CN103484112B - Rare-earth europium-activated single-component white-light fluorescent powder and preparation method thereof - Google Patents
Rare-earth europium-activated single-component white-light fluorescent powder and preparation method thereof Download PDFInfo
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- CN103484112B CN103484112B CN201310397729.2A CN201310397729A CN103484112B CN 103484112 B CN103484112 B CN 103484112B CN 201310397729 A CN201310397729 A CN 201310397729A CN 103484112 B CN103484112 B CN 103484112B
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Abstract
The invention discloses a rare-earth europium-activated single-component white-light fluorescent powder and a preparation method thereof. The chemical formula of the fluorescent powder is (Ca1-xEux)Zr(PO4)2 (0.005<=x<=0.10). The preparation method adopts a two-step solid-phase synthesis method in air, and comprises the following steps: 1. uniformly grinding and mixing CaCO3, ZrO2 and Eu2O3 used as raw materials, and igniting at the high temperature of 1100-1400 DEG C for 1-4 hours to prepare (Ca1-xEux)ZrO3; and 2. uniformly grinding and mixing the (Ca1-xEux)ZrO3 with a right amount of NH4H2PO4 or (NH4)2HPO4 or (NH4)3PO4, and igniting at the high temperature of 1100-1300 DEG C for 3-24 hours to synthesize the end product (Ca1-xEux)Zr(PO4)2. The obtained sample can emit white light under the 200-350nm ultraviolet irradiation, has wide light-emitting color range, and can cover the whole visible light wave range. By utilizing the characteristics of the fluorescent material matrix compound CaZr(PO4)2 in the crystal structure, the Eu<2+>/Eu<3+>-coactivated CaZr(PO4)2 white-light fluorescent material can be prepared in air without multiple rare earth ions or use of a reducing atmosphere. The preparation method is simple and safe, and is easy to operate and low in production cost.
Description
Technical field
The invention belongs to rare earth luminescent material field, relate in particular to europkium-activated single component white light fluorescent powder of a kind of rare earth and preparation method thereof.
Background technology
1973, Dutch Philips company proposed the phosphor of rare earth technology, the Y that is about to glow at first
2o
3: Eu
3+, green light CeMgAl
11o
19: Tb
3+baMgAl with blue light-emitting
10o
17: Eu
2+three kinds of fluorescent RE powders mix by a certain percentage, under the exciting of UV-light, send white light.Rare-earth trichromatic fluorescent powder, because of its advantage that possesses high light efficiency and specular simultaneously, is regarded as the advanced luminescent material of green energy conservation and is rapidly developed, and progressively substitutes the incandescent light of high energy consumption poor efficiency, becomes the extremely important lamp phosphor of lighting field.Yet white emitting fluorescent powder conventionally need to be modulated and form in proportion by the red, green, blue three primary colors fluorescent powder that contains different rare earths, modulation technique requires high, modulation process is loaded down with trivial details, and after multiple fluor doping, complex chemical composition, can affect the overall luminescent properties of white luminophor; Meanwhile, three primary colors fluorescent powder synthesis technique is different, and each fluorescent material all needs independent preparation, and preparation process is complicated; In addition Eu,
2+ion-activated fluorescent material, as BaMgAl
10o
17: Eu
2+, conventionally need to adopt any special measures such as reducing atmosphere to make complicated process of preparation, the higher and poor stability of cost.Therefore, the single component white light fluorescent powder of a kind of single rare earth doping that can prepare in air ambient of exploration exploitation has important scientific value and social benefit.
Summary of the invention
The object of the invention is to overcome problems of the prior art, a kind of europkium-activated single component white light fluorescent powder of rare earth of preparing under air ambient and preparation method thereof is provided, the method technological process simply, does not need reducing atmosphere, high-efficiency environment friendly.
The present invention utilizes phosphor host CaZr (PO
4)
2the feature of self three-dimensional netted crystalline structure, in air through high-temperature calcination, can be by part Eu
3+automatic reduction is Eu
2+, preparation Eu
2+and Eu
3+coactivated CaZr (PO
4)
2fluorescent material.This material under UV-irradiation, the Eu in substrate material
2+send the blue green light of 375～575nm, Eu
3+send the orange red light of 575～725nm, the Eu of suitable proportion
2+and Eu
3+two kinds of ion coexists can form white light emission.
To achieve these goals, the present invention realizes by the following technical solutions:
The europkium-activated single component white light fluorescent powder of rare earth of the present invention is Eu
2+and Eu
3+coactivated CaZr (PO
4)
2fluorescent material, its chemical constitution formula is (Ca
1-xeu
x) Zr (PO
4)
2, 0.005≤x≤0.10 wherein.
The preparation method of the europkium-activated single component white light fluorescent powder of rare earth of the present invention, adopts two step solid-phase synthesis, comprises following processing step:
(1) preparation (Ca
1-xeu
x) ZrO
3: by element chemistry, measure than taking raw materials of Ca CO
3(analytical pure), ZrO
2(analytical pure) and Eu
2o
3(99.9%), ground be mixed even after calcination 1～4 hour at 1100～1400 ℃ in air;
(2) synthetic (Ca
1-xeu
x) Zr (PO
4)
2: by cooled step (1) product and appropriate NH
4h
2pO
4or (NH
4)
2hPO
4or (NH
4)
3pO
4(analytical pure) is ground, calcination 3～24 hours at 1000～1300 ℃ in air;
(3) cooled step (2) product is pulverized, ground, obtain europkium-activated single component white light fluorescent powder.
Fluorescent material prepared by the present invention can emitting bright under uviolizing white light.Compared with prior art have the following advantages:
(1) this white emitting fluorescent powder is only by the substrate material CaZr (PO of single component
4)
2form with a small amount of rare earth element Eu, do not need multiple fluorescent material allotment.
(2) substrate material CaZr (PO
4)
2physicochemical property are stable, and Constitution Elements Ca, Zr, P, O are the tellurian element that is rich in, cheap being easy to get.
(3) in material preparation process, do not need to pass into any reducing gas, in air, calcining can realize part Eu
3+reduction, preparation cost is low, safe, simple to operation.
(4) the europkium-activated single component white light fluorescent powder excitation wavelength range of rare earth that the present invention makes is wide, is 200～350nm UV-light wave band; Illuminant colour field width, emission wavelength ranges is 375～725nm, covers whole visible light wave ranges.
Accompanying drawing explanation
Fig. 1 is CaZr (PO
4)
2powdery diffractometry standard card (35-0159) and embodiment 1 product (Ca
0.98eu
0.02) Zr (PO
4)
2x-ray powder diffraction figure.
Fig. 2 is embodiment 1 product (Ca
0.98eu
0.02) Zr (PO
4)
2exciting light spectrogram (λ
em=475nm).
Fig. 3 is the embodiment of the present invention 1 product (Ca
0.98eu
0.02) Zr (PO
4)
2emmission spectrum (λ
ex=254nm).
Fig. 4 is the embodiment of the present invention 1 product (Ca
0.98eu
0.02) Zr (PO
4)
2chromaticity coordinates figure.
Specific embodiments
Below by particular specific embodiment, also the present invention will be described in more detail by reference to the accompanying drawings.Should be understood that one or more method stepss that the present invention mentions do not repel before and after described combination step also there is other method steps, or can also insert other method steps before the step of clearly mentioning at these; Should also be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.And, except as otherwise noted, the numbering of various method steps is only for differentiating the convenient tool of various method steps, but not for limiting the ordering of various method steps or limiting the enforceable scope of the present invention, the change of its relativeness or adjustment, without essence change technology contents in the situation that, when being also considered as the enforceable category of the present invention.
Embodiment 1
Take raw materials of Ca CO
39.828g, Eu
2o
30.352g, ZrO
212.347g, CaCO wherein
3and ZrO
2for analytical pure, Eu
2o
3purity is 99.9%.Raw material is put into agate mortar, after adding appropriate dehydrated alcohol fully to grind, put into corundum crucible, be placed in process furnace, carry out first calcination under atmospheric environment, calcination temperature is 1300 ℃, and the reaction times is 3 hours, naturally cools to room temperature after reaction.The product that the first step is made and 23.052g NH
4h
2pO
4(analytical pure) puts into agate mortar, packs corundum crucible into after adding appropriate dehydrated alcohol to be ground, and carries out secondary calcination under atmospheric environment, and calcination temperature is 1200 ℃, and the reaction times is 6 hours.After having reacted, take out sample after naturally cooling to room temperature with stove, through pulverizing, grinding, obtain the europkium-activated single component white light fluorescent powder (Ca of rare earth
0.98eu
0.02) Zr (PO
4)
2.
Products obtained therefrom outward appearance is white in color, X-ray diffraction peak data and CaZr (PO
4)
2the diffraction data of PDF standard card #35-0159 consistent, as shown in Figure 1.As shown in Figure 2, its excitation wavelength range is wide, contains 200～350nm UV-light wave band for the excitation spectrum of monitoring 475nm emission wavelength.Fig. 3 is the emmission spectrum under 254nm ultraviolet excitation, and emission wavelength ranges is 375～725nm, covers whole visible light wave ranges.Wherein, the broadband emission of 375～575nm (being blue-greenish colour) is the Eu in substrate material
2+luminous, the spike transmitting (being orange red) of 575～725nm is the Eu in substrate material
3+luminous, Eu
2+and Eu
3+luminous through spontaneous colour mixture generation white light emission.Fig. 4 is the chromaticity coordinates figure of the present embodiment product, and the luminous chromaticity coordinates of this product is (0.305,0.290), very approaching with the chromaticity coordinates (0.33,0.33) of standard white light.
Embodiment 2
Take raw materials of Ca CO
39.728g, Eu
2o
30.528g, ZrO
212.347g, CaCO wherein
3and ZrO
2for analytical pure, Eu
2o
3purity is 99.9%.Raw material is put into agate mortar, after adding appropriate dehydrated alcohol fully to grind, put into corundum crucible, be placed in process furnace, carry out first calcination under atmospheric environment, calcination temperature is 1250 ℃, and the reaction times is 2 hours, naturally cools to room temperature after reaction.The product that the first step is made and 23.052g NH
4h
2pO
4(analytical pure) puts into agate mortar, packs corundum crucible into after adding appropriate dehydrated alcohol to be ground, and carries out secondary calcination under atmospheric environment, and calcination temperature is 1100 ℃, and the reaction times is 10 hours.After having reacted, take out sample after naturally cooling to room temperature with stove, through pulverizing, grinding, obtain the europkium-activated single component white light fluorescent powder (Ca of rare earth
0.97eu
0.03) Zr (PO
4)
2.Products obtained therefrom outward appearance is white in color, X-ray diffraction peak data and CaZr (PO
4)
2the diffraction data of PDF standard card #35-0159 consistent.Products obtained therefrom sends bright white light under 254nm UV-irradiation, and emission wavelength ranges is 375～725nm, covers whole visible light wave ranges.
Embodiment 3
Take raw materials of Ca CO
39.628g, Eu
2o
30.705g, ZrO
212.347g, CaCO wherein
3and ZrO
2for analytical pure, Eu
2o
3purity is 99.9%.Raw material is put into agate mortar, after adding appropriate dehydrated alcohol fully to grind, put into corundum crucible, be placed in process furnace, carry out first calcination under atmospheric environment, calcination temperature is 1200 ℃, and the reaction times is 4 hours, naturally cools to room temperature after reaction.The product that the first step is made and 23.052gNH
4h
2pO
4(analytical pure) puts into agate mortar, packs corundum crucible into after adding appropriate dehydrated alcohol to be ground, and carries out secondary calcination under atmospheric environment, and calcination temperature is 1100 ℃, and the reaction times is 24 hours.After having reacted, take out sample after naturally cooling to room temperature with stove, through pulverizing, grinding, obtain the europkium-activated single component white light fluorescent powder (Ca of rare earth
0.96eu
0.04) Zr (PO
4)
2.Products obtained therefrom outward appearance is white in color, X-ray diffraction peak data and CaZr (PO
4)
2the diffraction data of PDF standard card #35-0159 consistent.Products obtained therefrom sends bright white light under 254nm UV-irradiation, and emission wavelength ranges is 375～725nm, covers whole visible light wave ranges.
Embodiment 4
Take raw materials of Ca CO
39.227g, Eu
2o
31.409g, ZrO
212.344g, CaCO wherein
3and ZrO
2for analytical pure, Eu
2o
3purity is 99.9%.Raw material is put into agate mortar, after adding appropriate dehydrated alcohol fully to grind, put into corundum crucible, be placed in process furnace, carry out first calcination under atmospheric environment, calcination temperature is 1400 ℃, and the reaction times is 1 hour, naturally cools to room temperature after reaction.The product that the first step is made and 23.052gNH
4h
2pO
4(analytical pure) puts into agate mortar, packs corundum crucible into after adding appropriate dehydrated alcohol to be ground, and carries out secondary calcination under atmospheric environment, and calcination temperature is 1250 ℃, and the reaction times is 16 hours.After having reacted, take out sample after naturally cooling to room temperature with stove, through pulverizing, grinding, obtain the europkium-activated single component white light fluorescent powder (Ca of rare earth
0.92eu
0.08) Zr (PO
4)
2.Products obtained therefrom outward appearance is white in color, X-ray diffraction peak data and CaZr (PO
4)
2the diffraction data of PDF standard card #35-0159 consistent.Products obtained therefrom sends bright white light under 254nm UV-irradiation, and emission wavelength ranges is 375～725nm, covers whole visible light wave ranges.
The above; be only explanation embodiment of the present invention; not to any formal and substantial restriction of the present invention; should be understood that; for those skilled in the art; do not departing under the prerequisite of the inventive method some improvement of making and supplement and also should be considered as protection scope of the present invention.All those skilled in the art, without departing from the spirit and scope of the present invention, utilize a little change that disclosed above technology contents makes, modify the equivalent variations with differentiation, are equivalent embodiment of the present invention; , the change of any equivalent variations that all foundations essence technology of the present invention is done above-described embodiment, modify and differentiation meanwhile, all still belong to the scope of technical scheme of the present invention.
Claims (1)
1. the europkium-activated single component white light fluorescent powder of rare earth, is characterized in that, this fluorescent material is the Eu preparing under air atmosphere
2+and Eu
3+co-activation CaZr (PO
4)
2single component white light fluorescent material, its chemical constitution formula is (Ca
1-xeu
x) Zr (PO
4)
2, 0.005≤x≤0.025 wherein; This fluorescent material can emitting bright under the UV-irradiation of 200～350nm white light, its emission wavelength ranges is 375～725nm, cover whole visible light wave ranges, can be used as the white light emitting material of photodiode, display device, three-color fluorescent lamp and Field Emission Display.
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| CN104388085B (en) * | 2014-11-26 | 2016-06-29 | 中国计量学院 | A kind of white light LEDs phosphate orange fluorescent powder and preparation method thereof |
| CN105131952A (en) * | 2015-09-19 | 2015-12-09 | 青岛科技大学 | Color-adjustable LED fluorescent powder and preparation method thereof |
| CN105219382B (en) * | 2015-10-10 | 2017-05-31 | 广西师范学院 | Eu2+ Eu3+ codope fluoaluminate substrate fluorescent powders and its synthetic method and application |
| CN105670623B (en) * | 2015-12-31 | 2017-09-26 | 中南大学 | One kind is based on blue white light conversion phosphor and its preparation under ultraviolet excitation |
| CN111434749B (en) * | 2019-01-11 | 2021-05-04 | 厦门大学 | Near-ultraviolet excited warm white light fluorescent powder and preparation method and application thereof |
| CN112391165A (en) * | 2020-10-30 | 2021-02-23 | 新沂市锡沂高新材料产业技术研究院有限公司 | Preparation method of CaZr (PO4) 2-based fluorescent conversion material with high thermal stability |
| CN114316983B (en) * | 2021-12-29 | 2023-07-07 | 淮北师范大学 | Barium zirconium phosphate fluorescent matrix material and preparation method and application thereof |
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