CN107267148A - A kind of terbium ion doping zirconic acid lanthanum fluorescent material and preparation method thereof - Google Patents
A kind of terbium ion doping zirconic acid lanthanum fluorescent material and preparation method thereof Download PDFInfo
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- CN107267148A CN107267148A CN201710616281.7A CN201710616281A CN107267148A CN 107267148 A CN107267148 A CN 107267148A CN 201710616281 A CN201710616281 A CN 201710616281A CN 107267148 A CN107267148 A CN 107267148A
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- zirconic acid
- acid lanthanum
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
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- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The present invention relates to a kind of terbium ion doping zirconic acid lanthanum green light fluorescent powder and preparation method thereof, it is characterised in that its chemical composition is La2(1‑x)Tb2xZr2O7, 0.001≤x≤0.5.Fluorescent material is synthesized using sol-gel processing, can prepare that crystallinity is good, the uniform fluorescent material of chemical constituents analysis under relatively low heat treatment temperature, and the preparation of powder has the advantages that low cost, mass, favorable repeatability.
Description
Technical field
The present invention relates to a kind of preparation method of white semiconductor illumination green emitting phosphor.Exactly the present invention is a kind of
Rare earth terbium ion（Tb3+）Adulterate zirconic acid lanthanum（La2Zr2O7）Powder, and this powder body material preparation method.
Background technology
Semiconductor light-emitting-diode（LED）Light fixture is illuminating device of new generation, is to substitute fluorescent lamp and electricity-saving lamp, realize section
The new technology that can be lowered consumption.LED lamp has wide purposes, such as street lamp, pendent lamp, platform in outdoor lighting and room lighting field
Lamp, car light, torch etc..Also it is widely used in a variety of applications in display field, including advertising lamp box and large scale display screen.LED
Tool realizes that luminous physical arrangement is mainly the light launched near ultraviolet chip as exciting light, produces fluorescent material and is excited
Launch and light.The structure of fluorescent material LED lamp is played an important role from performance, it is necessary to develop different glow colors,
The fluorescent material for the performance such as luminous efficiency is high, thermal quenching effect is small is come the need for meeting light fixture.
Zirconic acid lanthanum has cubic crystal structure, and because the material has, fusing point is high, chemical stability is good, ionic conductivity
High, the low feature of thermal conductivity, is mainly used in thermal barrier coating and proton conductor material.Zirconic acid lanthanum does not have phase transformation below fusing point, warp
Cross multiple cycle sintering crystallite dimension and increase seldom.In addition, zirconic acid lanthanum also has certain photocatalysis performance, studied be used in is urged
Agent field.It is the premise for preparing high-temp heat barrier coating to synthesize lanthanum zirconate powder, the need for being also synthetic catalyst.It is common at present
The method of synthesis lanthanum zirconate powder have high-temperature solid phase reaction method, the precipitation method, hydro-thermal method, combustion method etc..
Rare earth ion doped zirconic acid lanthanum material mainly improves the physical property of zirconic acid lanthanum by adulterating, and improves thermal boundary and applies
Layer and light-catalysed performance, the Doped ions having been reported include cerium ion（Ce4+）, dysprosium ion（Dy3+）, praseodymium ion（Pr3+）、
Gadolinium ion（Gd3+）, samarium ion（Sm3+）, ytterbium ion（Yb3+）, erbium ion（Er3+）Deng.Due to the physical chemistry that zirconic acid lanthanum is stable
Matter is so as to fit in the matrix as luminescent material.There is doping europium ion at present（Eu3+）, cerium ion（Ce3+）, dysprosium from
Son（Dy3+）Deng the zirconic acid lanthanum fluorescent material of doping.Terbium ion（Tb3+）It is much practical fluorescent material with efficient green emission
Activator.Do not prepare the report of terbium ion doping zirconic acid lanthanum fluorescent material on sol-gel processing also so far.
The content of the invention
The present invention provides a kind of terbium ion doping zirconic acid lanthanum fluorescent material with green emission.
The fluorescent material chemical structural formula of the present invention is La2(1-x)Tb2xZr2O7。
The powder preparation method of the present invention is sol-gel processing.
The preparation method of the terbium ion doping zirconic acid lanthanum fluorescent material of above-mentioned green emission, it is comprised the following steps that：
（1）Choose raw material.Rare earth ion（La, Tb etc.）Corresponding metal oxide, or metal nitrate are chosen respectively；Zirconium source
Select five water zirconium nitrates；
（2）According to chemical formula La2(1-x)Tb2xZr2O7Metallic element stoichiometry precise raw material, x=0.001~0.5；
（3）When rare earths material is rare earth oxide, rare earth oxide is dissolved in the aqueous solution of dust technology first, rare earth is prepared
Nitrate aqueous solution., it is necessary to configure its aqueous solution according to suitable concentration when directly using rare earth nitrades.It is sufficiently stirred for
It is even, make the rear earth ions distribution in the aqueous solution uniform；
（4）Zirconium nitrate is dissolved in water, appropriate concentration is arrived in regulation；
（5）Rare earth nitrate aqueous solution is mixed with nitric acid aqueous zirconium, it is 0.5~2.0 mol/ to control metal cation concentration
L, after being sufficiently stirred for, adds appropriate citric acid or ethylenediamine tetra-acetic acid（EDTA）Deng complexing agent；
（6）Will（5）In prepared mixture solution contain in beaker, adjust pH value to 8~10 using dust technology and ammoniacal liquor,
Water bath processing 4~24 hours at a temperature of 50~90 DEG C, form wet gel；
（7）Wet gel is put and dried in an oven, xerogel is obtained, drying temperature is 70~120 DEG C, and drying time is 2~12
Hour；
（8）Xerogel is placed in crucible, is calcined in Muffle furnace or tube furnace, obtains fluorescent material, calcining heat is 1000~
1300 DEG C, calcination time is 2~8 hours.
Beneficial effects of the present invention：
（1）The fluorescent material that the present invention is provided is using zirconic acid lanthanum as matrix, and terbium ion is activator, launch wavelength in 400~600 nm,
Main emission peak is located at 544 nm, is green emission, and luminous intensity is big, and excitation and colour rendering are good.
（2）The present invention uses sol-gel processing, and this method has that synthesis temperature is low, process conditions controllability is good, composition
The advantages of molecular level is uniformly distributed, Preparation equipment is simple.Prepared fluorescent material particle diameter narrow distribution range, microstructure is near
It is dispersed preferable like spherical.
Brief description of the drawings
Fig. 1 is the XRD spectrum of the powder of embodiment 1.
Fig. 2 is the electron scanning micrograph of the powder of embodiment 1.
Fig. 3 is the excitation spectrum of the powder of embodiment 1.
Fig. 4 is the emission spectrum of the powder of embodiment 1.
Fig. 5 is the emission spectrum of the powder of embodiment 2.
Embodiment
With reference to embodiment, the present invention is described further.
Embodiment 1：Weigh 0.0325 g Tb4O7With 0.5389 g La2O3Powder, is placed in same beaker, adds dense
The mL of dust technology 9 for 5 mol/L is spent, heating stirring is dissolved to clear solution.10 mL deionized waters are added after cooling, are stirred
Uniform obtain contains Tb3+Ion and La3+The nitrate aqueous solution of ion.Weigh 1.4949 g Zr (NO3)4∙5H2O and 2.9326
G citric acids, are put into another beaker, add 150 mL deionized waters, and magnetic agitation is completely dissolved nitrate.Then will be upper
The solution mixing in 2 beakers is stated, 15 mL deionized waters is added, adds NH3∙H2O, adjusts the pH value of solution 8~9.Stir
Mix after 30 minutes, the beaker for filling above-mentioned mixed solution is placed in water bath, at a temperature of 60~80 DEG C, carry out water-bath anti-
Should, successively obtain colloidal sol and wet gel.Wet gel is put with beaker gradually to dry out at 105 DEG C in an oven, eventually forms dry
Gel.Xerogel is moved into corundum crucible, calcined in tube furnace, calcining heat is 1150 DEG C, calcination time is 6 hours,
Calcination atmosphere is air atmosphere.After natural cooling, the La with green emission is obtained1.9Tb0.1Zr2O7Fluorescent material.
Embodiment 2：Weigh 0.2542 g Tb4O7Powder adds the mL of dust technology 4 that concentration is 5 mol/L in beaker,
Heating stirring, is dissolved to after clear solution, cooling and adds 10 mL deionized waters, and the acquisition that stirs contains Tb3+The nitric acid of ion
Saline solution.Weigh 0.8833 g La (NO3)3∙6H2O、1.4597 g Zr(NO3)4∙5H2O and 2.8577 g citric acids, are put into
In another beaker, 150 mL deionized waters are added, magnetic agitation is completely dissolved nitrate.Then by above-mentioned 2 beakers
In solution mixing, add 10 mL deionized waters, add NH3∙H2O, adjusts the pH value of solution 8~9.Stirring 30 minutes
Afterwards, the beaker for filling above-mentioned mixed solution is placed in water bath, at a temperature of 60~80 DEG C, carries out water-bath and priority
Obtain colloidal sol and wet gel.Wet gel is put with beaker and handled 8 hours at 110 DEG C in an oven, forms xerogel.Xerogel is moved
Enter in corundum crucible, calcined in Muffle furnace, calcining heat is 1200 DEG C, calcination time is 2 hours, calcination atmosphere is air gas
Atmosphere.After natural cooling, the La with green emission is obtained1.2Tb0.8Zr2O7Fluorescent material.
Claims (6)
1. a kind of terbium ion doping zirconic acid lanthanum green light fluorescent powder, it is characterised in that consisting of the pyrochlore constitution shown in following formula,
Chemical composition：La2(1-x)Tb2xZr2O7, 0.001≤x≤0.5.
2. a kind of preparation method for preparing white light LEDs zirconic acid lanthanum base fluorescent powder as claimed in claim 1, its specific steps
It is as follows：
（1）Choose raw material.Rare earth ion（La, Tb etc.）Corresponding metal oxide, or metal nitrate are chosen respectively；Zirconium source
Select five water zirconium nitrates；
（2）According to chemical formula La2(1-x)Tb2xZr2O7Metallic element stoichiometry precise raw material；
（3）When rare earths material is rare earth oxide, rare earth oxide is dissolved in the aqueous solution of dust technology first, rare earth is prepared
Nitrate aqueous solution., it is necessary to configure its aqueous solution according to suitable concentration when directly using rare earth nitrades.It is sufficiently stirred for
It is even, make the rear earth ions distribution in the aqueous solution uniform；
（4）Zirconium nitrate is dissolved in water, appropriate concentration is formulated into；
（5）Rare earth nitrate aqueous solution is mixed with nitric acid aqueous zirconium, it is 0.5~2.0 mol/ to control metal cation concentration
L, after being sufficiently stirred for, adds appropriate citric acid or ethylenediamine tetra-acetic acid（EDTA）Deng complexing agent；
（6）Will（5）In prepared mixture solution contain in beaker, adjust pH value to 8~10 using dust technology and ammoniacal liquor,
Water bath processing 4~24 hours at a temperature of 50~90 DEG C, form wet gel；
（7）Wet gel is put and dried in an oven, xerogel is obtained, drying temperature is 70~120 DEG C, and drying time is 2~12
Hour；
（8）Xerogel is placed in crucible, is calcined in Muffle furnace or tube furnace, obtains fluorescent material, calcining heat is 1000~
1300 DEG C, calcination time is 2~8 hours.
3. the method that the sol-gel processing according to claims 2 prepares white light LEDs zirconic acid lanthanum base fluorescent powder, it is special
Levy and be, described activator is trivalent terbium ion（Tb3+）.
4. the method that the sol-gel processing according to claims 2 prepares white light LEDs zirconic acid lanthanum base fluorescent powder, it is special
Levy and be, described host material is zirconic acid lanthanum（La2Zr2O7）.
5. the method that the sol-gel processing according to claims 2 prepares white light LEDs zirconic acid lanthanum base fluorescent powder, it is special
Levy and be, described complexing agent is citric acid or EDTA.
6. the method that the sol-gel processing according to claims 2 prepares white light LEDs zirconic acid lanthanum base fluorescent powder, it is special
Levy and be, described zirconium source is zirconium nitrate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108624321A (en) * | 2017-11-21 | 2018-10-09 | 杭州显庆科技有限公司 | One kind Lu containing lithium2Zr2O7System phosphor |
| CN112661511A (en) * | 2021-01-13 | 2021-04-16 | 中国人民解放军国防科技大学 | Doped and modified rare earth zirconate powder and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007023293A2 (en) * | 2005-08-24 | 2007-03-01 | Southside Thermal Sciences (Sts) Limited | Luminescent material compositions and structures incorporating the same |
| CN101629078A (en) * | 2009-08-17 | 2010-01-20 | 浙江理工大学 | Method for preparing cubic shape green luminescent material of lanthanum zirconate doped with cerium and terbium |
| CN102718485A (en) * | 2012-06-27 | 2012-10-10 | 中国地质大学（武汉） | Cerium-doped lanthanum zirconate nano powder and preparation method thereof |
| CN102815941A (en) * | 2012-09-13 | 2012-12-12 | 中国科学院上海硅酸盐研究所 | Rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof |
| CN103396119A (en) * | 2013-08-25 | 2013-11-20 | 中国人民解放军国防科学技术大学 | Preparation method of single-phase pyrochlore-type La2Zr2O7 nano-powder |
| CN103553596A (en) * | 2013-10-29 | 2014-02-05 | 山东大学 | Preparation method of zirconic acid lanthanum ceramic fiber |
| CN105970015A (en) * | 2016-06-26 | 2016-09-28 | 浙江大学 | Method for preparing silver carbon nanotube and lanthanum zirconate composite electric contact material |
-
2017
- 2017-07-26 CN CN201710616281.7A patent/CN107267148A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007023293A2 (en) * | 2005-08-24 | 2007-03-01 | Southside Thermal Sciences (Sts) Limited | Luminescent material compositions and structures incorporating the same |
| CN101629078A (en) * | 2009-08-17 | 2010-01-20 | 浙江理工大学 | Method for preparing cubic shape green luminescent material of lanthanum zirconate doped with cerium and terbium |
| CN102718485A (en) * | 2012-06-27 | 2012-10-10 | 中国地质大学（武汉） | Cerium-doped lanthanum zirconate nano powder and preparation method thereof |
| CN102815941A (en) * | 2012-09-13 | 2012-12-12 | 中国科学院上海硅酸盐研究所 | Rare-earth-ion-doped lanthanum gadolinium zirconate transparent ceramic material and preparation method thereof |
| CN103396119A (en) * | 2013-08-25 | 2013-11-20 | 中国人民解放军国防科学技术大学 | Preparation method of single-phase pyrochlore-type La2Zr2O7 nano-powder |
| CN103553596A (en) * | 2013-10-29 | 2014-02-05 | 山东大学 | Preparation method of zirconic acid lanthanum ceramic fiber |
| CN105970015A (en) * | 2016-06-26 | 2016-09-28 | 浙江大学 | Method for preparing silver carbon nanotube and lanthanum zirconate composite electric contact material |
Non-Patent Citations (4)
| Title |
|---|
| YA-HONG XIE ET AL.: "Preparation of La1.9Ca0.1Zr2O6.95 with pyrochlore structure and its application in synthesis of ammonia at atmospheric pressure", 《SOLID STATE IONICS》 * |
| 刘仁源: "静电纺丝技术制备La2M2O7(M=Ti,Zr,Sn):RE3+纳米带与发光性质研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 刘树信 等: "原位合成La2Zr2O7-YSZ复合材料及高温热稳定性研究", 《中国粉体技术》 * |
| 胡龄之: "两种 FED 用氧化物基发光材料的制备及其发光性能研究", 《中国优秀硕士学位论文全文数据库基础科学辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108624321A (en) * | 2017-11-21 | 2018-10-09 | 杭州显庆科技有限公司 | One kind Lu containing lithium2Zr2O7System phosphor |
| CN112661511A (en) * | 2021-01-13 | 2021-04-16 | 中国人民解放军国防科技大学 | Doped and modified rare earth zirconate powder and preparation method and application thereof |
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