CN104974753A - Eu<3+>, Dy<3+>, Tb<3+> excited beta-Li2TiO3 single-substrate white-light fluorescent powder, and preparation method thereof - Google Patents

Eu<3+>, Dy<3+>, Tb<3+> excited beta-Li2TiO3 single-substrate white-light fluorescent powder, and preparation method thereof Download PDF

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CN104974753A
CN104974753A CN201510188941.7A CN201510188941A CN104974753A CN 104974753 A CN104974753 A CN 104974753A CN 201510188941 A CN201510188941 A CN 201510188941A CN 104974753 A CN104974753 A CN 104974753A
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tio
source
fluorescent powder
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宁青菊
曹舒尧
于成龙
王斐
高丹鹏
郝欣
江红涛
朱宛琳
王莉丽
王道益
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a preparation method of Eu<3+>, Dy<3+>, Tb<3+> excited beta-Li2TiO3 single-substrate white-light fluorescent powder. According to the invention, LiO2 particles are dissolved in distilled water, such that a LiOH solution with a molar concentration of 0.10-3.00 mol/L is prepared; a Ti source, a Eu source, a Dy source and a Tb source are added into the solution, and the mixture is well mixed; the mixture is subjected to a hydrothermal reaction for 1-20h under a temperature of 100-240 DEG C in a baking oven; a hydrothermal product is cooled in the oven, and is fetched; the hydrothermal product is dried, and is uniformly ground; the ground product is calcined for 6-36h under a temperature of 500-700 DEG C in a resistance furnace; the product is cooled in the furnace, and is ground, such that the fluorescent powder is obtained.

Description

A kind of Eu 3+, Dy 3+, Tb 3+activate β-Li 2tiO 3single-matrix white 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+, Dy 3+, Tb 3+: β-Li 2tiO 3single-matrix white fluorescent powder and preparation method.
[background technology]
By ultraviolet-near ultraviolet excitated red, green, blue three primary colors fluorescent powder composed emission white light, because its glow color is stablized, and colour rendering index is more excellent, becomes the focus of LED white emitting fluorescent powder research.The mode that the method generally adopts multiple matrix fluorescent material to mix, but absorb again owing to there is color between phosphor mixture, can cause energy waste, proportioning is difficult to the problem that regulates and controls.In addition, between different fluorescent material matrix, there is the different problem of rate of ageing, luminous efficiency and color reducibility can be caused further to receive impact, can cost be increased simultaneously.Therefore, under ultraviolet-near ultraviolet excitated, can the research of single-matrix fluorescent material of transmitting white very necessary.
2010, the people such as M.Mohapatra were calcined through long-time at 800 DEG C by high temperature solid-state method, have prepared Eu 3+, Dy 3+, Tb 3+: β-Li 2tiO 3single-matrix white fluorescent powder material, under 230nm ultraviolet excitation, there is multi-peak emission in fluorescent material within the scope of 450 ~ 680nm, and its chromaticity coordinates is x=0.355, y=0.392.In addition, Chinese invention patent discloses No. CN102732251A and reports a kind of Ba 9-x-yeu xmn yce z(SiO 4) 6the high temperature process heat method of (wherein, 0.03≤x≤0.20,0.05≤y≤0.30,0.02≤z≤0.15) single-matrix white fluorescent powder.This fluorescent material, under 390nm near ultraviolet excitation, can realize the broadband VISIBLE LIGHT EMISSION of 450 ~ 650nm.
At present, commercial fluorescent material all adopts high temperature solid-state method to prepare, 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 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+, Dy 3+, Tb 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.
Zhang Xia, Zhang Jiahua, Hao Zhendong. a kind of single-phase white-emitting phosphor being applicable near ultraviolet excitation and preparation method thereof [P]. Chinese invention patent, CN102732251A, 2012.
[summary of the invention]
The object of this invention is to provide a kind of Eu 3+, Dy 3+, Tb 3+activate β-Li 2tiO 3single-matrix white fluorescent powder and preparation method, solve particle uniformity difference, coating be poor, activator mixing is uneven and rare earth ion is difficult to enter β-Li 2tiO 3the problems such as lattice.The present invention can obtain submicron order Tb under later stage low temperature calcination 3+: β-Li 2tiO 3fluorescent material, even particle size distribution, color developing is good, and colour temperature is lower.
The technical solution adopted in the present invention is:
A kind of Eu 3+, Dy 3+, Tb 3+activate β-Li 2tiO 3the preparation method of single-matrix white fluorescent powder, 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, Eu source, Dy source, Tb 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.
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, 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, the pressure range of described high pressure vessel is 1 ~ 100Mpa.
Li:Ti=1.85 ~ 2.25:1 (atomic molar ratio), Eu 3+, Dy 3+, Tb 3+account for body material β-Li 2tiO 3volumetric molar concentration be respectively 0.1 ~ 10mol%.
The material of described high pressure vessel is tetrafluoroethylene, stainless steel or Hastelloy.
In described LiOH solution, add Ti source, Eu source, Dy source, Tb 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, Eu source, Dy source, Tb 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 Eu obtained based on aforesaid method 3+, Dy 3+, Tb 3+activate β-Li 2tiO 3single-matrix white fluorescent powder, the primary particle median size of this fluorescent material is 140nm.
The luminescent properties of this fluorescent material is: the chromaticity coordinates of colour developing is: x=0.31 ~ 0.35, y=0.29 ~ 0.34, and colour temperature is 4357K ~ 4879K.
Compared with prior art, the present invention at least has the following advantages:
1) the present invention adopts hydrothermal method to prepare submicron order Eu 3+, Dy 3+, Tb 3+: β-Li 2tiO 3high-purity white emitting fluorescent powder, under low temperature calcination, (500 ~ 700 DEG C) can make rare earth ion 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 order Eu by hydrothermal method 3+, Dy 3+, Tb 3+: β-Li 2tiO 3white fluorescence material, 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 order Eu prepared by the present invention 3+, Dy 3+, Tb 3+: β-Li 2tiO 3white fluorescence powder material, 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 white light color developing of gained fluorescent material is good, and colour temperature is lower.
[accompanying drawing explanation]
Fig. 1 is Eu prepared by example 1 3+, Dy 3+, Tb 3+: β-Li 2tiO 3the X ray diffracting spectrum of white emitting fluorescent powder.
Fig. 2 is Eu prepared by example 3 3+, Dy 3+, Tb 3+: β-Li 2tiO 3the field emission scanning electron microscope image of white emitting fluorescent powder.
Fig. 3 is Eu prepared by example 2 3+, Dy 3+, Tb 3+: β-Li 2tiO 3the utilizing emitted light spectrogram of white emitting fluorescent powder.
Fig. 4 is Eu prepared by example 5 3+, Dy 3+, Tb 3+: β-Li 2tiO 3the utilizing emitted light spectrogram of white emitting fluorescent powder.
Fig. 5 is Eu prepared by example 6 3+, Dy 3+, Tb 3+: β-Li 2tiO 3the utilizing emitted light spectrogram of white emitting fluorescent powder.
Fig. 6 is Eu prepared by example 4 3+, Dy 3+, Tb 3+: β-Li 2tiO 3the XYZ chromaticity diagram of white emitting fluorescent powder.
Fig. 7 is Eu prepared by example 7 3+, Dy 3+, Tb 3+: β-Li 2tiO 3the XYZ chromaticity diagram of white emitting fluorescent powder.
[specific 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 (material of this high pressure vessel 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) added appropriate distilled water in high pressure vessel in packing ratio, after abundant dissolving, 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+, Dy 3+, Tb 3+volumetric molar concentration be respectively 0.1 ~ 10mol% and (refer to Eu 3+, Dy 3+, Tb 3+account for body material β-Li respectively 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3, Dy 2o 3, Tb 4o 7powder.By TiO 2powder and Eu 2o 3, Dy 2o 3, Tb 4o 7powder 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 raw material in high pressure vessel is 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+, Dy 3+, Tb 3+: β-Li 2tiO 3powder;
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 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 2.25mol/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 is 0.5mol%, Dy 3+volumetric molar concentration is 1.0mol%, Tb 3+volumetric molar concentration is that 1.5mol% (refers to Eu 3+, Dy 3+, Tb 3+account for body material β-Li 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3, Dy 2o 3, Tb 4o 7powder.By TiO 2powder and Eu 2o 3, Dy 2o 3, Tb 4o 7powder 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 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+, Dy 3+, Tb 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 color developing good (chromaticity coordinates is x=0.35, y=0.34), colour temperature be 4751K, grain diameter is 134nm, be evenly distributed, phase purity be 100% submicron order Eu 3+, Dy 3+, Tb 3+: β-Li 2tiO 3white emitting fluorescent powder.
Embodiment 2
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 high pressure vessel;
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 is 7.5mol%, Dy 3+volumetric molar concentration is 10.0mol%, Tb 3+volumetric molar concentration is that 10.0mol% (refers to Eu 3+, Dy 3+, Tb 3+account for body material β-Li 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3, Dy 2o 3, Tb 4o 7powder.By TiO 2powder and Eu 2o 3, Dy 2o 3, Tb 4o 7powder 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 25kHz, and the treatment time is 20min, and raw material in high pressure vessel is 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+, Dy 3+, Tb 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 color developing good (chromaticity coordinates is x=0.35, y=0.33), colour temperature be 4746K, grain diameter is 149nm, be evenly distributed, phase purity be 100% submicron order Eu 3+, Dy 3+, Tb 3+: β-Li 2tiO 3white emitting fluorescent powder.
Embodiment 3
1) a certain amount of LiOHH 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 high pressure vessel;
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 is 0.5mol%, Dy 3+volumetric molar concentration is 1.0mol%, Tb 3+volumetric molar concentration is that 1.0mol% (refers to Eu 3+, Dy 3+, Tb 3+account for body material β-Li 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3, Dy 2o 3, Tb 4o 7powder.By TiO 2powder and Eu 2o 3, Dy 2o 3, Tb 4o 7powder 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 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+, Dy 3+, Tb 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 color developing good (chromaticity coordinates is x=0.35, y=0.33), colour temperature be 4859K, grain diameter is 130nm, be evenly distributed, phase purity be 100% submicron order Eu 3+, Dy 3+, Tb 3+: β-Li 2tiO 3white emitting fluorescent powder.
Embodiment 4
1) a certain amount of LiOHH 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 1.50mol/L in high pressure vessel;
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 is 0.2mol%, Dy 3+volumetric molar concentration is 0.1mol%, Tb 3+volumetric molar concentration is that 0.3mol% (refers to Eu 3+, Dy 3+, Tb 3+account for body material β-Li 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3, Dy 2o 3, Tb 4o 7powder.By TiO 2powder and Eu 2o 3, Dy 2o 3, Tb 4o 7powder 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 20kHz, and the treatment time is 18min, and raw material in high pressure vessel is 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+, Dy 3+, Tb 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 color developing good (chromaticity coordinates is x=0.31, y=0.29), colour temperature be 4679K, grain diameter is 144nm, be evenly distributed, phase purity be 100% submicron order Eu 3+, Dy 3+, Tb 3+: β-Li 2tiO 3white emitting fluorescent powder.
Embodiment 5
1) a certain amount of LiOHH 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 high pressure vessel;
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 is 6.5mol%, Dy 3+volumetric molar concentration is 8.0mol%, Tb 3+volumetric molar concentration is that 4.0mol% (refers to Eu 3+, Dy 3+, Tb 3+account for body material β-Li 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3, Dy 2o 3, Tb 4o 7powder.By TiO 2powder and Eu 2o 3, Dy 2o 3, Tb 4o 7powder 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 10kHz, and the treatment time is 24min, and raw material in high pressure vessel is 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+, Dy 3+, Tb 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 color developing good (chromaticity coordinates is x=0.34, y=0.33), colour temperature be 4357K, grain diameter is 171nm, be evenly distributed, phase purity be 100% submicron order Eu 3+, Dy 3+, Tb 3+: β-Li 2tiO 3white emitting fluorescent powder.
Embodiment 6
1) a certain amount of LiOHH 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 high pressure vessel;
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 is 1.5mol%, Dy 3+volumetric molar concentration is 0.5mol%, Tb 3+volumetric molar concentration is that 0.7mol% (refers to Eu 3+, Dy 3+, Tb 3+account for body material β-Li 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3, Dy 2o 3, Tb 4o 7powder.By TiO 2powder and Eu 2o 3, Dy 2o 3, Tb 4o 7powder 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 40kHz, and the treatment time is 15min, and raw material in high pressure vessel is 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+, Dy 3+, Tb 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 color developing good (chromaticity coordinates is x=0.35, y=0.34), colour temperature be 4457K, grain diameter is 165nm, be evenly distributed, phase purity be 100% submicron order Eu 3+, Dy 3+, Tb 3+: β-Li 2tiO 3white emitting fluorescent powder.
Embodiment 7
1) a certain amount of LiOHH 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 is 8.5mol%, Dy 3+volumetric molar concentration is 10.0mol%, Tb 3+volumetric molar concentration is that 10.0mol% (refers to Eu 3+, Dy 3+, Tb 3+account for body material β-Li 2tiO 3volumetric molar concentration), take appropriate Eu 2o 3, Dy 2o 3, Tb 4o 7powder.By TiO 2powder and Eu 2o 3, Dy 2o 3, Tb 4o 7powder 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 35kHz, and the treatment time is 12min, and raw material in high pressure vessel is 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+, Dy 3+, Tb 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 color developing good (chromaticity coordinates is x=0.35, y=0.32), colour temperature be 4879K, grain diameter is 138nm, be evenly distributed, phase purity be 100% submicron order Eu 3+, Dy 3+, Tb 3+: β-Li 2tiO 3white emitting 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+, Dy 3+, Tb 3+: β-Li 2tiO 3white emitting fluorescent powder particle diameter is less and be evenly distributed, and primary particle median size is at about 130nm.The result of Fig. 3, Fig. 4, Fig. 5 emmission spectrum shows, is under the near ultraviolet excitation of 359nm at wavelength, Eu 3+, Dy 3+, Tb 3+: β-Li 2tiO 3phosphor emission goes out the visible ray of 438 ~ 620nm.Fig. 6, Fig. 7 chromaticity diagram shows, Eu 3+, Dy 3+, Tb 3+: β-Li 2tiO 3the color developing of white emitting fluorescent powder is good, and chromaticity coordinates is near the mark white point (x=0.33, y=0.33).
Technological difficulties: high temperature solid-state method gained Eu 3+, Dy 3+, Tb 3+: β-Li 2tiO 3white fluorescence powder material, the large and skewness of grain diameter after high-temperature calcination, coating property is poor, and activator mixes uneven, causes light-emitting phosphor efficiency to reduce.Meanwhile, grain diameter conference causes most rare earth ion to be difficult to enter β-Li 2tiO 3lattice, material emission poor-performing.

Claims (10)

1. an Eu 3+, Dy 3+, Tb 3+activate β-Li 2tiO 3the preparation method of single-matrix white 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, Eu source, Dy source, Tb 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 Eu according to claim 1 3+, Dy 3+, Tb 3+activate β-Li 2tiO 3the preparation method of single-matrix white 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 Eu according to claim 1 3+, Dy 3+, Tb 3+activate β-Li 2tiO 3the preparation method of single-matrix white fluorescent powder, is characterized in that: according to atomic molar ratio, Li:Ti=1.85 ~ 2.25:1 (atomic molar ratio), Eu 3+, Dy 3+, Tb 3+account for body material β-Li 2tiO 3volumetric molar concentration be respectively 0.1 ~ 10mol%.
4. a kind of Eu according to claim 1 3+, Dy 3+, Tb 3+activate β-Li 2tiO 3the preparation method of single-matrix white fluorescent powder, is characterized in that: the material of described high pressure vessel is tetrafluoroethylene, stainless steel or Hastelloy, and the pressure range of this high pressure vessel is 1 ~ 100Mpa.
5. a kind of Eu according to claim 1 3+, Dy 3+, Tb 3+activate β-Li 2tiO 3the preparation method of single-matrix white fluorescent powder, it is characterized in that: in described LiOH solution, add Ti source, Eu source, Dy source, Tb source, adopt the mode of ultrasonic cleaning to ensure abundant dissolving, described ultrasonic frequency is 10 ~ 40kHz, and the treatment time is 10 ~ 30min.
6. a kind of Eu according to claim 1 3+, Dy 3+, Tb 3+activate β-Li 2tiO 3the preparation method of single-matrix white fluorescent powder, is characterized in that: described Ti source, Eu source, Dy source, Tb source join in LiOH solution simultaneously.
7. a kind of Eu according to claim 1 3+, Dy 3+, Tb 3+activate β-Li 2tiO 3the preparation method of single-matrix white 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 Eu according to claim 1 3+, Dy 3+, Tb 3+activate β-Li 2tiO 3the preparation method of single-matrix white 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 Eu obtained based on method described in claim 1 3+, Dy 3+, Tb 3+activate β-Li 2tiO 3single-matrix white fluorescent powder, is characterized in that: the primary particle median size of this fluorescent material is 140nm.
10. a kind of Eu according to claim 1 3+, Dy 3+, Tb 3+activate β-Li 2tiO 3single-matrix white fluorescent powder, is characterized in that: the luminescent properties of this fluorescent material is: the chromaticity coordinates of colour developing is: x=0.31 ~ 0.35, y=0.29 ~ 0.34, and colour temperature is 4357K ~ 4879K.
CN201510188941.7A 2015-04-20 2015-04-20 Eu<3+>, Dy<3+>, Tb<3+> excited beta-Li2TiO3 single-substrate white-light fluorescent powder, and preparation method thereof Pending CN104974753A (en)

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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN102746000A (en) * 2012-07-11 2012-10-24 中南大学 Method for preparing lithium titanate ceramic powder by hydrothermal method
CN103803642A (en) * 2014-03-03 2014-05-21 福建师范大学 Method for preparing nano octahedron Li2TiO3

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN102746000A (en) * 2012-07-11 2012-10-24 中南大学 Method for preparing lithium titanate ceramic powder by hydrothermal method
CN103803642A (en) * 2014-03-03 2014-05-21 福建师范大学 Method for preparing nano octahedron Li2TiO3

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CHENG-LONG YU ET AL.: "Monoclinic Li2TiO3 nano-particles via hydrothermal reaction: Processing and structure", 《CERAMICS INTERNATIONAL》 *
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