CN100392041C - Rare earth activated Y2SiO5 fluorescent powder, and its preparing method and use - Google Patents

Rare earth activated Y2SiO5 fluorescent powder, and its preparing method and use Download PDF

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Publication number
CN100392041C
CN100392041C CNB031496393A CN03149639A CN100392041C CN 100392041 C CN100392041 C CN 100392041C CN B031496393 A CNB031496393 A CN B031496393A CN 03149639 A CN03149639 A CN 03149639A CN 100392041 C CN100392041 C CN 100392041C
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fluorescent material
earth activated
rare
reducing atmosphere
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CN1580183A (en
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焦桓
钟鸣
荆西平
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Peking University
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Peking University
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Abstract

The present invention discloses rare earth activated Y2SiO5 fluorescent powder, and a preparation method and an application thereof. The rare earth activated Y2SiO5 fluorescent powder comprises the following components by the molar percentage of 30 to 80% of yttria or yttrium nitrate, 50t o 70 % of silicon dioxide, and 0.5 to 15% of lanthanide oxide or nitrate. The preparation method comprises the following steps: 1) the yttria dissolved in hot and concentrated nitric acid; after the reaction, silicone grease chemical compounds are added, and gel is formed at a constant temperature; 2) the gel is heated for 1 to 48 hours to obtain solidoid products; 3) the solidoid products are burnt for 1 to 48 hours in reducing atmosphere; 4) inorganic salt is added and is burnt for 1 to 48 hours in reducing atmosphere at a temperature of 800 to 1600 DEG C; 5) dilute acid is used for washing; after drying, the rare earth activated Y2SiO5 fluorescent powder is obtained. The prepared rare earth activated Y2SiO5 fluorescent powder has the advantages of high luminous intensity, controllable powder particle size and smooth particle surface, and can adopt to requirements of different devices, particularly occasions with special requirements, such as field emission, projection television, etc.

Description

A kind of rare-earth activated Y 2SiO 5Fluorescent material and its production and application
Technical field
The present invention relates to a kind of fluorescent material and its production and application, especially a kind of rare-earth activated Y 2SiO 5Fluorescent material and its production and application.
Background technology
At present, rare earth luminescent material has become the propping material in fields such as information demonstration, lighting source, photoelectric device, the high luminous intensity of fluorescent material and good micro-shape can improve the performance of indicating meter effectively, therefore, the research of novel fluorescent material and application are one of important research field of materials chemistry and materials physics always.Rare-earth activated Y 2SiO 5Owing to have advantages of higher stability and good luminous property, become one of fluorescent material that field emission display and projection TV select for use.Y 2SiO 5Fluorescent material sends the light of different colours because of different activator, and Eu activates and is red fluorescence powder, and Tb is a green emitting phosphor when activating, and Ce activates and is blue look fluorescent material, and Ce and Tb co-activation are green emitting phosphor.Y 2SiO 5Low temperature (X1) and two kinds of structure types of high temperature (X2) are arranged, when taking thermal structure, have luminescent properties preferably.Y 2SiO 5Fluorescent material has solid phase and two kinds of synthesis modes of liquid phase, the Y of solid phase synthesis 2SiO 5Light-emitting phosphor brightness is lower, powder granule size distribution inequality, and powder surface is coarse.Liquid phase synthetic Y 2SiO 5Fluorescent material brightness is higher, but exist in the synthesis technique between powder granule bonding serious, the purity of color of fluorescent material is low wait not enough.
The innovation and creation content
The purpose of this invention is to provide a kind of brightness height, the rare-earth activated Y that powder granule is evenly distributed 2SiO 5Fluorescent material and preparation method thereof.
A kind of rare-earth activated Y 2SiO 5Fluorescent material, form by the material of following molar percentage:
Yttrium oxide or Yttrium trinitrate 30-80%,
Silicon-dioxide 50-70%,
Lanthanide oxide or nitrate 0.5-15%.
Described lanthanide oxide is cerium oxide, europium sesquioxide or terbium sesquioxide, and nitrate is cerous nitrate, europium nitrate or Terbium trinitrate.
Described fluorescent material matrix is Y 2SiO 5High temperature phase (X2).
Described fluorescent material is Y 2SiO 5: Tb, Y 2SiO 5: Ce, Tb, Y 2SiO 5: Ce or Y 2SiO 5: Eu.
A kind of rare-earth activated Y 2SiO 5The preparation method of fluorescent material may further comprise the steps:
1) in heated and stirred equipment, yttrium oxide and lanthanide rare compound are dissolved in hot concentrated in, the back that reacts completely adds silicon ester compound, the pH value of regulator solution is 4-8, leaves standstill 1-48 hour the formation gel under 60-100 ℃ of constant temperature;
2) gel heated 1-48 hour under 300-600 ℃ of condition, obtained solid product;
3) after solid product grinds, in 400-1000 ℃ of scope, in the reducing atmosphere calcination 1-48 hour;
4) grind again after, add one or more inorganic salt, in 800-1600 ℃ of scope, in the reducing atmosphere calcination 1-48 hour;
5) dilute acid wash obtains rare-earth activated Y 2SiO 5Fluorescent material.
In above-mentioned preparation method, described silicon ester compound is preferably tetraethoxy; The mol ratio of Si/Y is between 0.8-1.2 in described yttrium oxide and the silicon ester compound.
General ammoniacal liquor and/or the nitric acid of adopting of described adjusting pH value.
Described inorganic salt are AlF 3, AlCl 3, Li 2CO 3, K 2CO 3, Na 2CO 3, LiF, LiCl, NaF, NaCl, CsF, CsCl, BaF 2, KF, KCl, (KPO 3) 6, (NaPO 3) 6, K 3PO 4, Na 3PO 4, Li 3PO 4, KH 2PO 4, NaH 2PO 4, K 2HPO 4, Na 2HPO 4, CaHPO 4, Ca (H 2PO 4) 2, Na 3BO 3, K 3BO 3, Li 3BO 3, Na 2SO 4, K 2SO 4, Li 2SO 4, BaSO 4, SrSO 4, MgSO 4In one or more, usage quantity is the 0.5%-100% of fluorescent material weight.
Described calcination is carried out in high-purity carbon-point, carbon dust, hydrogen and nitrogen mixture or hydrogen and argon gas gas mixture generation reducing atmosphere.
Described dilute acid wash obtains rare-earth activated Y 2SiO 5Fluorescent material is to boil 5-40 minute after adding the nitric acid of 1-15% or hydrochloric acid in the product that point to add after the inorganic salt calcination, and product is washed after drying with distillation and obtained rare-earth activated Y 2SiO 5Fluorescent material.
The content of lanthanide oxide, heat treatment time and temperature are the important factors of decision light-emitting phosphor performance.By composition, thermal treatment temp and the time of control fluorescent material, can prepare that luminous intensity height, powder particle are little, the slick negative ray blueness of particle surface and green emitting phosphor, and by kind that changes inorganic salt and granular size and the condition of surface that content can be regulated fluorescent material.
The present invention creatively adopts the auxiliary sol-gel method synthesizing rare-earth of fused salt fusion to activate Y 2SiO 5Fluorescent material can strengthen Y 2SiO 5Luminous efficiency, reduce granularity, improve the particle surface state, it is low to have a cost, the characteristics that product stability is high, the rare-earth activated Y of institute's synthetic 2SiO 5Fluorescent material is the micron-sized fluorescent material that contains yttrium, silicon, oxygen and different rare earth elements, have luminous intensity height, controlled, the slick advantage of particle surface of powder particle size, can be fit to the requirement of different components, especially have the occasion of particular requirement applicable to field emission and projection TV etc., have important industrial application value.
Description of drawings
Fig. 1 is Y 2SiO 5: the exciting light spectrogram of Ce
Fig. 2 is Y 2SiO 5: the emmission spectrum figure of Ce
Fig. 3 is Y 2SiO 5: the shape appearance figure of Ce
Fig. 4 is Y 2SiO 5: Tb excites and emmission spectrum figure
Fig. 5 is Y 2SiO 5: the shape appearance figure of Tb
Embodiment
Embodiment 1, prepare micron-sized Y 2SiO 5: the blue look fluorescent material of Ce
Raw material: comprise rare earth oxide, tetraethoxy, ammoniacal liquor, nitric acid, inorganic salts of yttrium and cerium etc.
Its preparation process is as follows:
1) in heating and stirring device, be the concentrated nitric acid dissolving rare earth oxide of 1: 1 heat with concentration, question response fully back added and the equimolar tetraethyl silicate of rare earth oxide, is 7 with the pH value of ammoniacal liquor regulator solution, 90 ℃ of constant temperature 2 days, complete to guarantee hydrolysis, obtain jel product;
2) jel product to remove water, ethanol and other organic composition wherein, obtains solid product 500 ℃ of heating 24 hours;
3) after abundant the grinding, about 700 ℃, calcination is 16 hours under the reducing atmosphere of hydrogen and nitrogen mixture generation;
4) grind again after, add and account for product weight 50%AlCl 3, about 1000 ℃, calcination is 16 hours under the reducing atmosphere of hydrogen and nitrogen mixture generation;
5) rare nitric acid of adding 10% boiled 30 minutes;
6) distilled water wash after drying obtains micron-sized Y 2SiO 5: the blue look fluorescent material of Ce.
The excitation spectrum of this fluorescent material as shown in Figure 1.The emmission spectrum of this fluorescent material as shown in Figure 2.As can be seen, the emmission spectrum of fluorescent material is the band(ed)spectrum that is positioned at 380-600nm.The pattern of fluorescent material as shown in Figure 3, the smooth surface of visible fluorescence powder, particle diameter is evenly distributed in the 2-5 mu m range.
Embodiment 2: prepare micron-sized Y 2SiO 5: the Tb green emitting phosphor
Raw material: comprise rare earth nitrate, tetraethoxy, ammoniacal liquor, nitric acid, inorganic salts of yttrium and terbium etc.
Its preparation process is as follows:
1) in heating and stirring device, uses the dissolved in distilled water rare earth nitrate, waiting to dissolve complete back and add the tetraethyl silicate that mole number equals rare earth nitrate 1/2nd, was 6 with the pH value of nitric acid regulator solution, 70 ℃ of constant temperature 1 day, complete to guarantee hydrolysis, obtain jel product;
2) gel to remove water, ethanol and other organic composition wherein, obtains solid product 400 ℃ of heating 40 hours;
3) after abundant the grinding, about 700 ℃, calcination is 16 hours under the reducing atmosphere of hydrogen and nitrogen mixture generation;
4) after abundant again the grinding, adding accounts for product weight 10%K 2CO 3, about 1000 ℃, calcination is 16 hours under the reducing atmosphere that high-purity carbon-point produces;
5) dilute hydrochloric acid of adding 10% boiled 40 minutes;
6) distilled water wash after drying obtains micron-sized Y 2SiO 5: the Tb green emitting phosphor.
This fluorescent material excite with emmission spectrum as shown in Figure 4.The pattern of this fluorescent material as shown in Figure 5, the smooth surface of visible fluorescence powder, even particle distribution.

Claims (9)

1. rare-earth activated Y 2SiO 5Fluorescent material is made up of the material of following molar percentage, and each component addition should equal absolutely:
Yttrium oxide 30-80%,
Silicon-dioxide 50-70%,
Lanthanide oxide 0.5-15%;
This rare-earth activated Y 2SiO 5Fluorescent material is to adopt the method that may further comprise the steps to prepare:
1) in heated and stirred equipment, yttrium oxide and lanthanide rare compound are dissolved in hot concentrated in, the back that reacts completely adds silicon ester compound, the pH value of regulator solution is 4-8, leaves standstill 1-48 hour the formation gel under 60-100 ℃ of constant temperature;
2) gel heated 1-48 hour under 300-600 ℃ of condition, obtained solid product;
3) after solid product grinds, in 400 ℃ of-1000 ℃ of scopes, in the reducing atmosphere calcination 1-48 hour;
4) grind again after, add inorganic salt, in 800-1600 ℃ of scope, in the reducing atmosphere calcination 1-48 hour;
5) behind the dilute acid wash, obtain rare-earth activated Y with distilled water wash and drying 2SiO 5Fluorescent material; Fluorescent material matrix is Y 2SiO 5The high temperature phase.
2. fluorescent material according to claim 1 is characterized in that: described lanthanide oxide is cerium oxide, europium sesquioxide or terbium sesquioxide.
3. fluorescent material according to claim 1 and 2 is characterized in that: described fluorescent material is Y 2SiO 5: Tb, Y 2SiO 5: Ce, Tb, Y 2SiO 5: Ce or Y 2SiO 5: Eu.
4. the described rare-earth activated Y of claim 1 2SiO 5The preparation method of fluorescent material may further comprise the steps:
1) in heated and stirred equipment, yttrium oxide and lanthanide rare compound are dissolved in hot concentrated in, the back that reacts completely adds silicon ester compound, the pH value of regulator solution is 4-8, leaves standstill 1-48 hour the formation gel under 60-100 ℃ of constant temperature;
2) gel heated 1-48 hour under 300-600 ℃ of condition, obtained solid product;
3) after solid product grinds, in 400 ℃ of-1000 ℃ of scopes, in the reducing atmosphere calcination 1-48 hour;
4) grind again after, add inorganic salt, in 800-1600 ℃ of scope, in the reducing atmosphere calcination 1-48 hour;
5) behind the dilute acid wash, obtain rare-earth activated Y with distilled water wash and drying 2SiO 5Fluorescent material.
5. preparation method according to claim 4 is characterized in that: silicon ester compound is a tetraethoxy; The mol ratio of Si/Y is between 0.8-1.2 in described yttrium oxide and the silicon ester compound; Described adjusting pH value is to adopt ammoniacal liquor and/or nitric acid.
6. preparation method according to claim 4 is characterized in that: described inorganic salt are AlF 3, AlCl 3, Li 2CO 3, K 2CO 3, Na 2CO 3, LiF, LiCl, NaF, NaCl, CsF, CsCl, BaF 2, KF, KCl, (KPO 3) 6, (NaPO 3) 6, K 3PO 4, Na 3PO 4, Li 3PO 4, KH 2PO 4, NaH 2PO 4, K 2HPO 4, Na 2HPO 4, CaHPO 4, Ca (H 2PO 4) 2, Na 3BO 3, K 3BO 3, Li 3BO 3, Na 2SO 4, K 2SO 4, Li 2SO 4, BaSO 4, SrSO 4, MgSO 4In one or more, usage quantity is the 0.5%-100% of fluorescent material weight.
7. preparation method according to claim 4 is characterized in that: described calcination is meant in reducing atmosphere in the reducing atmosphere of high-purity carbon-point, carbon dust, hydrogen and nitrogen mixture or hydrogen and the generation of argon gas gas mixture to be carried out.
8. preparation method according to claim 4 is characterized in that: described dilute acid wash obtains rare-earth activated Y 2SiO 5Fluorescent material is to boil 5-40 minute after adding the nitric acid of 1-15% or hydrochloric acid in the product that point to add after the inorganic salt calcination, and product is washed after drying with distillation and obtained rare-earth activated Y 2SiO 5Fluorescent material.
9. the application of the described fluorescent material of claim 1 in field emission display and projection TV.
CNB031496393A 2003-08-05 2003-08-05 Rare earth activated Y2SiO5 fluorescent powder, and its preparing method and use Expired - Fee Related CN100392041C (en)

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CN100519694C (en) * 2005-06-29 2009-07-29 北京大学 Y3(Al, ga)5O12rare earth fluorescent powder
CN1315984C (en) * 2005-08-02 2007-05-16 中国计量学院 Self-ignite preparation method of spherical nanometer Yttrium europium silicate fluorescent powder
CN1936673B (en) * 2005-09-23 2011-03-16 富明兴业有限公司 Fluorescent coating
CN1325604C (en) * 2005-11-30 2007-07-11 天津理工大学 MY(1-x)SiO4:Ax light-emitting film and its preparation method
CN104449679A (en) * 2014-12-25 2015-03-25 英特美光电（苏州）有限公司 LED (light-emitting diode) fluorescent powder cosolvent and application thereof
CN105754599A (en) * 2016-03-10 2016-07-13 华北水利水电大学 Monoclinic-system-structured superfine white nano fluorescent powder and preparation method thereof
CN109835910B (en) * 2017-11-28 2020-11-06 中国石油天然气股份有限公司 Preparation method of carrier silica gel
CN109233835A (en) * 2018-09-18 2019-01-18 江苏锐阳照明电器设备有限公司 A kind of LED light fluorescent powder and preparation method thereof can be reduced the reaction time
CN111017982B (en) * 2019-12-31 2022-02-01 中南大学 Nano-grade rare earth silicate powder material and application thereof
CN112300798A (en) * 2020-10-30 2021-02-02 东台市天源光电科技有限公司 High-color-rendering environment-friendly red fluorescent powder and preparation method thereof

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