CN100347267C - Garnet type gadolinium aluminate based fluorescent powder and method for making same - Google Patents

Garnet type gadolinium aluminate based fluorescent powder and method for making same Download PDF

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CN100347267C
CN100347267C CNB2005100561401A CN200510056140A CN100347267C CN 100347267 C CN100347267 C CN 100347267C CN B2005100561401 A CNB2005100561401 A CN B2005100561401A CN 200510056140 A CN200510056140 A CN 200510056140A CN 100347267 C CN100347267 C CN 100347267C
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fluorescent powder
preparation
powder
citric acid
solution
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CN1664063A (en
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罗岚
谭敦强
周浪
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Nanchang University
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Nanchang University
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Abstract

The present invention relates to garnet type gadolinium aluminate based fluorescent powder and a preparation method thereof. The chemical expression of the fluorescent powder is Gd3 (1-x)Al5O12: REx or Gd3Al5 (1-x)O12: REx, wherein RE is one or more of rare-earth elements, such as Eu, Pr, Ce, Tb, etc.; x is doping gram molecular weight and is larger than 0.01 and smaller than 0.1. The present invention has the preparation method that aluminum nitrate and rare-earth oxide are dissolved in a container with concentrated nitric acid in terms of stoichiometric ratio; a proper amount of citric acid of one to two times of the molar ratio of the citric acid and metal ions is added to mixed solution; the pH value of the solution is regulated to 3 to 7; the solution is stirred and heated at 70 to 80 DEG C to be transparent gel, pre-burnt at 400 to 500 DEG C and calcined at 900 to 1300 DEG C for more than 1.5 hours. The fluorescent powder prepared by the preparation method has the advantages of high color purity, high luminous intensity, uniform particle size distribution with the range of 40 nm to 100 nm, and simple and feasible technological process. Moreover, raw materials are cheap and accessible.

Description

Garnet type gadolinium aluminate based fluorescent powder and preparation method thereof
Technical field
The invention belongs to the luminescent powder preparation field, particularly rare-earth activated garnet type gadolinium aluminate based fluorescent powder and preparation method.
Background technology
Garnet type gadolinium aluminate (Gd 3Al 5O 12, be called for short GAG) and have excellent optical property, mechanical property and stable physicochemical property, its application is just attracted attention by people as the novel optical body material.GAG belongs to tetragonal spheroidal, and the kernel of fast growth, generation is smaller, big to distribution coefficient ideal, the uptake factor of admixture, and its crystal is a kind of ideal Solid State Laser body material.And the powder of other ion (mainly being rare earth element ion and transition metal ion) that mixes in GAG excites visible emitting down in ultraviolet and vacuum-ultraviolet light, X ray and high energy particle, be expected to be applied to fields such as cathode ray tube (CRT), Field Emission Display (FED), plasma flat-panel display, to improve the device resolution.
As a kind of novel material, the direct research of still unmatchful GAG powder preparing technology has only GdAlO at present 3(being called for short GAP) and Y 3Al 5O 12The research of (being called for short YAG) powder preparing.People such as J.W.M.Verweij adopt the solid reaction method to synthesize GAP (GdAlO 3) powder (Chemical Physics Letters 239 (1995) 51-55), with Gd 2O 3And Al 2O 3The powder uniform mixing, and under the high temperature more than 1450 ℃, heat-treat.This method technology is simple, easily produces in batches, and shortcoming is that thermal treatment temp is higher, easily introduces impurity in the mechanical milling process, and (impurity derives from the calcinate except that principal crystalline phase GAP, often residual a small amount of intermediate phase Gd 4Al 2O 9(being called for short GAM) and Gd 3Al 5O 12(being called for short GAG).In recent years, wet chemical method has been successfully applied to Y 3Al 5O 12Powder is synthetic." method for preparing the YAG powder " (patent No. JP200127071.4) as the people such as IKEGAMI TAKAYASU of Japan invention, make raw material with yttrium carbonate and kayserite, make the solution that contains carbonate and sulfonium ion, pH value by regulator solution forms precipitation, throw out is heat-treated, and obtaining particle diameter is the single-phase YAG powder of 40-400nm.People such as Liu Qian, Luo Lan (application number 310107829.3) is a raw material with the nitrate aqueous solution of Gd and Al, is jelling agent and spontaneously inflammable fuel with the citric acid, and the gel of acquisition is calcined between 800-1300 ℃, obtains particle diameter at the GAP of 40-100nm scope powder.
Summary of the invention
The fluorescent powder chemical expression of the present invention's preparation is as follows:
Gd 3 (1-x)Al 5O 12: RE xOr Gd 3Al 5 (1-x)O 12: RE x
RE is rare earth element elements such as (RE mainly are Eu, Pr, Ce, Tb) in the formula, and RE can be one or more of rare earth element), X is the doping gram molecular weight, 0.01＜x＜0.1 is pure Gd during X=0 3Al 5O 12
The present invention adopts so-gel process and burning building-up process to combine, and prepares fluorescent powder by the method for complexing between metal nitrate and the citric acid and redox reaction.
Preparation process of the present invention is as follows: press stoichiometric ratio with aluminum nitrate (Al (NO 3) 39H 2O) and Gd 2O 3, Eu 2O 3, Pr 6O 11, CeO 2Being dissolved in the container with concentrated nitric acid Deng in the rare earth oxide one or more, is 1～2 times amount by citric acid and metal ion mol ratio, adds an amount of citric acid, regulator solution pH value to 3～7 in mixing solutions.The container that fills mixing solutions is placed on the magnetic stirring apparatus,, obtain the transparence gel 70～80 ℃ of stirring heating.Gel is put into 400～500 ℃ of pre-burnings of box-type furnace, obtain forerunner's powder of grey black.Forerunner's powder obtains rose pink the finished product through 900～1300 ℃ of temperature calcination more than 1.5 hours.
The fluorescent powder purity of color height of the present invention preparation, luminous intensity is big, size distribution is even, and (scope is 40～100nm), technological process is simple, and raw material cheaply and be easy to get.
Description of drawings
Fig. 1 presses the fluorescence spectrum of GAG:Eu nano-powder under ultraviolet excitation of embodiment 1 preparation, and X-coordinate is wavelength (nm), and ordinate zou is a luminous intensity.
Fig. 2 presses the fluorescence spectrum of embodiment 2 preparation GAG:Pr nano-powders under burst of ultraviolel, and X-coordinate is wavelength (nm), and ordinate zou is a luminous intensity.
Fig. 3 presses the GAG:Eu of embodiment 3 preparations, and the fluorescence spectrum of Ce nano-powder under ultraviolet excitation, X-coordinate are wavelength (nm), and ordinate zou is a luminous intensity.
Fig. 4 presses the fluorescence spectrum of GAG:Tb nano-powder under ultraviolet excitation of embodiment 4 preparations, and X-coordinate is wavelength (nm), and ordinate zou is a luminous intensity.
Embodiment
The present invention will be further detailed with the following Examples.
Embodiment 1:
Get 18.75g aluminum nitrate (Al (NO 3) 39H 2O), 5.439g gadolinium sesquioxide (Gd 2O 3), 0.1056g europium sesquioxide (Eu 2O 3), 33.4g citric acid, and the concentrated nitric acid of capacity are dissolved in the deionized water, and stirring formation homogeneous solution and regulator solution pH value is 7.The beaker that fills this solution is placed on the magnetic stirring apparatus, be heated to 70 ℃ and do not stop to stir, form colloidal sol after a few hours.Continue to stir and heat until forming the transparence gel.Gel is put into box-type furnace be heated to 400 ℃ of forerunner's powder that form grey black.Forerunner's powder through 900 ℃ of calcinings of 1.5 hours, obtains Gd again 3Al 5O 12: the rose pink the finished product of Eu (5%molGd).Fig. 1 is Gd 3Al 5O 12: Eu 3+The fluorescence spectrum of nano powder under ultraviolet excitation shows light emitting ionic Eu 3+Enter the GAG lattice with the solid solution form, UV-light (254nm) excites down the emission red fluorescence.
Embodiment 2:
Get 18.75g aluminum nitrate (Al (NO 3) 39H 2O), 5.439g gadolinium sesquioxide (Gd 2O 3), 0.1016g Praseodymium trioxide (Pr 6O 11), 33.4g citric acid, and the concentrated nitric acid of capacity are dissolved in the deionized water, and stirring formation homogeneous solution and regulator solution pH value is 3.The beaker that fills this solution is placed on the magnetic stirring apparatus, be heated to 75 ℃ and do not stop to stir, form colloidal sol after a few hours.Continue to stir formation transparence gel.Gel is put into box-type furnace be heated to 450 ℃ of forerunner's powder that form grey black, finally obtained Gd in 2 hours through 1300 ℃ of temperature calcination 3Al 5O 12: the rose pink the finished product of Pr (5%molGd).Fig. 2 is Gd 3Al 5O 12: Pr 3+The fluorescence spectrum of nano powder under ultraviolet excitation shows that light emitting ionic Pr enters the GAG lattice with the solid solution form, excites emission red fluorescence down in UV-light (254nm).
Embodiment 3:
Get 18.75g aluminum nitrate (Al (NO 3) 39H 2O), 5.493g gadolinium sesquioxide (Gd 2O 3), 0.1056g europium sesquioxide (Eu 2O 3), 0.0103g oxidation Cerium (CeO 2), 33.4g citric acid, and the concentrated nitric acid of capacity are dissolved in the deionized water, and stirring formation homogeneous solution and regulator solution pH value is 5.The beaker that fills this solution is placed on the magnetic stirring apparatus, be heated to 80 ℃ and do not stop to stir, form colloidal sol after a few hours.Continue to stir formation transparence gel.Gel is put into box-type furnace be heated to 450 ℃ of forerunner's powder that form grey black, finally obtained Gd in 1.5 hours through 1200 ℃ of temperature calcination 3Al 5O 12: Eu, the finished product that Ce is rose pink.Fig. 3 is Gd 3Al 5O 12: Eu, the fluorescence spectrum of Ce nano powder under ultraviolet excitation.
Embodiment 4:
Get 18.75g aluminum nitrate (Al (NO 3) 39H 2O), 5.493g gadolinium sesquioxide (Gd 2O 3), 0.1121g terbium sesquioxide (Tb 4O 7), 33.4g citric acid, and the concentrated nitric acid of capacity are dissolved in the deionized water, and stirring formation homogeneous solution and regulator solution pH value is 4.The beaker that fills this solution is placed on the magnetic stirring apparatus, be heated to 70 ℃ and do not stop to stir, form colloidal sol after a few hours.Continue to stir formation transparence gel.Gel is put into box-type furnace be heated to 500 ℃ of forerunner's powder that form grey black, finally obtained Gd in 2 hours through 1000 ℃ of temperature calcination 3Al 5O 12: the finished product that Tb is rose pink.Fig. 4 is Gd 3Al 5O 12: the fluorescence spectrum of Tb nano powder under ultraviolet excitation, show light emitting ionic Tb solid solution enter the GAG lattice, excite down transmitting green fluorescence in UV-light (254nm).
Show stoichiometry and the significant parameter contrast of each embodiment
Example Al(NO 3) 39H 2O Gd 2O 3 Eu 2O 3 Pr 6O 11 CeO 2 Tb 4O 7 Citric acid pH Crystalline phase Illuminant colour
1 18.75 5.439 0.1056 0 0 0 33.4 7 GAG Red
2 18.75 5.439 0 0.1016 0 0 33.4 3 GAG Red
3 18.75 5.439 0.1056 0 0.0103 0 33.4 5 GAG Red
4 18.75 5.439 0 0 0 0.1121 33.4 4 GAG Green

Claims (5)

1, a kind of garnet type gadolinium aluminate based fluorescent powder is characterized in that chemical constitution formula is:
Gd 3 (1-x)Al 5O 12: RE xOr Gd 3Al 5 (1-x)O 12: RE x
RE is a rare earth element in the formula, and X is the doping gram molecular weight, 0.01＜x＜0.1.
2,, it is characterized in that rare earth element is one or more among Eu, Pr, Ce, the Tb according to the described fluorescent powder of claim 1.
3, according to claim 1 or 2 described fluorescent powders, the particle diameter that it is characterized in that powder is 40-100nm.
4, the preparation method of fluorescent powder according to claim 1 comprises technological processs such as solation, gelation, pre-burning, calcination, it is characterized in that adopting the synthetic method that combines of sol-gel and burning.
5, the preparation method of fluorescent material according to claim 4, it is characterized in that aluminum nitrate, rare earth oxide being dissolved in the container with concentrated nitric acid by stoichiometric ratio, it by citric acid and metal ion mol ratio 1～2 times amount, in mixing solutions, add citric acid, regulator solution pH value to 3～7, be heated with stirring to the transparence gel at 70～80 ℃, 400～500 ℃ of pre-burnings are again through 900～1300 ℃ of temperature calcination more than 1.5 hours.
CNB2005100561401A 2005-03-21 2005-03-21 Garnet type gadolinium aluminate based fluorescent powder and method for making same Expired - Fee Related CN100347267C (en)

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CN103289697A (en) * 2012-03-02 2013-09-11 河南森源电气股份有限公司 Preparation method of high-performance YAG (yttrium aluminium garnet) yellow fluorescent powder
CN103031128A (en) * 2012-04-05 2013-04-10 长春理工大学 Preparation method of thulium and europium single/co-doped lutetium gallium garnet phosphor
CN103849386B (en) * 2014-02-24 2015-11-18 中国计量学院 A kind of colloidal sol auto-combustion method prepares the method for aluminate blue fluorescent powder
CN105112054B (en) * 2015-08-24 2017-12-12 济南大学 A kind of Tb3+Adulterate yttrium aluminmiu garnet new phosphorses
CN108046768B (en) * 2017-12-23 2020-05-05 东北大学 Gadolinium gallium aluminum scintillation ceramic double doped with rare earth ions and preparation method thereof
CN111253073A (en) * 2020-01-21 2020-06-09 徐州凹凸光电科技有限公司 Method for preparing gadolinium-aluminum-garnet-based white-light glass ceramic by adopting sol-gel method
CN111269720A (en) * 2020-03-06 2020-06-12 厦门稀土材料研究所 Rare earth doped double long afterglow nano material and its preparation method and use
CN116282239A (en) * 2023-03-01 2023-06-23 中国科学技术大学 Co-doped SrRuO with high coercivity 3 Material and preparation method thereof

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JP2001004753A (en) * 1999-06-23 2001-01-12 Hitachi Medical Corp Oxide phosphor and radiation detector using it as well as x-ray ct apparatus
CN1398817A (en) * 2002-08-28 2003-02-26 中国科学院上海硅酸盐研究所 Prepn of ion doped yttrium aluminium garnet nano-powder
CN1523077A (en) * 2003-09-05 2004-08-25 �й���ѧԺ�����о��� Method for preparing rare earth oxide group nanometer luminescent powder
CN1528856A (en) * 2003-10-09 2004-09-15 中国科学院上海硅酸盐研究所 Aluminic gadolinium-base luminescent film material chip and preparing method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001004753A (en) * 1999-06-23 2001-01-12 Hitachi Medical Corp Oxide phosphor and radiation detector using it as well as x-ray ct apparatus
CN1398817A (en) * 2002-08-28 2003-02-26 中国科学院上海硅酸盐研究所 Prepn of ion doped yttrium aluminium garnet nano-powder
CN1523077A (en) * 2003-09-05 2004-08-25 �й���ѧԺ�����о��� Method for preparing rare earth oxide group nanometer luminescent powder
CN1528856A (en) * 2003-10-09 2004-09-15 中国科学院上海硅酸盐研究所 Aluminic gadolinium-base luminescent film material chip and preparing method thereof

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