CN1281707C - Rare earth containing oxide red luminescent materials and method for preparing same - Google Patents
Rare earth containing oxide red luminescent materials and method for preparing same Download PDFInfo
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- CN1281707C CN1281707C CN 200410009747 CN200410009747A CN1281707C CN 1281707 C CN1281707 C CN 1281707C CN 200410009747 CN200410009747 CN 200410009747 CN 200410009747 A CN200410009747 A CN 200410009747A CN 1281707 C CN1281707 C CN 1281707C
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Abstract
The present invention provides a red luminescent material containing rare earth oxides and a preparation method thereof. The red luminescent material is expressed as the following chemical formula: (Y<1-x-y-z>Gd<x>Al<y>Eu<z>)2O3, wherein the content x of the Gd as a component of base materials is more than 0 and at most 0.7, the content y of the Al as a component of the base materials is more than 0 and less than 0.26, and the content z of the Eu as an activator is at least 0.02 and at most 0.12. Y2O3, Gd2O3, Al2O3 and Eu2O3 are ignited at 1280 DEG C in order to generate solid solution (YGdAlEu)2O3 in a cubic structure, and partial rare earth elements, such as Y and Gd, are replaced by a non rare earth element Al. The present invention has the advantages of high material chemical stability, high luminance, good monochromaticity, relatively lower cost, simple preparation method and easy operation, and is suitable for batch production.
Description
Technical field
The invention belongs to the luminescent material technical field, a kind of red luminescent material of oxide compound that contains rare earth and preparation method thereof particularly is provided, reduced cost, be applicable to suitability for industrialized production.
Background technology
It must be pure monochromaticity well red (the sharp line emission of the about 612nm of wavelength) that red material in the three primary colors fluorescent powder requires its emmission spectrum, and the red illuminating material that is applied to luminescent lamp at present is Y
2O
3: Eu
3+, Y
2O
3: Eu
3+Ultraviolet ray excited down at 254nm, produce Eu
3+Charge transfer state excite, then a topmost spectral line is that wavelength is the line spectrum of 611nm in the transition radiation of Chan Shenging, this has just in time satisfied in the three primary colours white spectrum requirement to red composition wavelength.
Along with science and technology development, be to improve the luminescent properties of three-basic-colour lamp powder, people have done many experimental studies, but do not see as yet so far aspect the new red illuminating material of exploitation big breakthrough being arranged, and are just improving Y
2O
3: Eu
3+Size-grade distribution, improve its luminous intensity, improve aspects such as stability of photoluminescence some progress are arranged.Chinese patent CN1506493A has proposed at a cube Y
2O
3: Eu
3+Introduce the Gd ion in the system and make it part replacement Y, obtain the rare earth oxide red fluorescence powder.But yttrium, gadolinium cost an arm and a leg as rare earth element, and a large amount of the use causes product cost to raise.So improve luminescent properties, reduce cost, simplify preparation technology and be still the problem that three primary colours rouge and powder is demanded urgently studying.
Summary of the invention
The purpose of this invention is to provide a kind of red luminescent material of oxide compound and synthetic method thereof that contains rare earth.Solved yttrium, gadolinium as rare earth element, cost an arm and a leg, a large amount of problems that cause product cost to raise of using.Materials chemistry good stability, luminosity height, monochromaticity are good, cost reduces relatively.
Chemical constitution of the present invention is (Y
1-x-y-zGd
xAl
yEu
z)
2O
3, 0＜x≤0.7 wherein, x is the content of matrix components Gd; 0＜y＜0.26, y is the content of matrix components Al; 0.02≤z≤0.12, z is the content of activator Eu.
The red illuminating material that contains the oxide compound of rare earth of the present invention is by Y
2O
3, Gd
2O
3, Al
2O
3And Eu
2O
3Through 1280 ℃ of high temperature sinterings, form (YGdAlEu) with cubic structure
2O
3Solid solution, thereby have the advantages that chemical stability is good, luminosity is high, monochromaticity is good, and, reduce product cost because non-rare earth Al to the part replacement of rare earth element y, Gd, causes rare earth element dosage to reduce.
The method for preparing the red illuminating material of the described oxide compound that contains rare earth comprises the steps:
(1) with purity is 99.99% Y respectively
2O
3, Gd
2O
3, Eu
2O
3And the above Al (OH) of purity assay
3Be dissolved in analytically pure nitric acid, be made into the rare earth nitrate solution and the aluminum nitrate solution of desired concn, determine after its accurate concentration stand-byly with sodium ethylene diamine tetracetate (EDTA) complexometry, it is stand-by that other joins the analytical pure ammonium oxalate solution.
(2) by (Y
1-x-y-zGd
xAl
yEu
z)
2O
3Chemical constitution after getting the rare earth nitrate solution of different mol ratio and aluminum nitrate solution and mixing, at 75～80 ℃, adds excessive analytical pure ammonium oxalate solution and (is 120～200%mol) of theoretical consumption, obtains mixed precipitation (pH is 4～5).Washing is filtered to neutral, in 100～130 ℃ of oven dry down.
(3) above-mentioned mixed precipitation is packed in the corundum crucible, put it into High Temperature Furnaces Heating Apparatus,, advance the mode that heat goes out, be decomposed into mixed oxide with heat 850～950 ℃ of following constant temperature 1.5～2.5 hours.
(4) with behind above-mentioned mixed oxide fragmentation, the porphyrize, in the corundum crucible of packing into, advance the mode that heat goes out with heat, in High Temperature Furnaces Heating Apparatus in 1250～1300 ℃ of following constant temperature 2.5～3.0 hours.
(5) firing product obtains product after conventional processing such as porphyrize, washing, filtration, oven dry, promptly contains the red luminescent material of oxide compound of rare earth.
Characteristics of the present invention are:
(1) proposed partly to replace rare earth element in the rare earth oxide luminescent material, formed the red fluorescent material of new europkium-activated oxide compound and formed with non-rare earth Al;
(2) this fluorescent material is cubic structure in the time of 1280 ℃, does not have dephasign to exist.Fig. 1 is (Y
0.26Gd
0.50Al
0.20Eu
0.04)
2O
3The XRD figure spectrum;
(3) emmission spectrum of this fluorescent material and present widely used red fluorescence powder Y
2O
3: Eu (cube phase) is identical, sees Fig. 2;
(4) under the identical preparation condition, the luminous intensity of this fluorescent material is apparently higher than Y
2O
3: Eu;
(5) Al partly replaces rare earth element and causes the fluorescent material cost to descend;
(6) the activator concentration scope is clear and definite, and as shown in Figure 3, optimum concn is 0.06mol;
(7) use the coprecipitation method mixing raw material, improved mixing efficiency, shortened milling time, reduced calcination temperature;
(8) simple, the easy handling of this fluorescent material manufacture method, suitable batch production.
Description of drawings
Fig. 1 is the present invention (Y
0.26Gd
0.50Al
0.20Eu
0.04)
2O
3The XRD figure of fluorescent material.Wherein, X-coordinate is diffraction angle 2 θ, and ordinate zou is an intensity.
Fig. 2 is the present invention (Y
0.26Gd
0.50Al
0.20Eu
0.04)
2O
3The emmission spectrum figure of fluorescent material.Wherein, X-coordinate is a wavelength X, and ordinate zou is an intensity.
Fig. 3 is light-emitting phosphor intensity of the present invention and activator Eu
3+The graph of a relation of concentration.Wherein, X-coordinate is Eu
3+Content, ordinate zou is an intensity.
Embodiment
Embodiment 1: respectively with Y
2O
3, Eu
2O
3, Al
2O
3, Gd
2O
3Be dissolved in nitric acid, be made into nitrate solution, determine that with EDTA its concentration is respectively C (Y)=0.2058molL
-1, C (Eu)=0.01936molL
-1, C (Gd)=0.4120molL
-1, C (Al)=0.02108molL
-1Accurately measure the Y (NO of above-mentioned concentration respectively
3)
3Solution 23.49ml, Eu (NO
3)
3Solution 15.94ml puts into same beaker, mixes and be heated to 80 ℃ on constant temperature magnetic force heating stirrer.Other takes by weighing ammonium oxalate (NH
4)
2C
2O
4H
2O solid 1.32g, be dissolved in the less water, ammonium oxalate solution is slowly joined in the beaker that fills mixed nitrate solution, obtain white and mix oxalate precipitation, pH is 4, filter, washing after 100 ℃ of oven dry, is put into corundum crucible to neutral, advance heat with heat and go out mode, obtain mixed oxide its constant temperature 2 hours in 900 ℃ High Temperature Furnaces Heating Apparatus.The mixed oxide of coming out of the stove cooling back is broken, in agate mortar, behind the porphyrize, put into corundum crucible again, advance heat with heat and go out mode, 1280 ℃ of following constant temperature 3 hours.The product of will coming out of the stove cooling back is broken, uses the agate mortar porphyrize, obtains (Y
1-x-y-zGd
xAl
yEu
z)
2O
3Consist of (Y in the series
0.94Eu
0.06)
2O
3Red fluorescence powder, under the 254nm ultraviolet excitation, its relative luminous intensity is 100%.
Embodiment 2: accurately measure the Y (NO of concentration with embodiment 1 respectively
3)
3Solution 4.25ml, Eu (NO
3)
3Solution 11.30ml, Gd (NO
3)
3Solution 6.20ml puts into same beaker, and other takes by weighing ammonium oxalate (NH
4)
2C
2O
4H
2O solid 0.93g, all the other conditions obtain molecular composition and are (Y with embodiment 1
0.24Gd
0.70Eu
0.06)
2O
3Red fluorescence powder, under the 254nm ultraviolet excitation, its relative luminous intensity is 105%.
Embodiment 3: accurately measure the Y (NO of concentration with embodiment 1 respectively
3)
3Solution 5.58ml, Eu (NO
3)
3Solution 13.69ml, Gd (NO
3)
3Solution 5.04ml, Al (NO
3)
3Solution 44.01ml puts into same beaker, and other takes by weighing ammonium oxalate (NH
4)
2C
2O
4H
2O solid 1.88g, all the other conditions obtain molecular composition and are (Y with embodiment 1
0.26Gd
0.47Al
0.21Eu
0.06)
2O
3Red fluorescence powder, under the 254nm ultraviolet excitation, its relative luminous intensity is 117%.
Embodiment 4-embodiment 14: change Y (NO among the embodiment 3
3)
3Solution, Gd (NO
3)
3Solution, Al (NO
3)
3Solution, Eu (NO
3)
3Solution, ammonium oxalate (NH
4)
2C
2O
4H
2O solid consumption, the stoichiometric ratio synthetic sample according to molecular formula in the table 1 obtains red fluorescence powder, and under the 254nm ultraviolet excitation, its relative luminous intensity is also listed in the table 1.
Table 1 embodiment 4-embodiment 14 and relative luminous intensity thereof
| Embodiment | Molecular formula | Relative luminous intensity (%) |
| 4 | (Y 0.26Gd 0.60Al 0.10Eu 0.04) 2O 3 | 105 |
| 5 | (Y 0.26Gd 0.55Al 0.15Eu 0.04) 2O 3 | 108 |
| 6 | (Y 0.26Gd 0.52Al 0.18Eu 0.04) 2O 3 | 110 |
| 7 | (Y 0.26Gd 0.49Al 0.21Eu 0.04) 2O 3 | 114 |
| 8 | (Y 0.26Gd 0.40Al 0.30Eu 0.04) 2O 3 | 102 |
| 9 | (Y 0.16Gd 0.70Al 0.10Eu 0.04) 2O 3 | 89.5 |
| 10 | (Y 0.06Gd 0.70Al 0.20Eu 0.04) 2O 3 | 110 |
| 11 | (Y 0.01Gd 0.70Al 0.25Eu 0.04) 2O 3 | 101 |
| 12 | (Y 0.26Gd 0.51Al 0.21Eu 0.02) 2O 3 | 34.3 |
| 13 | (Y 0.26Gd 0.45Al 0.21Eu 0.08) 2O 3 | 100 |
| 14 | (Y 0.26Gd 0.43Al 0.21Eu 0.10) 2O 3 | 41.0 |
Claims (2)
1, a kind of red luminescent material of oxide compound that contains rare earth, it is characterized in that: chemical constitution is: (Y
1-x-y-zGd
xAl
yEu
z)
2O
3, 0＜x≤0.7 wherein, x is the content of matrix components Gd; 0＜y＜0.26, y is the content of matrix components Al; 0.02≤z≤0.12, z is the content of activator Eu.
2, a kind of method for preparing the described luminescent material of claim 1 is characterized in that:
A, with purity 99.99% Y respectively
2O
3, Gd
2O
3, Eu
2O
3And the above Al (OH) of purity assay
3Be dissolved in analytically pure nitric acid, be made into the rare earth nitrate solution and the aluminum nitrate solution of desired concn, determine after its accurate concentration stand-byly with the sodium ethylene diamine tetracetate complexometry, it is stand-by that other joins the analytical pure ammonium oxalate solution;
B, by (Y
1-x-y-zGd
xAl
yEu
z)
2O
3Chemical constitution is after getting the rare earth nitrate solution of different mol ratio and aluminum nitrate solution and mixing, at 75～80 ℃, add excessive analytical pure ammonium oxalate solution, be 120～200%mol of theoretical consumption, obtaining mixed precipitation pH is 4～5, washing is filtered to neutral, in 100～130 ℃ of oven dry down;
C, above-mentioned mixed precipitation is packed in the corundum crucible, put it into High Temperature Furnaces Heating Apparatus,, advance the mode that heat goes out, be decomposed into mixed oxide with heat 850～950 ℃ of following constant temperature 1.5～2.5 hours;
D, with behind above-mentioned mixed oxide fragmentation, the porphyrize, in the corundum crucible of packing into, advance the mode that heat goes out with heat, in High Temperature Furnaces Heating Apparatus in 1250～1300 ℃ of following constant temperature 2.5～3.0 hours;
E, firing product obtain product after porphyrize, washing, filtration, oven dry conventional processing, promptly contain the red luminescent material of oxide compound of rare earth.
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|---|---|---|---|
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|---|---|---|---|
| CN 200410009747 CN1281707C (en) | 2004-11-05 | 2004-11-05 | Rare earth containing oxide red luminescent materials and method for preparing same |
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|---|---|
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| CN1281707C true CN1281707C (en) | 2006-10-25 |
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Owner name: ACER COMPUTER (CHINA) CO., LTD. Free format text: FORMER OWNER: BEIDA FANGZHENG SCIENCE + TECHNOLOGY COMPUTER SYSTEM CO., LTD., SHANGHAI Effective date: 20101029 |
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Effective date of registration: 20101104 Address after: 100085 B, block 12D-1B, building 8, information road, Haidian District, Beijing Patentee after: Minmetals (Beijing) Rare Earth Research Institute Co Ltd Address before: 100083 Haidian District, Xueyuan Road, No. 30, Patentee before: University of Science and Technology Beijing |