CN104893721A - Submicron Eu<3+>: beta-Li2TiO3 high-purity red fluorescent powder and preparation method thereof - Google Patents

Submicron Eu<3+>: beta-Li2TiO3 high-purity red fluorescent powder and preparation method thereof Download PDF

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CN104893721A
CN104893721A CN201510223883.7A CN201510223883A CN104893721A CN 104893721 A CN104893721 A CN 104893721A CN 201510223883 A CN201510223883 A CN 201510223883A CN 104893721 A CN104893721 A CN 104893721A
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tio
red light
submicron
fluorescent powder
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于成龙
高丹鹏
郝欣
王斐
曹舒尧
李建
惠怀兵
郭颖艳
江红涛
王莉丽
宁青菊
朱宛琳
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a preparation method of submicron Eu<3+>: beta-Li2TiO3 high-purity red fluorescent powder. The preparation method comprises dissolving Li2O particles in distilled water to obtain a LiOH solution with a mole concentration of 0.10-3.00mol/L, adding a Ti source and an Eu source into the solution, carrying out mixing to obtain a uniform mixture, carrying out a hydrothermal reaction process in an oven at a temperature of 100-240 DEG C for 1-20h, carrying out furnace cooling, taking out the hydrothermal reaction product, carrying out drying, carrying out uniform grinding, carrying out calcination in an electric resistance furnace at a temperature of 500-700 DEG C for 6-36h, carrying out furnace cooling and carrying out grinding.

Description

A kind of submicron Eu 3+: β-Li 2tiO 3high-purity red light fluorescent powder and preparation method
[technical field]
The invention belongs to wet chemistry method and prepare phosphor technologies field, be specifically related to a kind of submicron Eu 3+: β-Li 2tiO 3the preparation method of high-purity red light fluorescent powder.
[background technology]
At present, rare earth luminescent material has become the core material in the fields such as information displaying, lighting source, photoelectric device.Wherein, what be most widely used is to be excited by ultraviolet-near ultraviolet (200 ~ 450nm) and to produce the phosphor material powder of different glow color.The high luminous intensity of fluorescent material, high color purity and uniform particle size significantly can improve the use properties of photoelectric device.Red light fluorescent powder is one of important composition of three primary colors fluorescent powder, and current red light fluorescent powder body material mainly comprises aluminate, silicate and titanate etc., but there are differences in luminous intensity and purity of color.
The people such as M.Mohapatra have prepared Eu through long-time calcining by high temperature solid-state method at 800 DEG C 3+: β-Li 2tiO 3fluorescent material, under 394nm near ultraviolet excitation, Eu 3+: β-Li 2tiO 3only there is strong VISIBLE LIGHT EMISSION at 611nm place in fluorescent material, its commplementary wave length place luminous intensity is very weak.Compared with present commercial red light fluorescent powder, Eu 3+: β-Li 2tiO 3the red light color purity of fluorescent material is high, luminous intensity is high, is a kind of red light fluorescent powder material of excellent performance.At present, the Eu reported 3+: β-Li 2tiO 3the preparation method of fluorescent material is high temperature solid-state method, and after high-temperature calcination, the particle diameter of powder is comparatively large, and skewness, luminescent properties is poor.Meanwhile, activator mixing is uneven, causes light-emitting phosphor efficiency to reduce, have impact on fluorescent material actual use properties in the devices greatly.And phosphor material powder grain diameter prepared by hydrothermal method is little, even particle size distribution, rare earth ion are easy to enter in substrate material lattice, and the coating property in the application of fluorescent material later stage can be improved.So far, not yet occur that hydrothermal method prepares Eu 3+: β-Li 2tiO 3the relevant report of fluorescent material.
Reference:
M.Mohapatraa,Y.P.Naik,P.Natarajan,et al.Rare earth doped lithium titanate (Li 2TiO 3)for potential phosphor applications[J].Journal of Luminescence,2010,130:2402-2406.
[summary of the invention]
The invention provides a kind of submicron Eu 3+: β-Li 2tiO 3high-purity red light fluorescent powder and preparation method, solve that particle uniformity difference, coating are poor, the uneven and Eu of activator mixing 3+be difficult to enter β-Li 2tiO 3the problems such as lattice.The present invention can obtain submicron order Eu under later stage low temperature calcination 3+: β-Li 2tiO 3fluorescent material, even particle size distribution, red light color purity is high, and luminous intensity is high.
The present invention is by the following technical solutions:
A kind of submicron Eu 3+: β-Li 2tiO 3the preparation method of high-purity red light fluorescent powder, by Li 2o particle makes with hydrothermal synthesis method the LiOH solution that volumetric molar concentration is 0.10 ~ 3.00mol/L, then add Ti source and Eu source wherein, ensure to mix, more in an oven in 100 ~ 240 DEG C of insulation 1 ~ 20h, hydrothermal product is taken out after furnace cooling, after this hydrothermal product drying, grinding is even, in resistance furnace, 6 ~ 36h is calcined at 500 ~ 700 DEG C, last furnace cooling, grinding.
By Li 2the concrete grammar that O particle makes LiOH solution with hydrothermal synthesis method is: by Li 2o particle is placed in high pressure vessel, the pressure range of this high pressure vessel is 1 ~ 100Mpa, be 20% ~ 70% (referring to that distilled water volume accounts for the ratio of high pressure vessel volume) added distilled water in this high pressure vessel in packing ratio, after abundant dissolving, obtain the LiOH solution that volumetric molar concentration is 0.10 ~ 3.00mol/L.
According to atomic molar ratio, Li:Ti=1.85 ~ 2.25:1; Eu 3+account for body material β-Li 2tiO 3volumetric molar concentration be 0.1 ~ 10mol%.
The material of described high pressure vessel is tetrafluoroethylene, stainless steel or Hastelloy.
In described LiOH solution, add Ti source and Eu source, adopt the mode of ultrasonic cleaning to ensure abundant dissolving, described ultrasonic frequency is 10 ~ 40kHz, and the treatment time is 10 ~ 30min.
Described Ti source and Eu source join in LiOH solution simultaneously.
The concrete grammar of described hydrothermal product drying is: dry in air atmosphere under 80 DEG C of conditions.
When hydrothermal product is dry, forbid to outwell supernatant liquor, forbid to clean, all product convection dryings.
A kind of submicron Eu obtained based on aforesaid method 3+: β-Li 2tiO 3high-purity red light fluorescent powder, the primary particle median size of this fluorescent material is 140nm.
Compared with prior art, the present invention at least has the following advantages:
1) the present invention adopts hydrothermal method to prepare submicron Eu 3+: β-Li 2tiO 3high-purity red light fluorescent powder, under low temperature calcination, (500 ~ 700 DEG C) can make Eu 3+mix β-Li 2tiO 3lattice, and realize VISIBLE LIGHT EMISSION.Compared with traditional high temperature solid-state method, hydrothermal method energy consumption is lower, operating procedure simple, is applicable to suitability for industrialized production.
2) the present invention prepares submicron Eu by hydrothermal method 3+: β-Li 2tiO 3high-purity red light fluorescent powder, compared with conventional solid-state method, gained grain diameter is little and be evenly distributed, and is conducive to improving the coating property in the application of fluorescent material later stage.
3) submicron Eu prepared by the present invention 3+: β-Li 2tiO 3high-purity red light fluorescent powder, after calcining, body material surpasses born of the same parents' structural development well, and rare earth ion easily enters lattice and realizes transmission ofenergy, and its photoluminescence performance easily regulates and controls.The red light color purity of gained fluorescent material is high, and luminous intensity is high.
[accompanying drawing explanation]
Fig. 1 is Eu prepared by example 1 3+: β-Li 2tiO 3the X ray diffracting spectrum of red light fluorescent powder.
Fig. 2 is Eu prepared by example 2 3+: β-Li 2tiO 3the field emission scanning electron microscope image of red light fluorescent powder.
Fig. 3 is Eu prepared by example 1 3+: β-Li 2tiO 3the emmission spectrum of red light fluorescent powder.
Fig. 4 is Eu prepared by example 3 3+: β-Li 2tiO 3the emmission spectrum of red light fluorescent powder.
Fig. 5 is Eu prepared by example 4 3+: β-Li 2tiO 3the emmission spectrum of red light fluorescent powder.
Fig. 6 is Eu prepared by example 5 3+: β-Li 2tiO 3the emmission spectrum of red light fluorescent powder.
Fig. 7 is Eu prepared by example 7 3+: β-Li 2tiO 3the emmission spectrum of red light fluorescent powder.
Fig. 8 is Eu prepared by example 6 3+: β-Li 2tiO 3the XYZ chromaticity diagram of red light fluorescent powder.
[concrete embodiment]
Concrete grammar of the present invention is as follows:
1) a certain amount of Li is taken 2o particle is placed in high pressure vessel, and (this high pressure vessel material is tetrafluoroethylene, stainless steel, Hastelloy etc., pressure range 1 ~ 100Mpa) in, be 20% ~ 70% (referring to that distilled water volume accounts for the ratio of high pressure vessel volume) in high pressure vessel, added appropriate distilled water, Li in packing ratio 2after O fully dissolves, in high pressure vessel, form the LiOH solution that concentration is 0.10 ~ 3.00mol/L;
2) in the atomic molar ratio of Li:Ti=1.85 ~ 2.25:1, appropriate TiO is taken 2powder.According to Eu 3+volumetric molar concentration be that 0.1 ~ 10mol% (refers to Eu 3+account for body material β-Li 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3powder.By TiO 2powder and Eu 2o 3powder adds in the high pressure vessel of step 1 jointly;
3) step 2 mesohigh container is placed in Ultrasonic Cleaners, carries out supersound process, ultrasonic frequency is 10 ~ 40kHz, and the treatment time is 10 ~ 30min, and three kinds of raw materials in high pressure vessel are fully mixed;
4) high pressure vessel in step 3 is placed in baking oven, at 100 ~ 240 DEG C, insulation 1 ~ 20h, takes out after furnace cooling;
5) by step 4 gained hydrothermal product under 80 DEG C of conditions, carry out drying (note, all products of hydro-thermal gained carry out drying, forbid to outwell supernatant liquor, forbid cleaning) in air atmosphere, obtain hydro-thermal presoma;
6) by the grinding of step 5 gained hydro-thermal presoma evenly, be placed in chamber type electric resistance furnace, at 500 ~ 700 DEG C, calcine 6 ~ 36h, take out after furnace cooling and grind, obtain final product Eu 3+: β-Li 2tiO 3fluorescent material;
Below in conjunction with example and accompanying drawing, the present invention is described in further detail:
Embodiment 1
1) a certain amount of Li is taken 2o particle is placed in high pressure vessel, is 70% (referring to that distilled water volume accounts for the ratio of high pressure vessel volume) added appropriate distilled water in high pressure vessel in packing ratio, after fully dissolving, forms the LiOH solution that concentration is 1.00mol/L in high pressure vessel;
2) in the ratio of Li:Ti=2.05:1 (atomic molar ratio), appropriate TiO is taken 2powder.According to Eu 3+volumetric molar concentration be that 1.0mol% (refers to Eu 3+account for body material β-Li 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3powder.By TiO 2powder and Eu 2o 3powder adds in the high pressure vessel of step 1 jointly;
3) liner of step 2 mesohigh container is placed in Ultrasonic Cleaners, carries out supersound process, ultrasonic frequency is 35kHz, and the treatment time is 12min, and three kinds of raw materials in high pressure vessel are fully mixed;
4) high pressure vessel in step 3 is placed in baking oven, at 100 DEG C, insulation 10h, takes out after furnace cooling;
5) by step 4 gained hydrothermal product under 80 DEG C of conditions, carry out drying (note, all products of hydro-thermal gained carry out drying, forbid to outwell supernatant liquor, forbid cleaning) in air atmosphere, obtain hydro-thermal presoma;
6) by the grinding of step 5 gained hydro-thermal presoma evenly, be placed in chamber type electric resistance furnace, at 670 DEG C, calcine 10h, take out after furnace cooling and grind, obtain final product Eu 3+: β-Li 2tiO 3powder;
7) by X-ray diffraction (XRD), Discriminating materials is carried out to product.By field emission scanning electron microscope (FE-SEM), morphology observation is carried out to product.Luminescent properties test is carried out by fluorescence spectrophotometer.Finally obtain that red light color purity is high, luminous intensity is high, grain diameter is 134nm, be evenly distributed, phase purity be 100% submicron order Eu 3+: β-Li 2tiO 3red light fluorescent powder.
Embodiment 2
1) a certain amount of Li is taken 2o particle is placed in high pressure vessel, is 65% (referring to that distilled water volume accounts for the ratio of high pressure vessel volume) added appropriate distilled water in high pressure vessel in packing ratio, after fully dissolving, forms the LiOH solution that concentration is 2.50mol/L in high pressure vessel;
2) in the ratio of Li:Ti=2.00:1 (atomic molar ratio), appropriate TiO is taken 2powder.According to Eu 3+volumetric molar concentration be that 6.5mol% (refers to Eu 3+account for body material β-Li 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3powder.By TiO 2powder and Eu 2o 3powder adds in the high pressure vessel of step 1 jointly;
3) liner of step 2 mesohigh container is placed in Ultrasonic Cleaners, carries out supersound process, ultrasonic frequency is 15kHz, and the treatment time is 10min, and three kinds of raw materials in high pressure vessel are fully mixed;
4) high pressure vessel in step 3 is placed in baking oven, at 180 DEG C, insulation 1h, takes out after furnace cooling;
5) by step 4 gained hydrothermal product under 80 DEG C of conditions, carry out drying (note, all products of hydro-thermal gained carry out drying, forbid to outwell supernatant liquor, forbid cleaning) in air atmosphere, obtain hydro-thermal presoma;
6) by the grinding of step 5 gained hydro-thermal presoma evenly, be placed in chamber type electric resistance furnace, at 580 DEG C, calcine 36h, take out after furnace cooling and grind, obtain final product Eu 3+: β-Li 2tiO 3powder;
7) by X-ray diffraction (XRD), Discriminating materials is carried out to product.By field emission scanning electron microscope (FE-SEM), morphology observation is carried out to product.Luminescent properties test is carried out by fluorescence spectrophotometer.Finally obtain that red light color purity is high, luminous intensity is high, grain diameter is 149nm, be evenly distributed, phase purity be 100% submicron order Eu 3+: β-Li 2tiO 3red light fluorescent powder.
Embodiment 3
1) a certain amount of Li is taken 2o particle is placed in high pressure vessel, is 40% (referring to that distilled water volume accounts for the ratio of high pressure vessel volume) added appropriate distilled water in high pressure vessel in packing ratio, after fully dissolving, forms the LiOH solution that concentration is 3.00mol/L in water heating kettle;
2) in the ratio of Li:Ti=1.95:1 (atomic molar ratio), appropriate TiO is taken 2powder.According to Eu 3+volumetric molar concentration be that 10.0mol% (refers to Eu 3+account for body material β-Li 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3powder.By TiO 2powder and Eu 2o 3powder adds in the high pressure vessel of step 1 jointly;
3) liner of step 2 mesohigh container is placed in Ultrasonic Cleaners, carries out supersound process, ultrasonic frequency is 10kHz, and the treatment time is 24min, and three kinds of raw materials in high pressure vessel are fully mixed;
4) high pressure vessel in step 3 is placed in baking oven, at 200 DEG C, insulation 20h, takes out after furnace cooling;
5) by step 4 gained hydrothermal product under 80 DEG C of conditions, carry out drying (note, all products of hydro-thermal gained carry out drying, forbid to outwell supernatant liquor, forbid cleaning) in air atmosphere, obtain hydro-thermal presoma;
6) by the grinding of step 5 gained hydro-thermal presoma evenly, be placed in chamber type electric resistance furnace, at 500 DEG C, calcine 24h, take out after furnace cooling and grind, obtain final product Eu 3+: β-Li 2tiO 3powder;
7) by X-ray diffraction (XRD), Discriminating materials is carried out to product.By field emission scanning electron microscope (FE-SEM), morphology observation is carried out to product.Luminescent properties test is carried out by fluorescence spectrophotometer.Finally obtain that red light color purity is high, luminous intensity is high, grain diameter is 141nm, be evenly distributed, phase purity be 100% submicron order Eu 3+: β-Li 2tiO 3red light fluorescent powder.
Embodiment 4
1) a certain amount of Li is taken 2o particle is placed in high pressure vessel, is 35% (referring to that distilled water volume accounts for the ratio of high pressure vessel volume) added appropriate distilled water in high pressure vessel in packing ratio, after fully dissolving, forms the LiOH solution that concentration is 1.75mol/L in water heating kettle;
2) in the ratio of Li:Ti=2.10:1 (atomic molar ratio), appropriate TiO is taken 2powder.According to Eu 3+volumetric molar concentration be that 0.10mol% (refers to Eu 3+account for body material β-Li 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3powder.By TiO 2powder and Eu 2o 3powder adds in the high pressure vessel of step 1 jointly;
3) liner of step 2 mesohigh container is placed in Ultrasonic Cleaners, carries out supersound process, ultrasonic frequency is 20kHz, and the treatment time is 18min, and three kinds of raw materials in high pressure vessel are fully mixed;
4) high pressure vessel in step 3 is placed in baking oven, at 240 DEG C, insulation 12h, takes out after furnace cooling;
5) by step 4 gained hydrothermal product under 80 DEG C of conditions, carry out drying (note, all products of hydro-thermal gained carry out drying, forbid to outwell supernatant liquor, forbid cleaning) in air atmosphere, obtain hydro-thermal presoma;
6) by the grinding of step 5 gained hydro-thermal presoma evenly, be placed in chamber type electric resistance furnace, at 650 DEG C, calcine 6h, take out after furnace cooling and grind, obtain final product Eu 3+: β-Li 2tiO 3powder;
7) by X-ray diffraction (XRD), Discriminating materials is carried out to product.By field emission scanning electron microscope (FE-SEM), morphology observation is carried out to product.Luminescent properties test is carried out by fluorescence spectrophotometer.Finally obtain that red light color purity is high, luminous intensity is high, grain diameter is 139nm, be evenly distributed, phase purity be 100% submicron order Eu 3+: β-Li 2tiO 3red light fluorescent powder.
Embodiment 5
1) a certain amount of Li is taken 2o particle is placed in high pressure vessel, is 50% (referring to that distilled water volume accounts for the ratio of high pressure vessel volume) added appropriate distilled water in high pressure vessel in packing ratio, after fully dissolving, forms the LiOH solution that concentration is 0.25mol/L in water heating kettle;
2) in the ratio of Li:Ti=1.85:1 (atomic molar ratio), appropriate TiO is taken 2powder.According to Eu 3+volumetric molar concentration be that 0.50mol% (refers to Eu 3+account for body material β-Li 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3powder.By TiO 2powder and Eu 2o 3powder adds in the high pressure vessel of step 1 jointly;
3) liner of step 2 mesohigh container is placed in Ultrasonic Cleaners, carries out supersound process, ultrasonic frequency is 30kHz, and the treatment time is 30min, and three kinds of raw materials in high pressure vessel are fully mixed;
4) high pressure vessel in step 3 is placed in baking oven, at 120 DEG C, insulation 18h, takes out after furnace cooling;
5) by step 4 gained hydrothermal product under 80 DEG C of conditions, carry out drying (note, all products of hydro-thermal gained carry out drying, forbid to outwell supernatant liquor, forbid cleaning) in air atmosphere, obtain hydro-thermal presoma;
6) by the grinding of step 5 gained hydro-thermal presoma evenly, be placed in chamber type electric resistance furnace, at 600 DEG C, calcine 20h, take out after furnace cooling and grind, obtain final product Eu 3+: β-Li 2tiO 3powder;
7) by X-ray diffraction (XRD), Discriminating materials is carried out to product.By field emission scanning electron microscope (FE-SEM), morphology observation is carried out to product.Luminescent properties test is carried out by fluorescence spectrophotometer.Finally obtain that red light color purity is high, luminous intensity is high, grain diameter is 175nm, be evenly distributed, phase purity be 100% submicron order Eu 3+: β-Li 2tiO 3red light fluorescent powder.
Embodiment 6
1) a certain amount of Li is taken 2o particle is placed in high pressure vessel, is 60% (referring to that distilled water volume accounts for the ratio of high pressure vessel volume) added appropriate distilled water in high pressure vessel in packing ratio, after fully dissolving, forms the LiOH solution that concentration is 0.10mol/L in water heating kettle;
2) in the ratio of Li:Ti=2.25:1 (atomic molar ratio), appropriate TiO is taken 2powder.According to Eu 3+volumetric molar concentration be that 2.00mol% (refers to Eu 3+account for body material β-Li 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3powder.By TiO 2powder and Eu 2o 3powder adds in the high pressure vessel of step 1 jointly;
3) liner of step 2 mesohigh container is placed in Ultrasonic Cleaners, carries out supersound process, ultrasonic frequency is 25kHz, and the treatment time is 20min, and three kinds of raw materials in high pressure vessel are fully mixed;
4) high pressure vessel in step 3 is placed in baking oven, at 160 DEG C, insulation 6h, takes out after furnace cooling;
5) by step 4 gained hydrothermal product under 80 DEG C of conditions, carry out drying (note, all products of hydro-thermal gained carry out drying, forbid to outwell supernatant liquor, forbid cleaning) in air atmosphere, obtain hydro-thermal presoma;
6) by the grinding of step 5 gained hydro-thermal presoma evenly, be placed in chamber type electric resistance furnace, at 700 DEG C, calcine 12h, take out after furnace cooling and grind, obtain final product Eu 3+: β-Li 2tiO 3powder;
7) by X-ray diffraction (XRD), Discriminating materials is carried out to product.By field emission scanning electron microscope (FE-SEM), morphology observation is carried out to product.Luminescent properties test is carried out by fluorescence spectrophotometer.Finally obtain that red light color purity is high, luminous intensity is high, grain diameter is 166nm, be evenly distributed, phase purity be 100% submicron order Eu 3+: β-Li 2tiO 3red light fluorescent powder.
Embodiment 7
1) a certain amount of Li is taken 2o particle is placed in high pressure vessel, is 20% (referring to that distilled water volume accounts for the ratio of high pressure vessel volume) added appropriate distilled water in high pressure vessel in packing ratio, after fully dissolving, forms the LiOH solution that concentration is 0.50mol/L in water heating kettle;
2) in the ratio of Li:Ti=1.90:1 (atomic molar ratio), appropriate TiO is taken 2powder.According to Eu 3+volumetric molar concentration be that 1.50mol% (refers to Eu 3+account for body material β-Li 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3powder.By TiO 2powder and Eu 2o 3powder adds in the high pressure vessel of step 1 jointly;
3) liner of step 2 mesohigh container is placed in Ultrasonic Cleaners, carries out supersound process, ultrasonic frequency is 40kHz, and the treatment time is 15min, and three kinds of raw materials in high pressure vessel are fully mixed;
4) high pressure vessel in step 3 is placed in baking oven, at 110 DEG C, insulation 3h, takes out after furnace cooling;
5) by step 4 gained hydrothermal product under 80 DEG C of conditions, carry out drying (note, all products of hydro-thermal gained carry out drying, forbid to outwell supernatant liquor, forbid cleaning) in air atmosphere, obtain hydro-thermal presoma;
6) by the grinding of step 5 gained hydro-thermal presoma evenly, be placed in chamber type electric resistance furnace, at 550 DEG C, calcine 30h, take out after furnace cooling and grind, obtain final product Eu 3+: β-Li 2tiO 3powder;
7) by X-ray diffraction (XRD), Discriminating materials is carried out to product.By field emission scanning electron microscope (FE-SEM), morphology observation is carried out to product.Luminescent properties test is carried out by fluorescence spectrophotometer.Finally obtain that red light color purity is high, luminous intensity is high, grain diameter is 145nm, be evenly distributed, phase purity be 100% submicron order Eu 3+: β-Li 2tiO 3red light fluorescent powder.
Fig. 1 X-ray diffraction result shows, the submicron fluorescent material phase purity of preparation is high, and super born of the same parents' structural development is good.Fig. 2 scanning electron microscope image shows, Eu prepared by the method 3+: β-Li 2tiO 3red light fluorescent powder particle diameter is less and be evenly distributed, and mean particle size is about 149nm.The result of Fig. 3, Fig. 4, Fig. 5, Fig. 6, Fig. 7 emmission spectrum shows, wavelength to be the near-ultraviolet light of 394nm and wavelength be 465nm blue-light excited under, Eu 3+: β-Li 2tiO 3phosphor emission go out wavelength be 618nm ( 5d 0→ 7f 2) visible ray.Fig. 8 XYZ chromaticity diagram result shows, under 394nm near ultraviolet excitation, and Eu 3+: β-Li 2tiO 3the utilizing emitted light of fluorescent material is positioned at red light region, and chromaticity coordinates is (x=0.63, y=0.37).
Technological difficulties: high temperature solid-state method gained Eu 3+: β-Li 2tiO 3red light fluorescent powder material, the large and skewness of grain diameter after high-temperature calcination, coating property is poor.Meanwhile, activator mixing is uneven, and cause light-emitting phosphor efficiency to reduce, grain diameter conference causes most Eu 3+be difficult to enter β-Li 2tiO 3lattice, material emission poor-performing.

Claims (9)

1. a submicron Eu 3+: β-Li 2tiO 3the preparation method of high-purity red light fluorescent powder, is characterized in that: by Li 2o particle is dissolved in distilled water, makes the LiOH solution that volumetric molar concentration is 0.10 ~ 3.00mol/L, then adds Ti source and Eu source wherein, guarantee mixes, hydro-thermal reaction 1 ~ 20h at 100 ~ 240 DEG C in an oven again, takes out hydrothermal product after furnace cooling, after this hydrothermal product drying, grinding evenly, in resistance furnace, at 500 ~ 700 DEG C, calcine 6 ~ 36h, last furnace cooling, grinding.
2. a kind of submicron Eu according to claim 1 3+: β-Li 2tiO 3the preparation method of high-purity red light fluorescent powder, is characterized in that: by Li 2the concrete grammar that O particle makes LiOH solution is: by Li 2o particle is placed in high pressure vessel, and be 20% ~ 70% in this high pressure vessel, add distilled water by packing ratio, after fully dissolving, obtain the LiOH solution that volumetric molar concentration is 0.10 ~ 3.00mol/L, the pressure range of described high pressure vessel is 1 ~ 100Mpa.
3. a kind of submicron Eu according to claim 1 3+: β-Li 2tiO 3the preparation method of high-purity red light fluorescent powder, is characterized in that: according to atomic molar ratio, Li:Ti=1.85 ~ 2.25:1; Eu 3+account for body material β-Li 2tiO 3volumetric molar concentration be 0.1 ~ 10mol%.
4. a kind of submicron Eu according to claim 1 3+: β-Li 2tiO 3the preparation method of high-purity red light fluorescent powder, is characterized in that: the material of described high pressure vessel is tetrafluoroethylene, stainless steel or Hastelloy.
5. a kind of submicron Eu according to claim 1 3+: β-Li 2tiO 3the preparation method of high-purity red light fluorescent powder, is characterized in that: in described LiOH solution, add Ti source and Eu source, and adopt the mode of ultrasonic cleaning to ensure to mix, described ultrasonic frequency is 10 ~ 40kHz, and the treatment time is 10 ~ 30min.
6. a kind of submicron Eu according to claim 1 3+: β-Li 2tiO 3the preparation method of high-purity red light fluorescent powder, is characterized in that: described Ti source and Eu source join in LiOH solution simultaneously.
7. a kind of submicron Eu according to claim 1 3+: β-Li 2tiO 3the preparation method of high-purity red light fluorescent powder, is characterized in that: the concrete grammar of described hydrothermal product drying is: dry in air atmosphere under 80 DEG C of conditions.
8. a kind of submicron Eu according to claim 1 3+: β-Li 2tiO 3the preparation method of high-purity red light fluorescent powder, is characterized in that: when hydrothermal product is dry, forbid to outwell supernatant liquor, forbids to clean, all product convection dryings.
9. a kind of submicron Eu obtained based on method described in claim 1 3+: β-Li 2tiO 3high-purity red light fluorescent powder, is characterized in that: the primary particle median size of this fluorescent material is 140nm.
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Application publication date: 20150909