CN104910911A - Novel garnet-based spherical red phosphor - Google Patents

Novel garnet-based spherical red phosphor Download PDF

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CN104910911A
CN104910911A CN201510153771.9A CN201510153771A CN104910911A CN 104910911 A CN104910911 A CN 104910911A CN 201510153771 A CN201510153771 A CN 201510153771A CN 104910911 A CN104910911 A CN 104910911A
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garnet
fluorescent material
preparation
spherical red
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李金凯
陈奇
滕鑫
刘宗明
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University of Jinan
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University of Jinan
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Abstract

The invention provides a novel garnet-based spherical red phosphor, a chemical formula is [(GdxLu1-x)0.95Eu0.05]3Al5O12((Gd,Lu)AG:Eu<3+>). The synthetic method of the phosphor takes rare earth nitrate and an Al(NO3)3(or NH4Al(SO4)2) solution according to stoichiometric ratio to obtain a mother salting liquid, the mother salting liquid is mixed with an urea precipitating agent, and then steps of heating, stirring and insulation to obtain the suspending liquid, the obtained deposition is centrifuged, washed, and dried to obtain the white precursor powder, and (Gd, Lu) AG:Eu<3+> garnet fluorescence particle can be obtained through calcining. The phosphor particle is in a spherical shape, dispersibility is uniform, fluorescence is excellent, and the garnet-based spherical red phosphor is expected to a novel generation illumination display material.

Description

The spherical red fluorescent material of a kind of novel garnet-base
Technical field
The present invention relates to a kind of fluorescent material and the preparation method that are applied to the fields such as illumination and display.。
Background technology
It is little that photodiode (LED) has electric current, and luminous intensity is high, and response is fast, the advantages such as the life-span is long, and volume is little, and as a kind of high-level efficiency, the green solid light source of low cost, has been widely used in the fields such as illumination and display.Along with the development of LED technology and the universal of solid state lighting, traditional LED light source can not meet the growing demand of people gradually.
Now widely used YAG (Y 3al 5o 12) be fluorescent material (such as YAG:Ce fluorescent material), there is energy conversion rate low, the problems such as luminous efficiency is not high, and product granularity is uneven, thus affect the luminous intensity of LED.Therefore on the basis of YAG system fluorescent material, a kind of novel high-quality fluorescent material is developed significant.
Summary of the invention
Technical problem to be solved by this invention is to provide one (Gd, Lu) AG:Eu 3+spherical red fluorescent material and preparation method, this fluorescent material more traditional YAG and LuAG system fluorescent material has clear superiority.A) Gd (157) and Lu (175) nucleidic mass close to and all far above Y (89), this is made to be that novel fluorescent material has higher theoretical density, thus effectively can improve its radiation dynamics, preferably for scintillator material; B) Gd 3+ion can sensitization Eu 3+the red emission of ion, thus strengthen fluorescence property; C) the fluorescent grain sphericity prepared of this technique is high and be uniformly dispersed, and effectively can improve the resolving power of fluorescence components and parts, be easy to self-assembly and be fine and close fluorescent layer thus reduce to greatest extent, to exciting scattering of light, to present optimal luminescent efficiency.
For achieving the above object, the present invention takes following scheme:
The spherical red fluorescent material of a kind of novel garnet-base, preparation method comprises the following steps:
(1) by powdery rare earth oxide compound (Gd 2o 3, Lu 2o 3and Eu 2o 3) be dissolved in appropriate salpeter solution, heating for dissolving also removes excessive nitric acid, is made into rare earth nitrate solution;
(2) by appropriate urea, rare earth nitrate and Al (NO 3) 3(or NH 4al (SO 4) 2) solution is according to [(Gd x lu 1- x ) 0.95eu 0.05] AG stoichiometric ratio mixing, add deionized water and be made into the solution that volume is 1L;
(3) in 40-60min, be heated to 90 ± 5 DEG C after getting step (2) gained solution stirring 1h, insulation 2h obtains suspension liquid;
(4) step (3) gained suspension liquid is naturally cooled to 50 ± 1 DEG C, by centrifugal, cleaning, the white precursor powder of dry acquisition;
(5) precursor powder of step (4) gained is calcined 4h at 900-1100 DEG C and obtain (Gd, Lu) AG:Eu 3+garnet fluorescent particle.
Fluorescent material prepared by the present invention can be used for manufacturing photodiode, for fields such as illumination, signal lamp, backlight, personal communication apparatus and medical treatment.
The present invention has prepared a kind of spherical red fluorescent material by coprecipitation method.By optimized fabrication method, preferably suitable precipitation agent and precipitant concentration, preferred aluminium salt kind and proportioning, optimize the processing parameters such as reactant concn, temperature of reaction, reaction times and calcining temperature, prepared (Gd, Lu) AG:Eu of excellent performance 3+spherical red fluorescent material.
Accompanying drawing explanation
Fig. 1 is through 1100 DEG C of calcining 4h gained [(Gd x lu 1- x ) 0.95eu 0.05] 3al 5o 12(x=0-0.4) the XRD figure spectrum of spherical red fluorescent material.
Fig. 2 is through 1100 DEG C of calcining 4h gained [(Gd x lu 1- x ) 0.95eu 0.05] 3al 5o 12(x=0.1-0.4) the FE-SEM shape appearance figure of spherical red fluorescent material.
Fig. 3 is through 1100 DEG C of calcining 4h gained [(Gd x lu 1- x ) 0.95eu 0.05] 3al 5o 12the exciting of spherical red fluorescent material (PLE, left) and launch (PL, the right side) spectrum.Embedded figure is the change of 592nm fluorescence intensity with Gd content.
Embodiment
Below by concrete example, set forth the present invention further.
Embodiment 1
The spherical red fluorescent material of a kind of novel garnet-base, preparation method is as follows:
Raw materials used: Lu 2o 3(99.99%), Gd 2o 3(99.99%), Eu 2o 3(99.99%), Al (NO 3) 39H 2o (99.0%), NH 4al (SO 4) 2(99.0%), urea (CO (NH 2) 2, 99.0%);
(1) by powdery Lu 2o 3, Gd 2o 3and Eu 2o 3be dissolved in respectively in hot nitric acid, remove excessive HNO 3be made into rare earth nitrate solution;
(2) by Gd 3+ion: Lu 3+ion: Eu 3+ion: Al 3+ion mol ratio 0:2.85:0.15:5 measures rare earth nitrate, Al (NO 3) 3and NH 4al (SO 4) 2(mol ratio is 1:1) solution, urea concentration is R=40, mixes, and adds deionized water and is made into 1L solution;
(3) 1h is stirred to the mixed solution that step (2) obtains, in 60min, mixed solution is heated to 90 ± 5 DEG C and obtains suspension liquid after being incubated 2h;
(4) centrifugal after the suspension liquid that step (3) obtains being naturally cooled to 50 ± 1 DEG C, cleaning is carried out and drying to obtained precipitation, obtains (Gd, Lu) AG:Eu 3+white precursor powder;
(5) step (4) is obtained (Gd, Lu) AG:Eu 3+precursor powder, in 1100 DEG C of calcining 4h, finally obtains the spherical red fluorescent material of garnet-base.
Embodiment 2
The spherical red fluorescent material of a kind of novel garnet-base, preparation method is as follows:
Raw materials used: Lu 2o 3(99.99%), Gd 2o 3(99.99%), Eu 2o 3(99.99%), Al (NO 3) 39H 2o (99.0%), NH 4al (SO 4) 2(99.0%), urea (CO (NH 2) 2, 99.0%);
(1) by powdery Lu 2o 3, Gd 2o 3and Eu 2o 3be dissolved in respectively in hot nitric acid, remove excessive HNO 3be made into rare earth nitrate solution;
(2) by Gd 3+ion: Lu 3+ion: Eu 3+ion: Al 3+ion mol ratio 0.285:2.565:0.15:5 measures rare earth nitrate, Al (NO 3) 3and NH 4al (SO 4) 2(mol ratio is 1:1) solution, urea concentration is R=40, mixes, and adds deionized water and is made into 1L solution;
(3) 1h is stirred to the mixed solution that step (2) obtains, in 60min, mixed solution is heated to 90 ± 5 DEG C and obtains suspension liquid after being incubated 2h;
(4) centrifugal after the suspension liquid that step (3) obtains being naturally cooled to 50 ± 1 DEG C, cleaning is carried out and drying to obtained precipitation, obtains (Gd, Lu) AG:Eu 3+white precursor powder;
(5) step (4) is obtained (Gd, Lu) AG:Eu 3+precursor powder, in 1100 DEG C of calcining 4h, finally obtains the spherical red fluorescent material of garnet-base.
Fig. 2 (a) is through 1100 DEG C of calcining 4h gained [(Gd x lu 1- x ) 0.95eu 0.05] 3al 5o 12(x=0.1) the FE-SEM shape appearance figure of spherical red fluorescent material, visible prepared fluorescent powder has good sphericity, and is uniformly dispersed.
Embodiment 3
The spherical red fluorescent material of a kind of novel garnet-base, preparation method is as follows:
Raw materials used: Lu 2o 3(99.99%), Gd 2o 3(99.99%), Eu 2o 3(99.99%), Al (NO 3) 39H 2o (99.0%), NH 4al (SO 4) 2(99.0%), urea (CO (NH 2) 2, 99.0%);
(1) by powdery Lu 2o 3, Gd 2o 3and Eu 2o 3be dissolved in respectively in hot nitric acid, remove excessive HNO 3be made into rare earth nitrate solution;
(2) by Gd 3+ion: Lu 3+ion: Eu 3+ion: Al 3+ion mol ratio 0.57:2.28:0.15:5 measures rare earth nitrate, Al (NO 3) 3and NH 4al (SO 4) 2(mol ratio is 1:1) solution, urea concentration is R=40, mixes, and adds deionized water and is made into 1L solution;
(3) 1h is stirred to the mixed solution that step (2) obtains, in 60min, mixed solution is heated to 90 ± 5 DEG C and obtains suspension liquid after being incubated 2h;
(4) centrifugal after the suspension liquid that step (3) obtains being naturally cooled to 50 ± 1 DEG C, cleaning is carried out and drying to obtained precipitation, obtains (Gd, Lu) AG:Eu 3+white precursor powder;
(5) step (4) is obtained (Gd, Lu) AG:Eu 3+precursor powder, in 1100 DEG C of calcining 4h, finally obtains the spherical red fluorescent material of garnet-base.
Fig. 2 (b) is through 1100 DEG C of calcining 4h gained [(Gd x lu 1- x ) 0.95eu 0.05] 3al 5o 12(x=0.2) the FE-SEM shape appearance figure of spherical red fluorescent material.
Embodiment 4
The spherical red fluorescent material of a kind of novel garnet-base, preparation method is as follows:
Raw materials used: Lu 2o 3(99.99%), Gd 2o 3(99.99%), Eu 2o 3(99.99%), Al (NO 3) 39H 2o (99.0%), NH 4al (SO 4) 2(99.0%), urea (CO (NH 2) 2, 99.0%);
(1) by powdery Lu 2o 3, Gd 2o 3and Eu 2o 3be dissolved in respectively in hot nitric acid, remove excessive HNO 3be made into rare earth nitrate solution;
(2) by Gd 3+ion: Lu 3+ion: Eu 3+ion: Al 3+ion mol ratio 0.855:1.995:0.15:5 measures rare earth nitrate, Al (NO 3) 3and NH 4al (SO 4) 2(mol ratio is 1:1) solution, urea concentration is R=40, mixes, and adds deionized water and is made into 1L solution;
(3) 1h is stirred to the mixed solution that step (2) obtains, in 60min, mixed solution is heated to 90 ± 5 DEG C and obtains suspension liquid after being incubated 2h;
(4) centrifugal after the suspension liquid that step (3) obtains being naturally cooled to 50 ± 1 DEG C, obtained precipitation is carried out cleaning and drying, obtain (Gd, Lu) AG:Eu 3+white precursor powder;
(5) step (4) is obtained (Gd, Lu) AG:Eu 3+precursor powder, in 1100 DEG C of calcining 4h, finally obtains the spherical red fluorescent material of garnet-base.
Fig. 2 (c) is through 1100 DEG C of calcining 4h gained [(Gd x lu 1- x ) 0.95eu 0.05] 3al 5o 12(x=0.3) the FE-SEM shape appearance figure of spherical red fluorescent material.
Embodiment 5
The spherical red fluorescent material of a kind of novel garnet-base, preparation method is as follows:
Raw materials used: Lu 2o 3(99.99%), Gd 2o 3(99.99%), Eu 2o 3(99.99%), Al (NO 3) 39H 2o (99.0%), NH 4al (SO 4) 2(99.0%), urea (CO (NH 2) 2, 99.0%);
(1) by powdery Lu 2o 3, Gd 2o 3and Eu 2o 3be dissolved in respectively in hot nitric acid, remove excessive HNO 3be made into rare earth nitrate solution;
(2) by Gd 3+ion: Lu 3+ion: Eu 3+ion: Al 3+ion mol ratio 1.14:1.71:0.15:5 measures rare earth nitrate, Al (NO 3) 3and NH 4al (SO 4) 2(mol ratio is 1:1) solution, urea concentration is R=40, mixes, and adds deionized water and is made into 1L solution;
(3) 1h is stirred to the mixed solution that step (2) obtains, in 60min, mixed solution is heated to 90 ± 5 DEG C and obtains suspension liquid after being incubated 2h;
(4) centrifugal after the suspension liquid that step (3) obtains being naturally cooled to 50 ± 1 DEG C, obtained precipitation is carried out cleaning and drying, obtain (Gd, Lu) AG:Eu 3+white precursor powder;
(5) step (4) is obtained (Gd, Lu) AG:Eu 3+precursor powder, in 1100 DEG C of calcining 4h, finally obtains the spherical red fluorescent material of garnet-base.
Fig. 2 (d) is through 1100 DEG C of calcining 4h gained [(Gd x lu 1- x ) 0.95eu 0.05] 3al 5o 12(x=0.4) the FE-SEM shape appearance figure of spherical red fluorescent material.
Fig. 1 is through 1100 DEG C of calcining 4h gained [(Gd x lu 1- x ) 0.95eu 0.05] 3al 5o 12(x=0-0.4) the XRD figure spectrum of fluorescent material.As seen from the figure, use the fluorescent material prepared by aforesaid method to be pure phase, and diffraction peak increase with Gd content and continuously to low angle drift, illustrate that Gd has been solidly soluted in garnet crystal lattice.
Fig. 3 is through 1100 DEG C of calcining 4h gained [(Gd x lu 1- x ) 0.95eu 0.05] 3al 5o 12the exciting of spherical red fluorescent material (PLE, left) and launch (PL, the right side) spectrum.Visible sample x=0.1-0.4 with xthe excitation spectrum of=0 is different, and the former has occurred Gd at 275 nm places 3+'s f-fcharacteristic transition 8s 7/2→ 6i j.The appearance at this characteristic transition peak illustrates to there is Gd 3+→ Eu 3+non-radiative energy transmits.As seen from the figure, the excitation intensity of sample and emissive porwer all increase with the increase of Gd content, and the former is mainly due to Gd 3+electronegativity (1.20) lower than Lu 3+electronegativity (1.27).The increase of Gd content causes [Gd x lu 1- x ] 3+the average electronegativity of combination reduces, to O 2pthe binding force of orbital electron weakens, thus O 2-→ Eu 3+charge transtion is more prone to generation, CTB excitation intensity increases.The latter is mainly due to Gd 3+→ Eu 3+caused by transmission ofenergy.Gd content by x=0 is increased to xwhen=0.4, the fluorescence intensity of material adds the embedded figure of 35%(Fig. 3).

Claims (6)

1. the spherical red fluorescent material of novel garnet-base, is characterized in that comprising chemical constitution formula is [(Gd x lu 1- x ) 0.95eu 0.05] 3al 5o 12component, x value is 0-0.4.
2. a preparation method for the spherical red fluorescent material of novel garnet-base, is characterized in that, comprise the following steps:
(1) by rare earth oxide (Gd 2o 3, Lu 2o 3and Eu 2o 3) be dissolved in hot nitric acid and be made into rare earth nitrate solution;
(2) by Gd 3+ion: Lu 3+ion: Eu 3+ion: Al 3+ion mol ratio 0-1.14:1.71-2.85:0.15:5, measures rare earth nitrate, Al (NO 3) 3or NH 4al (SO4) 2, urea soln mixes, and adds deionized water and is made into the solution that volume is 1L;
(3) be heated to 90 ± 5 DEG C through 40-60 min after step (2) gained mixed solution being stirred 1h, insulation 2h, obtains suspension liquid;
(4) step (3) gained suspension liquid is naturally cooled to 50 ± 1 DEG C, obtain white precursor powder by centrifugal, cleaning, drying;
(5) step (4) gained precursor powder is calcined 4h at 900-1100 DEG C and finally obtain (Gd, Lu) AG:Eu 3+garnet phosphor powder.
3. preparation method as claimed in claim 2, it is characterized in that, selected precipitation agent is urea, concentration R (CO (NH 2)/(Ln 3++ Al 3+))=20-100.
4. preparation method as claimed in claim 2, is characterized in that, Al 3+ion source is in Al (NO 3) 3and NH 4al (SO 4) 2, mol ratio is 1:1.
5. preparation method as claimed in claim 2, it is characterized in that, the calcining temperature of presoma is 1100 DEG C.
6. preparation method as claimed in claim 2, it is characterized in that, the calcination atmosphere of presoma is air atmosphere.
CN201510153771.9A 2015-04-02 2015-04-02 Novel garnet-based spherical red phosphor Pending CN104910911A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114015088A (en) * 2021-09-18 2022-02-08 东北师范大学 Preparation method and application of organic-inorganic nano composite scintillator material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114015088A (en) * 2021-09-18 2022-02-08 东北师范大学 Preparation method and application of organic-inorganic nano composite scintillator material
CN114015088B (en) * 2021-09-18 2024-04-16 东北师范大学 Preparation method and application of organic-inorganic nano composite scintillator material

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