 1mol/L, rear dropping ammoniacal liquor, regulator solution pH to 9 continues to stir 1h.Last filtration washing oven dry throw out, pre-treatment 1.5h under air atmosphere 800 degree in the lower 1300 ℃ of heat preservation sintering 3h of air atmosphere, is cooled to room temperature again, grinds and namely obtains La
0.7Gd
0.1Eu
0.2AlO
3Luminescent material.This material can red-emitting under cathode-ray exciting, good luminous performance, and purity of color is high.
Embodiment 5La
0.9Tb
0.1AlO
3
At first take by weighing nine water aluminum nitrate 2.0632g (5.5mmol), be dissolved in the 25ml deionized water, be stirred and heated to 40 degree, add fast ammoniacal liquor, regulator solution pH to 8, continue to stir 0.5h, and then be heated to 70 degree, continue to stir 1h, drip again the Terbium trinitrate solution that lanthanum nitrate hexahydrate that 4.5ml concentration is 1mol/L and 1ml concentration are 0.5mol/L, rear dropping ammoniacal liquor, regulator solution pH to 9 continues to stir 1.5h.Last filtration washing oven dry throw out, pre-treatment 2h under air atmosphere 800 degree in the lower 1400 ℃ of heat preservation sintering 1h of reducing atmosphere, is cooled to room temperature again, grinds and namely obtains La
0.9Tb
0.1AlO
3Luminescent material.This material can transmitting green light under cathode-ray exciting, good luminous performance, and purity of color is high.Fig. 4 is the luminescent spectrum of luminescent material under cathode-ray exciting that present embodiment prepares.
Embodiment 6La
0.65Lu
0.2Tb
0.15AlO
3
At first take by weighing nine water aluminum nitrate 1.9132g (5.1mmol), be dissolved in the 15ml deionized water, be stirred and heated to 45 degree, add fast ammoniacal liquor, regulator solution pH to 8, continue to stir 0.5h, and then be heated to 70 the degree, continue to stir 1h, add the ammonium oxalate solution that 15ml concentration is 0.3mol/L again, dripping 3.25ml concentration is the lanthanum nitrate hexahydrate of 1mol/L, 1ml concentration is the lutecium nitrate solution of 1mol/L and the Terbium trinitrate solution that 1.5ml concentration is 0.5mol/L, rear dropping ammoniacal liquor, regulator solution pH to 9 continues to stir 2h.Last filtration washing oven dry throw out, pre-treatment 2h under air atmosphere 800 degree in the lower 1300 ℃ of heat preservation sintering 4h of reducing atmosphere, is cooled to room temperature again, grinds and namely obtains La
0.65Lu
0.2Tb
0.15AlO
3Luminescent material.This material can transmitting green light under cathode-ray exciting, good luminous performance, and purity of color is high.
Should be understood that above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (5)
1. the preparation method of a lanthanum aluminate light-emitting material comprises the steps:
According to chemical general formula La
1-x-yRe
yLn
xAlO
3The stoichiometric ratio of middle Al provides the source compound of Al and is configured to the Al deionized water solution; Wherein, Ln is at least a among Tm, Tb, Sm or the Eu, and Re is at least a among Y, Gd or the Lu, and the span of x is that the span of 0.001～0.2, y is 0～0.2 times of 1-x;
In above-mentioned Al deionized water solution, add alkaline solution, regulate the pH value to 8 of Al deionized water solution, make nano aluminium oxide colloidal sol;
In above-mentioned nano aluminium oxide colloidal sol, add sinking agent, drip respectively subsequently the aqueous solution that contains La ion and Ln ion, then add alkaline solution, regulate the pH value to 9 of whole mixing solutions, stir, filter, dry throw out;
Above-mentioned throw out is carried out thermal pretreatment and sintering processes successively, and cooling, grinding make described lanthanum aluminate light-emitting material; In the described preheating treatment procedure, the thermal pretreatment temperature is 600～900 ℃, and be 0.5～2h warm up time; In the described sintering processes, the sintering processes temperature is 1200～1500 ℃, and sintering time is 0.5～5h.
2. preparation method according to claim 1 is characterized in that, the span of x is 0.001～0.15.
3. preparation method according to claim 1 is characterized in that, in the described Al deionized water solution layoutprocedure, the source chemical combination of Al is aluminum nitrate.
4. preparation method according to claim 1 is characterized in that, described alkaline solution is ammoniacal liquor.
5. preparation method according to claim 1 is characterized in that, in the described preheating treatment procedure, the thermal pretreatment temperature is 800 ℃.
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| CN108793266A (en) * | 2017-05-02 | 2018-11-13 | 上海大学 | A kind of method that sol-gal process prepares blue cobalt aluminate |
| CN111019654A (en) * | 2019-12-31 | 2020-04-17 | 北京印刷学院 | Auxiliary combustion method for preparing LaYAlO3: method for preparing Eu fluorescent powder material |
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Non-Patent Citations (5)
| Title |
|---|
| Junjie Wu，Bing Yan.Sol–gel composition of hybrid precursors to synthesize RExGd1− |
| Junjie Wu,Bing Yan.Sol–gel composition of hybrid precursors to synthesize RExGd1−xAlO3:Eu3+ (RE = La, Y) phosphors.《Journal of Alloys and Compounds》.2006,第432卷第293-297页. * |
| Synthesis and Luminescent Properties of LaAlO3:RE3+ (RE =Tm, Tb) Nanocrystalline Phosphors via a Sol-Gel Process;Xiaoming Liu et al;《Journal of Physical Chemistry C》;20090420;第113卷;第8478－8483页 * |
| xAlO3:Eu3+(RE=La Y) phosphors.《Journal of Alloys and Compounds》.2006 |
| XiaomingLiuetal.SynthesisandLuminescentPropertiesofLaAlO3:RE3+(RE=Tm Tb) Nanocrystalline Phosphors via a Sol-Gel Process.《Journal of Physical Chemistry C》.2009 |
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