A kind of sodium lanthanum vanadate based luminescent material, preparation method and application thereof
Technical field
The present invention relates to a kind of europium ion Eu
3+The vanadate based luminescent material, preparation method and the application that activate belong to inorganic fluorescent material technical field.
Background technology
The rare-earth vanadate luminescent powder is a kind of important luminous host.Be luminescent material chemistry and the thermostability height of matrix with the rare-earth vanadate, in high voltage mercury lamp, plasma flat-plate demonstration and Field Emission Display, be widely used.The sixties in last century, emitting red light powder YVO
4: Eu is developed success, in order to replacing non-rare earth red fluorescent powder, and makes brightness improve 40%.But along with the expansion of modern science and technology and fluorescent material Application Areas, YVO
4: the Eu red fluorescence powder more and more can not satisfy the needs of development.For example, YVO
4: Eu is low near ultraviolet and blue region launching efficiency.
Chinese invention patent CN 101591540A " a kind of rare-earth vanadate LaVO
4: the preparation method of Eu red fluorescence powder " fluorescent material that a kind of vanadic acid lanthanum is mixed europium is disclosed, utilize microwave-hydrothermal method to prepare, it is low to have temperature of reaction, the advantage that the reaction times is short.Chinese invention patent CN 102191060A " a kind of vanadate fluorescent material and preparation method thereof " discloses a kind of fluorescent material of rear-earth-doped vanadic acid yttrium, and prepared fluorescent material is launched the ruddiness that centre wavelength is 615 nanometers under the exciting light of 314 nm.Among the Chinese invention patent CN 102399558A " a kind of vanadate red fluorescence powder, preparation method and application ", disclose the vanadate red fluorescence powder, its molecular formula is NaM
IILa1
-x-y(VO
4)
2: Eu
x, RI
II y, M wherein
IIBe alkaline-earth metal magnesium ion Mg
2+, calcium ion Ca
2+, strontium ion Sr
2+, barium ion Ba
2+With zine ion Zn
2+In a kind of, perhaps two or more combination, R
IIIBe rare earth samarium ion Sm
3+, gadolinium ion Gd
3+, terbium ion Tb
3+, dysprosium ion Dy
3+, lutetium ion Lu
3+And ruthenium ion Y
3+In at least a, x is europium ion Eu
3+The molar percentage coefficient that mixes, 0.0001≤x≤0.6; Y is rare earth ion R
IIIReplace lanthanum ion La
3+The molar percentage coefficient, 0.0001≤y≤0.6.In technique scheme, Eu
3+The red fluorescence powder of the vanadate matrix that activates is a little less than near ultraviolet and blue region absorption.
The result of study of existing document shows Eu
3+The rare-earth vanadate based luminescent material Na that activates
3La
8-xEu
xV
3O
21Do not appear in the newspapers.
Summary of the invention
The present invention seeks in order to overcome Eu in the prior art
3+The vanadate red fluorescence powder that activates absorbs weak weak point near ultraviolet and blue region, provides a kind of degree of crystallinity height, luminous efficiency is remarkable, the preparation method is simple, sodium lanthanum vanadate based luminescent material, preparation method and the application thereof of environmental protection.
For reaching above goal of the invention, the technical solution used in the present invention provides a kind of sodium lanthanum vanadate based luminescent material, and its chemical formula is Na
3La
8-xEu
xV
3O
21, wherein, x is Eu
3+Doping, 0.0001≤x≤0.25; Described luminescent material has strong exciting light near 300 nanometers and 450 nanometers, its emission light is near 621 nanometers red luminous.
A kind of method for preparing sodium lanthanum vanadate based luminescent material of the present invention is to adopt high temperature solid-state method, may further comprise the steps:
1. with contain composite and sodium ion composite, contain the compound of lanthanum ion, the compound that contains the compound of europium ion and contain vanadium ion is raw material, presses general formula Na
3La
8-xEu
xV
3O
21, the stoichiometric ratio of corresponding element takes by weighing each raw material in 0.0001≤x≤0.25, mixes after the grinding;
2. be precalcining 1~2 time under 300~600 ℃, air atmosphere with the raw material that mixes in temperature, insulation 3~6 h are cooled to room temperature naturally;
Powder after the precalcining is fully ground, and under air atmosphere, with 1000~1200 ℃ temperature calcining, insulation 6~10h obtains a kind of europium ion Eu behind the naturally cooling
3+The sodium lanthanum vanadate based luminescent material Na that activates
3La
8-xEu
xV
3O
21, wherein x is Eu
3+Doping, 0.0001≤x≤0.25.
Prepare in the technical scheme of sodium lanthanum vanadate based luminescent material at employing high temperature solid-state method of the present invention, the described composite and sodium ion composite that contains is one or more combination in yellow soda ash, sodium bicarbonate, SODIUMNITRATE, the sodium oxide.The described compound that contains europium ion is a kind of in europium sesquioxide, the europium nitrate, or two kinds combination.The described compound that contains vanadium ion is a kind of in Vanadium Pentoxide in FLAKES, the vanadous oxide, or two kinds combination.The described compound that contains lanthanum ion is a kind of in lanthanum trioxide, the lanthanum nitrate, or two kinds combination.
The method of another kind of preparation sodium lanthanum vanadate based luminescent material of the present invention is to adopt hydrothermal method, may further comprise the steps:
1. press general formula Na
3La
8-xEu
xV
3O
21The stoichiometric ratio of middle corresponding element takes by weighing the oxide compound that contains lanthanum ion and europium ion, is that the concentrated nitric acid of 3~5 times of lanthanum atoms and europium atom is rare earth nitrate solution with two kinds of compound dissolutions with mole number, with the deionized water dilution of 5~10 times of volumes;
2. press general formula Na
3La
8-xEu
xV
3O
21The stoichiometric ratio of middle corresponding element takes by weighing NaNO
3And NH
4VO
3, be to be dissolved in the water respectively under 50~70 ℃ the condition in temperature, be configured to NaNO
3And NH
4VO
3Solution;
3. under the magnetic agitation condition, with NaNO
3Solution and NH
4VO
3Solution joins in the rare earth nitrate solution that 1. step obtain, and the citric acid that adds mole number again and be 1~3 times of rare earth atom is complexing agent, obtains mixing solutions; The pH value of regulating mixing solutions with ammoniacal liquor and nitric acid is 5~8, stirs 1~2 h;
4. the solution that 3. step is obtained is poured in the reactor, adds deionized water and makes liquor capacity reach 70~80% of reactor volume, and the sealing back is to be incubated 4~8h under 170~200 ℃ the condition at oven temperature, and cooling obtains throw out by centrifugal treating; After throw out deionized water wash, oven dry, obtain a kind of europium ion Eu
3+The sodium lanthanum vanadate based luminescent material Na that activates
3La
8-xEu
xV
3O
21, wherein x is Eu
3+Doping, 0.0001≤x≤0.25.
Technical solution of the present invention also comprises a kind of application of described sodium lanthanum vanadate based luminescent material, described luminescent material is cooperated with an amount of blueness and green emitting phosphor, apply and be packaged in outside ultraviolet and the blue-ray LED diode chip for backlight unit, preparation white light LEDs illuminating device.
Compare with the prior art scheme, the technical solution of the present invention advantage is:
1, with existing red vanadate fluorescent material such as YVO
4: Eu
3+, LaVO
4: Eu
3+Compare, red fluorescence powder by the technical solution of the present invention preparation has stronger exciting near near ultraviolet (300 nanometers) and near blue region (450 nanometers), it is cooperated with an amount of blueness and green emitting phosphor, apply and be packaged in outside ultraviolet and the blue-ray LED diode chip for backlight unit, preparation white light LEDs illuminating device.
2, with other sulfide Y
2O
2S:Eu
3+, halogenide etc. compares for the red fluorescence powder of substrate material, the preparation process of substrate material of the present invention is pollution-free, safety, environmental protection.
3, prepared powder degree of crystallinity height, chemistry and Heat stability is good, luminous efficiency obviously improves.
Description of drawings
Fig. 1 is the embodiment of the invention 1 prepared Na
3La
7.99Eu
0.01V
3O
21The X-ray powder diffraction spectrogram of material sample;
Fig. 2 is the embodiment of the invention 1 prepared Na
3La
7.99Eu
0.01V
3O
21The emmission spectrum figure that material sample monitors at ambient temperature;
Fig. 3 is the embodiment of the invention 2 prepared Na
3La
7.9Eu
0.1V
3O
21The X-ray powder diffraction spectrogram of material sample and the contrast of standard spectrogram;
Fig. 4 is the embodiment of the invention 2 prepared Na
3La
7.9Eu
0.1V
3O
21What material sample monitored at ambient temperature excites and emmission spectrum figure;
Fig. 5 is the embodiment of the invention 2 prepared Na
3La
7.9Eu
0.1V
3O
21The decay of luminescence graphic representation that material sample monitors at ambient temperature.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment technical solution of the present invention is described further.
Embodiment 1
According to chemical formula Na
3La
7.99Eu
0.01V
3O
21In the stoichiometric ratio of each element, take by weighing Na respectively
2CO
30.795 gram, La
2O
36.512 gram, Eu
2O
30.009 gram, V
2O
51.365 gram.In agate mortar, grind, and fully mix.The powder that mixes is carried out first time calcining under air atmosphere, temperature is 300 ℃, is incubated 3 h, takes out sample after being cooled to room temperature naturally.Powder after the calcining is for the first time fully ground in agate mortar again, carry out sintering second time under air atmosphere, temperature is 600 ℃, is incubated 6 h, be cooled to room temperature naturally after the taking-up sample grind again.To grind uniform powder 1000 ℃ of calcinings down, be incubated 6 h, finally obtain Na behind the naturally cooling
3La
7.99Eu
0.01V
3O
21Red luminescent phosphor.
Referring to accompanying drawing 1, it is the prepared Na of present embodiment
3La
7.99Eu
0.01V
3O
21The X-ray powder diffraction collection of illustrative plates of material sample.As seen from Figure 1, the prepared Na of present embodiment
3La
7.99Eu
0.01V
3O
21Material is that pure phase and degree of crystallinity are more complete.
Referring to accompanying drawing 2, it is the prepared Na of present embodiment
3La
7.99Eu
0.01V
3O
21The emmission spectrum figure that material sample monitors at ambient temperature.As shown in Figure 2, the prepared Na of present embodiment
3La
7.99Eu
0.01V
3O
21Material main based on 621 nanometers near wavelength red luminous, and luminous intensity is higher.
Embodiment 2
According to chemical formula Na
3La
7.9Eu
0.1V
3O
21In the stoichiometric ratio of each element, take by weighing 1.275 gram NaNO
3Be dissolved in the 30 ml water, take by weighing 1.755 g NH
4VO
3Dissolving is gone in the 40 ml water, and 50 ℃ of water-baths are configured to solution respectively; Take by weighing 6.439 gram La again
2O
3With 0.09 gram Eu
2O
3Being dissolved in 24 ml concentration is in the concentrated nitric acid of 2.5 mol/ml, and dilutes with deionized water; With NaNO
3And NH
4VO
3Solution slowly joins in the rare earth nitrate solution under the magnetic agitation, adds the 0.04mol citric acid again as complexing agent; Be 6 by rare nitric acid and ammoniacal liquor regulator solution PH, fully stir again after the deionized water dilution, getting the solution of reactor capacity 80 % pours in the hydrothermal reaction kettle, insulation 6 h in 180 ℃ of baking ovens, with the solution centrifugal taking precipitate that obtains, and obtain red fluorescence powder Na with oven dry behind the deionized water wash
3La
7.9Eu
0.1V
3O
21
Referring to accompanying drawing 3, it is the prepared Na of present embodiment
3La
7.9Eu
0.1V
3O
21The X-ray powder diffraction collection of illustrative plates of material sample and the comparison diagram of standard spectrum.As seen from Figure 3, the prepared Na of present embodiment
3La
7.9,Eu
0.1V
3O
21Material is that pure phase and degree of crystallinity are more complete.
Referring to accompanying drawing 4, it is the prepared Na of present embodiment
3La
7.9Eu
0.1V
3O
21What material sample monitored at ambient temperature excites and emmission spectrum figure.As shown in Figure 4, the prepared Na of present embodiment
3La
7.9Eu
0.1V
3O
21Material is under 333 nanometer excitation wavelengths, produce stronger luminous, mainly red luminous based on 621 nano wave lengths, it and near ultraviolet LED chip emission wavelength are very identical, it is cooperated an amount of blueness and green emitting phosphor, and apply and be packaged in outside ultraviolet and the blue-ray LED diode chip for backlight unit, can be applicable to prepare the White-light LED illumination device.
Referring to accompanying drawing 5, it is the prepared Na of present embodiment
3La
7.9Eu
0.1V
3O
21Material sample decay of luminescence graphic representation, as can be seen from Figure 5, the prepared Na of present embodiment
3La
7.9Eu
0.1V
3O
21The luminous decay life-span of material can be applied in the luminescent material illumination and display device of display device, three-color fluorescent lamp and Field Emission Display fully.
Embodiment 3
According to chemical formula Na
3La
7.75Eu
0.25V
3O
21In the stoichiometric ratio of each element, take by weighing NaNO respectively
31.275 gram, La
2O
36.316 gram, Eu
2O
30.22 gram, V
2O
31.125 gram.In agate mortar, grind, and fully mix.The powder that mixes is calcined under air atmosphere, and temperature is 500 ℃, is incubated 5 h, takes out sample after being cooled to room temperature naturally.Grind again, will grind uniform powder 1200 ℃ of calcinings down, be incubated 10 h, finally obtain Na behind the naturally cooling
3La
7.75Eu
0.25V
3O
21Red luminescent phosphor.
The obtained Na of present embodiment
3La
7.75Eu
0.25V
3O
21Material sample constitutional features, emmission spectrum information, similar to embodiment 1.
Embodiment 4
According to chemical formula Na
3La
7.8Eu
0.2V
3O
21In the stoichiometric ratio of each element, take by weighing 1.275 gram NaNO
3Be dissolved in the 30 ml water, take by weighing 1.755 gram NH
4VO
3Dissolving is gone in the 40 ml water, and 70 ℃ of water-baths are configured to solution respectively; Take by weighing 6.357 gram La again
2O
3With 0.18 gram Eu
2O
3Being dissolved in 24 ml concentration is in the concentrated nitric acid of 2.5 mol/ml, and dilutes with deionized water; With NaNO
3And NH
4VO
3Solution slowly joins in the rare earth nitrate solution under the magnetic agitation, adds 0.06 mol citric acid again as complexing agent; Be 6 by rare nitric acid and ammoniacal liquor regulator solution PH, fully stirring after the deionized water dilution, is got the solution of reactor capacity 80% and is poured in the hydrothermal reaction kettle again, insulation 5 h in 200 ℃ of baking ovens, with the solution centrifugal taking precipitate that obtains, and obtain red fluorescence powder Na with oven dry behind the deionized water wash
3La
7.8Eu
0.2V
3O
21
The obtained Na of present embodiment
3La
7.8Eu
0.2V
3O
21The material sample constitutional features, excite and emmission spectrum information, similar to embodiment 2.
Embodiment 5
According to chemical formula Na
3La
7.85Eu
0.15V
3O
21In the stoichiometric ratio of each element, take by weighing NaHCO respectively
30.84 gram, NaNO
30.425 gram, La
2O
36.398 gram, Eu (NO
3)
36H
2O 335 grams, V
2O
31.125 gram.In agate mortar, grind, and fully mix.The powder that mixes is carried out first time calcining under air atmosphere, temperature is 400 ℃, is incubated 5 h, takes out sample after being cooled to room temperature naturally.The powder of calcining is for the first time fully ground in agate mortar again, carry out sintering second time under air atmosphere, temperature is 500 ℃, is incubated 4 h, be cooled to room temperature naturally after the taking-up sample grind again.To grind uniform powder 1100 ℃ of calcinings down, be incubated 8 h, finally obtain Na behind the naturally cooling
3La
7.85Eu
0.15V
3O
21Red luminescent phosphor.
The obtained Na of present embodiment
3La
7.85Eu
0.15V
3O
21Material sample constitutional features and emmission spectrum information are similar to Example 1.