CN1212367C - Red RE oxide luminophor and its prepn - Google Patents

Red RE oxide luminophor and its prepn Download PDF

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Publication number
CN1212367C
CN1212367C CN 02144731 CN02144731A CN1212367C CN 1212367 C CN1212367 C CN 1212367C CN 02144731 CN02144731 CN 02144731 CN 02144731 A CN02144731 A CN 02144731A CN 1212367 C CN1212367 C CN 1212367C
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rare earth
earth oxide
oxide red
red fluorescence
ball
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CN1506439A (en
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王晓君
谢宜华
刘行仁
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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Abstract

The present invention belongs to the technical field of luminescent materials and relates to fluorescent powder which can emit red fluorescence under the excitation of electron beams or vacuum ultraviolet rays. More specially, the present invention relates to rare earth oxide red fluorescent powder and a preparation method thereof. The fluorescent powder provided by the present invention is expressed as the following chemical formula: (Y<1-x-y-z>Gd<x>Eu<y>)2O3, wherein the x is at most 0.9, and the y is at least 0.01 and at most 0.1. Solid solution of (Y, Gd)2O3 and (Y, Gd, Eu)2O3 in a cubic structure generates at a high temperature of 1250 DEG C by introducing Gd ions in a Y2O3: Eu cubic system. The solid solution is made into the rare earth oxide red fluorescent powder by selecting materials, mixing the materials, sintering the mixed materials and treating the sintered material finally. The present invention has the characteristics as the following: firstly, the fluorescent powder is still in a cubic structure after being sintered at more than 1250 DEG C, and the crystallization quality of crystals is good; secondly, the concentration range of an activator is satisfied; thirdly, the calcination temperature is reduced by using additives, the luminance is enhanced, and the crystal growth is promoted; fourthly, the preparation technology is simple, and the method is easy to operate.

Description

Rare earth oxide red fluorescence powder and preparation method thereof
Technical field: the invention belongs to field of light emitting materials, relate to the fluorescent material of emission red fluorescence under electron beam or excited by vacuum ultraviolet, is a kind of rare earth oxide red fluorescence powder and manufacture method thereof.
Background technology: can excite material luminous under the situation a lot, these materials can be applied in fields such as demonstration as fluorescent material, for example cube type Gd 2O 3Common cube of type Gd 2O 3The transformation temperature that changes monocline type into is greatly about 1250 ℃, promptly at the Gd that obtains more than 1250 ℃ 2O 3Be monocline.According to a cube type Gd 2O 3This character, can prepare a cube type Gd 2O 3Fluorescent powder for matrix.But with a cube type Gd 2O 3The fluorescent material for preparing for matrix has monocline, and the light-emitting phosphor efficient of monocline is low.Use Eu 3+Activated cubic oxide yttrium is widely used in the new technologies such as demonstration, video picture, lighting source at electron beam or vacuum ultraviolet-excited down red-emitting, but along with the development of these technology, Y 2O 3: Eu 3+Luminescent properties can not satisfy the demand, people require to provide performance more good luminescent material.
Summary of the invention: the present invention is at a cube Y 2O 3: Eu 3+Introduce the Gd ion in the system and make it part replacement Y, Y under 1250 ℃ of high temperature 2O 3And Gd 2O 3And Y 2O 3, Gd 2O 3And Eu 2O 3Formation have cubic structure (Y, Gd) 2O 3(Y, Gd, Eu) 2O 3Solid solution.The new Solid solution of this class is that very stable class matter homophase is replaced Solid solution, has good luminescent properties.By at a cube Y 2O 3: Eu 3+Introduce the Gd ion in the system, purpose provides the good rare earth oxide red fluorescence powder of a kind of luminosity height, purity of color and prepares the method for this fluor
The present invention passes through at a cube Y 2O 3: Eu 3+Introduce the Gd ion in the system and make it part replacement Y, Y under 1250 ℃ of high temperature 2O 3And Gd 2O 3And Y 2O 3, Gd 2O 3And Eu 2O 3Formation have cubic structure (Y, Gd) 2O 3(Y, Gd, Eu) 2O 3Solid solution obtains the rare earth oxide red fluorescence powder.
The present invention is at a cube Y 2O 3: Eu 3+After introducing the Gd ion in the system, Y in the system 2O 3And Gd 2O 3And Y 2O 3, Gd 2O 3And Eu 2O 3Formation have cubic structure (Y, Gd) 2O 3(Y, Gd, Eu) 2O 3Solid solution, its chemical expression is as follows:
(Y 1-x-yGd xEu y) 2O 3
Wherein x is the content of matrix components Gd, and content is 0＜x≤0.9, and y is the content of activator Eu, and content is 0.01≤y≤0.1.Fluor matrix part is made up of the oxide compound of Gd and Y, and the activator material is for containing Eu 3+Oxide compound.
Rare earth oxide red fluorescence powder of the present invention, when the content of matrix components Gd in 0＜x≤0.9 scope, be higher than Gd 2O 3Transformation temperature (1250 ℃) time, (Y 1-x-yGd xEu y) 2O 3Fluorescent material is body-centered cubic structure still, has luminosity height, characteristics that purity of color is good.
The present invention is Y under 1250 ℃ of high temperature 2O 3And Gd 2O 3, Y 2O 3, Gd 2O 3And Eu 2O 3Formation have cubic structure (Y, Gd) 2O 3(Y, Gd, Eu) 2O 3Solid solution is that very stable class matter homophase is replaced Solid solution, has good luminescent properties.
Rare earth oxide red fluorescence powder step of preparation process of the present invention is as follows:
1, selects materials
By (Y 1-x-yGd xEu y) 2O 3The chemical expression metering is than the Y that takes by weighing a certain amount of 99.99% purity 2O 3, Gd 2O 3, Eu 2O 3And the above boric acid of purity assay, metal fluoride and metal carbonate in one or more.Wherein, boric acid, metal fluoride and metal carbonate are additives, and metal fluoride can be CaF 2, metal carbonate can be K 2CO 3Or Li 2CO 3The additive add-on is 0.1～0.5wt%.
2, batch mixing
Y with above-mentioned 99.99% purity 2O 3, Gd 2O 3, Eu 2O 3And the above H of purity assay 3BO 3, CaF 2, K 2CO 3, Li 2CO 3In a kind of or one to three kind as raw material, in the ball grinder of packing into, put into agate ball, the weight ratio of ball and raw material is 1: 1, the ball milling time is more than 10 hours.
3, sintering
In the above-mentioned raw materials of ball mill mixing is packed alumina crucible or corundum crucible into, add a cover and put into high temperature sintering furnace.When packing in the alumina crucible, raw material is a room temperature.Raw material in alumina crucible rises to 1250～1400 ℃ with stove, and constant temperature 1～2 hour stops to heat up, and reduces to below 1000 ℃ with stove and takes out.
4, aftertreatment
Above-mentioned raw materials obtains the white powder product through burning till.With the product white powder fragmentation that obtains, in the ball grinder of packing into, add entry and φ 3mm glass sphere, wherein the ratio of product white powder powder, water and glass sphere is: powder: water: ball ≈ 1: 1: 1, ball milling 2～4 hours.Powder behind the ball milling and water become the powder slurry, and powder is starched in the beaker of packing into, use 2%HCl solution stirring 2～4 hours, then are washed till neutrality with 70～80 ℃ of hot deionized waters.Sieve through 400 orders, 110～130 ℃ of oven dry in baking oven obtain fluorescent material behind the suction filtration.The fluorescent material of oven dry is sieved through 260 orders again, and detect, promptly obtain red fluorescence powder of the present invention.
Characteristics of the present invention are: (1) obtains cubic structure (Y at high temperature more than 1250 ℃ 1-x-yGd xEu y) 2O 3Fluorescent material, even Gd content is up to 90% o'clock, i.e. (Y 0.06Gd 0.90Eu 0.04) 2O 3The time, material is a cubic structure still, does not have monocline Gd 2O 3Dephasign exists.As Fig. 1 is (Y 0.06Gd 0.90Eu 0.04) 2O 3The XRD figure of fluorescent material (2 θ=18 °～74 °), this is a typical body-centered cubic structure, and diffraction peak is very strong, and (FWHM) is narrow for the half-breadth height, and the crystal structure quality is good; (2) high temperature that is obtained cube (Y, Gd) 2O 3: the emmission spectrum of Eu fluorescent material and cube Y 2O 3: Eu and cube Gd 2O 3: Eu is identical, as shown in Figure 2; (3) satisfied activator concentration scope is arranged, as shown in Figure 3, optimum concn is 0.04mol; (4) select for use a small amount of boric acid, metal fluoride and metal carbonate as additive, not only reduced calcination temperature, and improve luminosity, promote crystal growth; (5) manufacturing process is simple, easy handling, suitable batch production.
Description of drawings:
Fig. 1 is (Y 0.06Gd 0.90Eu 0.04) 2O 3The XRD figure of fluorescent material (2 θ=18 °～74 °);
Fig. 2 be cube (Y, Gd) 2O 3: Eu, Y 2O 3: Eu, Gd 2O 3: the emmission spectrum figure of Eu fluorescent material;
Fig. 3 is light-emitting phosphor intensity and activator Eu 3+The graph of a relation of concentration.
Embodiment:
Embodiment 1, take by weighing Y 2O 3100g, Eu 2O 37g, BaF 20.1g, H 3BO 30.3g, above-mentioned raw materials is packed in the ball grinder, put into agate ball, the weight ratio of ball and raw material is 1: 1, the ball milling time is more than 10 hours.The material of the mixing corundum crucible of packing into is put into high temperature sintering furnace in the lump, the sintering oven temperature is raised to 1270 ℃, constant temperature 2 hours is treated that furnace temperature is reduced to take out crucible below 1000 ℃ and be cooled to room temperature.The material fragmentation of will coming out of the stove in the ball grinder of packing into, adds entry and φ 3mm glass sphere, powder: water: ball ≈ 1: 1: 1, and ball milling is 2 hours at a slow speed.Powder is starched in the beaker of packing into, used 2-5%HCl solution stirring 2 hours, then be washed till neutrality, sieve 120 ℃ of oven dry in baking oven behind the suction filtration through 400 orders with 70-80 ℃ of hot deionized water.The fluorescent material of oven dry is sieved through 260 orders again, promptly obtain (Y after testing 1-x-yGd xEu y) 2O 3Red-emitting phosphors, relative luminous intensity is 100 under cathode-ray exciting.
Embodiment 2, take by weighing Y 2O 380g, Gd 2O 324g, Eu 2O 36g, BaF 20.1g, H 3BO 30.3g all the other conditions are with embodiment 1, relative luminous intensity is 98 under cathode-ray exciting.
Embodiment 3, take by weighing Y 2O 370g, Gd 2O 322g, Eu 2O 313g, BaF 20.1g, H 3BO 30.3g all the other conditions are with embodiment 1, relative luminous intensity is 87.2 under cathode-ray exciting.
Embodiment 4, take by weighing Y 2O 360g, Gd 2O 344g, Eu 2O 36g, BaF 20.1g, H 3BO 30.3g,, all the other conditions are with embodiment 1, and relative luminous intensity is 102.4 under cathode-ray exciting.
Embodiment 5, take by weighing Y 2O 350g, Gd 2O 339.5g, Eu 2O 311.5g, BaF 20.1g, H 3BO 30.3g all the other conditions are with embodiment 1, relative luminous intensity is 91.6 under cathode-ray exciting.
Embodiment 6, take by weighing Y 2O 340g, Gd 2O 357g, Eu 2O 35g, BaF 20.1g, H 3BO 30.3g,, all the other conditions are with embodiment 1, and relative luminous intensity is 101.6 under cathode-ray exciting.
Embodiment 7, take by weighing Y 2O 340g, Gd 2O 363g, Eu 2O 312g, BaF 20.35g, H 3BO 30.6g all the other conditions are with embodiment 1, relative luminous intensity is 89.8 under cathode-ray exciting.
Embodiment 8, take by weighing Y 2O 320g, Gd 2O 386g, Eu 2O 35g, BaF 20.1g, H 3BO 30.3g all the other conditions are with embodiment 1, relative luminous intensity is 97.3 under cathode-ray exciting.
Embodiment 9, take by weighing Y 2O 320g, Gd 2O 3107g, Eu 2O 313g, BaF 20.4g, H 3BO 30.7g all the other conditions are with embodiment 1, relative luminous intensity is 86.5 under cathode-ray exciting.
Embodiment 10, take by weighing Y 2O 370g, Gd 2O 330g, Eu 2O 36g, BaF 20.1g, H 3BO 30.3g all the other conditions are with embodiment 1, relative luminous intensity is 103.1 under cathode-ray exciting.

Claims (7)

1, a kind of rare earth oxide red fluorescence powder is characterized in that at a cube Y 2O 3: Eu 3+Introduce the Gd ion in the system and make it part replacement Y, Y under 1250 ℃ of high temperature 2O 3And Gd 2O 3And Y 2O 3, Gd 2O 3And Eu 2O 3Formation have cubic structure (Y, Gd) 2O 3(Y, Gd, Eu) 2O 3Solid solution, its chemical expression is: (Y 1-x-yGd xEu y) 2O 3, wherein x is the content of matrix components Gd, and value is 0＜x≤0.9, and y is the content of activator Eu, and value is 0.01≤y≤0.1, also includes additive in the Solid solution.
2, rare earth oxide red fluorescence powder according to claim 1, it is characterized in that the additive that is comprised be in boric acid, metal fluoride, the metal carbonate one or more.
3, rare earth oxide red fluorescence powder according to claim 2 is characterized in that the additive metal fluorochemical is CaF 2, metal carbonate is K 2CO 3Or Li 2CO 3
4, rare earth oxide red fluorescence powder according to claim 3 is characterized in that the additive add-on is 0.1-0.5wt%.
5, the preparation method of rare earth oxide red fluorescence powder according to claim 1, include select materials, batch mixing, sintering and last handling process, it is characterized in that by (Y 1-x-yGd xEu y) 2O 3The chemical expression metering is than the Y that takes by weighing a certain amount of 99.99% purity 2O 3, Gd 2O 3, Eu 2O 3And the above additive of purity assay; With above-mentioned Y 2O 3, Gd 2O 3, Eu 2O 3And additive packs in the ball grinder, puts into agate ball, ball mill mixing; Raw material behind the ball mill mixing is packed in alumina crucible or the corundum crucible, add a cover and put into the high temperature sintering furnace sintering; The white powder product fragmentation that sintering is obtained, pack in the ball grinder, add entry and φ 3mm glass sphere, powder behind the ball milling and water become the powder slurry, and powder is starched in the beaker of packing into, use 2%HCl solution stirring 2～4 hours, then be washed till neutrality with 70～80 ℃ of hot deionized waters, sieve through 400 orders, 110～130 ℃ of oven dry in baking oven obtain fluorescent material behind the suction filtration.
6, the preparation method of rare earth oxide red fluorescence powder according to claim 5 is characterized in that the agate ball that batch mixing is used and the weight ratio of raw material are 1: 1, and the ball milling time is more than 10 hours; Under the room temperature batch mixing is packed in the alumina crucible, rise to 1250～1400 ℃ with stove, constant temperature 1～2 hour stops to heat up, and reduces to below 1000 ℃ with stove and takes out; White powder product in the aftertreatment: water: glass sphere ≈ 1: 1: 1.
7, the preparation method of rare earth oxide red fluorescence powder according to claim 5 is characterized in that the fluorescent material of oven dry is sieved through 260 orders again.
CN 02144731 2002-12-07 2002-12-07 Red RE oxide luminophor and its prepn Expired - Fee Related CN1212367C (en)

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CN1331982C (en) * 2004-10-11 2007-08-15 北京有色金属研究总院 Phosphor powder of composite oxide in use for white light LED and fabricated electric light source
CN100540629C (en) * 2007-11-12 2009-09-16 中国科学院长春光学精密机械与物理研究所 Near ultraviolet or blue-light excited red fluorescence powder and preparation method thereof
CN100575451C (en) * 2008-01-24 2009-12-30 同济大学 A kind of red nano-fluorescent powder and preparation method thereof
CN102888223A (en) * 2012-09-07 2013-01-23 彩虹集团电子股份有限公司 Manufacture method for red fluorescent powder for three-primary-color energy saving lamp

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