CN102660263A - Eu<2+>-activated chorine calcium silicate salt fluorescent powder and preparation method and application thereof - Google Patents
Eu<2+>-activated chorine calcium silicate salt fluorescent powder and preparation method and application thereof Download PDFInfo
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- CN102660263A CN102660263A CN2012101363357A CN201210136335A CN102660263A CN 102660263 A CN102660263 A CN 102660263A CN 2012101363357 A CN2012101363357 A CN 2012101363357A CN 201210136335 A CN201210136335 A CN 201210136335A CN 102660263 A CN102660263 A CN 102660263A
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Abstract
The invention relates to Eu<2+>-activated chorine calcium silicate salt fluorescent powder and a preparation method and an application thereof, which belong to the technical field of organic luminescent materials. The chemical formula of the fluorescent powder is Ca10-xEuxSi6O21Cl2, wherein x is more than or equal to 0.0001 and is less than or equal to 5. The Eu<2+>-activated chorine calcium silicate salt fluorescent powder emits bright green fluorescent light under the activation of near ultraviolet light of 350-400 nanometers, has high luminescent intensity, wide excitation wavelength, high stability and high color rendering property, and is matched with the emitting wavelength of a near ultraviolet semiconductor chip. The preparation method adopted in the invention is simple and has high repeatability; and an obtained product has stable quality, and is easy for operation and industrial production.
Description
Technical field
The present invention relates to a kind of Eu
2+Luminous, the preparation method of activated chlorine Calucium Silicate powder and application belong to the phosphor technical field.
Background technology
White light LEDs has energy-conserving and environment-protective, highly effective and safe, firm advantage such as reliable, is following light source of new generation, is containing huge economic benefit and social benefit.Along with (closely) ultraviolet LED chip technology constantly develops, what the exploitation exploration was novel can have important Research Significance and practical value with three primary colors fluorescent powder at the LED that near-ultraviolet light effectively excites.The excitation spectrum of this type fluorescent material should be complementary with the emmission spectrum of ultraviolet LED chip, and requirement can produce the VISIBLE LIGHT EMISSION that satisfies the white light requirement under the exciting of (closely) UV-light, have higher light energy use efficiency; Fluorescent material should have better physical stability, chemicalstability and good anti-damp moisture resistance simultaneously, can not react with packaged material, semi-conductor chip; Fluorescent material needs to bear long-time ultraviolet photon bombardment; The phosphor particle size is even respectively, and particle diameter generally is in micron or submicron rank below 8 microns, is fit to the practicability of fluorescent material powder.
Silicate substrate fluorescent material has good research and practical application foreground because chemical property and physical properties are more stable, paid close attention to by the investigator, is a kind of good white light LEDs luminous host.At first, the zwitterion major part of silicate combines silicon-oxy tetrahedron [SiO with the ionic linkage that has than the strong covalent bond characteristic
4]
4-Connect through being total to push up, different arranging situations is arranged, form island, isolated ring-type, continuous chain, continuous stratiform and five kinds of different structures of three-dimensional framework, have excellent chemical stability and thermostability, crystal property and light transmission.In addition, the silicate substrate phosphor raw material is rich and easy to get, and is cheap, and sintering temperature is lower than aluminate substrate fluorescent powder, and synthesis technique flexibility is extensive, can effectively reduce cost.The green silicate substrate fluorescent powder that can under (closely) ultraviolet, effectively excite of development of new will promote the development of LED lighting engineering, and will be significant.
At present, the ion-activated silicate luminescent material of rare earth ion or transition metal has obtained many investigators' concern.Like Chinese invention patent (CN102191057A) " a kind of method of optimizing silicate green fluorescent powder material crystalline form ", it is the green emitting phosphor of matrix that a kind of silicate is provided, prescription adopt chemical formula be (Ba, A)
1-xSiO
4: xEu, 0＜x＜1.0 wherein, A is Ca or Sr element; The low-temperature synthetic method of the disclosed a kind of silicate green fluorescent powder of Chinese invention patent (CN101805607A), it is aCaO-Mg-2SiO that prescription adopts chemical general formula
2-bCaCl
2: xEu, 1.6≤a≤2,1≤b≤3,0.01≤x, 0.07; Chinese invention patent (CN1788069A) is disclosed to be a kind of light-emitting device that contains silicate fluorescent phosphors, and it is Sr that prescription adopts chemical formula
xBa
yCa
zSiO
4: Eu, wherein, x, y and z are the numerical value between about 0-2 independently of one another, what do not add restriction comprises 0.001 and 2.
At present, with Eu
2+The green fluorescence powder of activated chlorine Calucium Silicate powder appears in the newspapers.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists; Provide a kind of percent crystallinity high; Luminous intensity and luminous efficiency height, excitation wave length and width, stability and color developing are good; Raw materials cost is cheap, and preparation technology is simple, is easy to chlorine calsil fluorescent material, preparation method and the application thereof of suitability for industrialized production.
For reaching the foregoing invention purpose, the technical scheme that the present invention adopts provides a kind of chlorine calsil fluorescent material, and its chemical formula is Ca
10-xEu
xSi
6O
21Cl
2, wherein, 0.0001＜x≤5; It is by bivalent rare earth ion europium ion Eu
2+Activate, under 350～400nm near ultraviolet excitation, send bright green glow.
A kind of method of chlorine calsil fluorescent material adopts the solid state sintering synthesis method, comprises the steps:
(1) presses chemical formula Ca
10-xEu
xSi
6O
21Cl
2In the stoichiometric ratio of each element, wherein 0.0001＜x≤5 take by weighing respectively and contain calcium ion Ca
2+Compound, contain europium ion Eu
3+Compound, contain silicon ion Si
4+Compound, contain cl ions Cl
-Compound, grind and mix and obtain mixture;
(2) mixture is calcined under air atmosphere, calcining temperature is 300～1000 ℃, and calcination time is 1～10 hour, repeats this step 0～3 time;
(3) the mixture naturally cooling that step (2) is obtained after grinding and mixing, is calcined in reducing atmosphere, and calcining temperature is 1100～1500 ℃, and calcination time is 1～10 hour, obtains a kind of green emitting phosphor.
Described calcium ions Ca
2+Compound be a kind of in quicklime, lime carbonate, calcium hydroxide, nitrocalcite, calcium sulfate, the caoxalate, or their arbitrary combination;
The described europium ion Eu that contains
3+Compound be europium sesquioxide, europium nitrate, oxalic acid europium and Eu
3+Organic complex in a kind of, or their arbitrary combination;
The described silicon Si that contains
4+Compound be a kind of in silicon-dioxide, silicic acid, the tetraethoxy, or their arbitrary combination.
The described chlorine Cl that contains
-Compound be a kind of in ammonium chloride, hydrochloric acid, hypochlorous acid, the calcium chloride, or their arbitrary combination.
The calcining temperature of step (2) is 350～950 ℃, and calcination time is 2～9 hours.
The calcining temperature of step (3) is 1150～1450 ℃, and calcination time is 2～9 hours.
The reducing atmosphere of step (3) is a kind of in following three kinds of atmosphere, or their arbitrary combination:
(1) hydrogen, or the volume ratio of hydrogen and nitrogen is the mixed gas of 1:0.2～85;
(2) CO gas;
(3) carbon granules or various gac are at air: the gas that middle burning is produced.
A kind of application of chlorine calsil fluorescent material cooperates it with suitable blueness and red fluorescence powder, applies and is packaged in outside the InGaN diode, preparation White-light LED illumination device.
Compared with prior art, the remarkable advantage of technical scheme of the present invention is:
1. the substrate material that technical scheme of the present invention provides be easy to realize the reduction of the divalence of rare earth ion, and the bivalent rare earth ion can stable existence among this matrix.(light that 350～400nm) radiating InGaN tube cores excite matches its excitation area, therefore, can be applied near ultraviolet (in the LED fluorescent material that 350～400nm) radiating InGaN tube cores excite with the near ultraviolet of using at present.
2. the fluorescent material that makes has good luminous intensity, stability, color developing and granularity, helps realizing the high-power LED of preparation.
3. the CIE coordinate of the fluorescent material that makes is x=0.0818, and y=0.8152 sends green light under ultraviolet excitation, cooperates blueness and red fluorescence powder can prepare white light LEDs.
Description of drawings
Fig. 1 is the X-ray powder diffraction collection of illustrative plates and the standard card PDF#48-0827 (Ca of the material sample of embodiment of the invention preparation
10Si
6O
21Cl
2) comparison;
Fig. 2 is that the material sample of embodiment of the invention preparation excites the emmission spectrum figure that obtains down at 400nm;
Fig. 3 is the material sample excitation spectrum under 535nm respectively of embodiment of the invention preparation;
Fig. 4 is that the material sample of embodiment of the invention preparation excites the decay of luminescence figure that obtains down at 535nm.
Embodiment
Below in conjunction with accompanying drawing and embodiment technical scheme of the present invention is further described.
Embodiment 1
According to chemical formula Ca
9.5Eu
0.5Si
6O
21Cl
2In the stoichiometric ratio of each element, take by weighing CaCl respectively
2: 0.2775 gram, Eu
2O
3: 0.22 gram, CaCO
3: 1.875 grams, SiO
2: 0.902 gram.After they are ground in agate mortar and mix, select air atmosphere to calcine for the first time, temperature is 650 ℃, and calcination time 2 hours is chilled to room temperature then, takes out sample.After first time incinerating raw material, grind the compound thorough mixing evenly once more, among reducing atmosphere, 1250 ℃ of sintering for the second time down, sintering time is 7 hours, cooling causes room temperature and promptly obtains title product.
Referring to accompanying drawing 1, it is X-ray powder diffraction collection of illustrative plates and standard card PDF#48-0827 (Ca by the material sample of present embodiment technical scheme preparation
10Si
6O
21Cl
2) comparison.The XRD test result shows that prepared material is pure phase material.
Referring to accompanying drawing 2; Can find out the emmission spectrum figure that under near ultraviolet excitated, obtains the material sample monitoring 400nm for preparing by the present invention's technology; Emission peak is a broadband; Main peak is positioned near the 500nm, under ultraviolet excitation, sends green light, cooperates blueness and red fluorescence powder can prepare white light LEDs.
Referring to accompanying drawing 3, from finding out that to monitoring the exciting light spectrogram that obtains under the 535nm excitation peak is asymmetric broadband by the material sample of the present invention's technology preparation.
Referring to accompanying drawing 4, it is the decay of luminescence figure of material sample under 535nm by the preparation of present embodiment technical scheme.
Embodiment 2
According to chemical formula Ca
9Eu
1Si
6O
21Cl
2In the stoichiometric ratio of each element, take by weighing NH respectively
4The Cl:0.267 gram, Eu
2O
3: 0.44 gram, CaCO
3: 2.25 grams, SiO
2: 0.902 gram.After in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 800 ℃, and calcination time 1.5 hours is chilled to room temperature then, takes out sample.After first time incinerating raw material, grind the compound thorough mixing evenly once more, among reducing atmosphere, 1300 ℃ of sintering for the second time down, sintering time is 6 hours, cooling causes room temperature and promptly obtains title product.Main structure properties, excitation spectrum, emmission spectrum are similar with embodiment 1.
Embodiment 3
According to chemical formula Ca
8.5Eu
1.5Si
6O
21Cl
2In the stoichiometric ratio of each element, take by weighing NH respectively
4The Cl:0.267 gram, Eu
2O
3: 0.66 gram, Ca (NO
3)
24H
2The O:5.018 gram, SiO
2: 0.902 gram.After in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 550 ℃, and calcination time 4 hours is chilled to room temperature then, takes out sample.After first time incinerating raw material, grind the compound thorough mixing evenly once more, among reducing atmosphere, 1300 ℃ of sintering for the second time down, sintering time is 8 hours, cooling causes room temperature and promptly obtains title product.Main structure properties, excitation spectrum, emmission spectrum are similar with embodiment 1.
Embodiment 4
According to chemical formula Ca
8Eu
2Si
6O
21Cl
2In the stoichiometric ratio of each element, take by weighing NH respectively
4The Cl:0.267 gram, Eu
2O
3: 0.88 gram, CaCO
3: 2.002 grams, SiO
2: 0.902 gram.After in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, calcining temperature is 950 ℃, and calcination time 2.5 hours is chilled to room temperature then, takes out sample.After first time incinerating raw material, grind the compound thorough mixing evenly once more, among reducing atmosphere, 1300 ℃ of sintering for the second time down, sintering time is 7 hours, cooling causes room temperature and promptly obtains title product.Main structure properties, excitation spectrum, emmission spectrum are similar with embodiment 1.
Embodiment 5
According to chemical formula Ca
7.5Eu
2.5Si
6O
21Cl
2In the stoichiometric ratio of each element, take by weighing CaCl respectively
2: 0.2775 gram, Eu
2O
3: 1.1 grams, CaCO
3: 1.376 grams, SiO
2: 0.902 gram.After in agate mortar, grinding and mixing, calcining for the first time among the air atmosphere, temperature is 600 ℃, calcination time 6 hours is chilled to room temperature then, takes out sample.Grind the compound thorough mixing evenly once more, among reducing atmosphere, 1250 ℃ of sintering for the second time down, sintering time is 9 hours, cooling causes room temperature, promptly obtains title product.Main structure properties, excitation spectrum, emmission spectrum are similar with embodiment 1.
Embodiment 6
According to chemical formula Ca
7Eu
3Si
6O
21Cl
2In the stoichiometric ratio of each element, take by weighing CaCl respectively
2: 0.2775 gram, Eu
2O
3: 1.32 grams, Ca (NO
3)
24H
2The O:2.95 gram, SiO
2: 0.902 gram.After in agate mortar, grinding and mixing, calcining for the first time among the air atmosphere, temperature is 750 ℃, calcination time 5 hours is chilled to room temperature then, takes out sample.Grind the compound thorough mixing evenly once more, among reducing atmosphere, 1300 ℃ of sintering for the second time down, sintering time is 8 hours, cooling causes room temperature, promptly obtains title product.Main structure properties, excitation spectrum, luminescent spectrum are similar with embodiment 1.
Embodiment 7
According to chemical formula Ca
6.5Eu
3.5Si
6O
21Cl
2In the stoichiometric ratio of each element, take by weighing NH respectively
4The Cl:0.267 gram, Eu
2O
3: 1.54 grams, CaCO
3: 1.126 grams, SiO
2: 0.902 gram.After in agate mortar, grinding and mixing, calcining for the first time among the air atmosphere, temperature is 750 ℃, calcination time 5 hours is chilled to room temperature then, takes out sample.Grind the compound thorough mixing evenly once more, among reducing atmosphere, 1400 ℃ of sintering for the second time down, sintering time is 7 hours, cooling causes room temperature, promptly obtains title product.Main structure properties, excitation spectrum, emmission spectrum are similar with embodiment 1.
Claims (10)
1. chlorine calsil fluorescent material, it is characterized in that: its chemical formula is Ca
10-xEu
xSi
6O
21Cl
2, wherein, 0.0001＜x≤5; It is by bivalent rare earth ion europium ion Eu
2+Activate, under 350～400nm near ultraviolet excitation, send bright green glow.
2. a method for preparing chlorine calsil fluorescent material as claimed in claim 1 adopts the solid state sintering synthesis method, it is characterized in that comprising the steps:
(1) presses chemical formula Ca
10-xEu
xSi
6O
21Cl
2In the stoichiometric ratio of each element, wherein 0.0001＜x≤5 take by weighing respectively and contain calcium ion Ca
2+Compound, contain europium ion Eu
3+Compound, contain silicon ion Si
4+Compound, contain cl ions Cl
-Compound, grind and mix and obtain mixture;
(2) mixture is calcined under air atmosphere, calcining temperature is 300～1000 ℃, and calcination time is 1～10 hour, repeats this step 0～3 time;
(3) the mixture naturally cooling that step (2) is obtained after grinding and mixing, is calcined in reducing atmosphere, and calcining temperature is 1100～1500 ℃, and calcination time is 1～10 hour, obtains a kind of green emitting phosphor.
3. the preparation method of a kind of chlorine calsil fluorescent material according to claim 2 is characterized in that: described calcium ions Ca
2+Compound be a kind of in quicklime, lime carbonate, calcium hydroxide, nitrocalcite, calcium sulfate, the caoxalate, or their arbitrary combination.
4. the preparation method of a kind of chlorine calsil fluorescent material according to claim 2 is characterized in that: the described europium ion Eu that contains
3+Compound be europium sesquioxide, europium nitrate, oxalic acid europium and Eu
3+Organic complex in a kind of, or their arbitrary combination.
5. the preparation method of a kind of chlorine calsil fluorescent material according to claim 2 is characterized in that: the described silicon Si that contains
4+Compound be a kind of in silicon-dioxide, silicic acid, the tetraethoxy, or their arbitrary combination.
6. the preparation method of a kind of chlorine calsil fluorescent material according to claim 2 is characterized in that: the described chlorine Cl that contains
-Compound be a kind of in ammonium chloride, hydrochloric acid, hypochlorous acid, the calcium chloride, or their arbitrary combination.
7. the preparation method of a kind of chlorine calsil fluorescent material according to claim 2 is characterized in that: the calcining temperature of step (2) is 350～950 ℃, and calcination time is 2～9 hours.
8. the preparation method of a kind of chlorine calsil fluorescent material according to claim 2 is characterized in that: the calcining temperature of step (3) is 1150～1450 ℃, and calcination time is 2～9 hours.
9. the preparation of a kind of chlorine calsil fluorescent material according to claim 2 is characterized in that: the reducing atmosphere of step (3) is a kind of in following three kinds of atmosphere, or their arbitrary combination:
(1) hydrogen, or the volume ratio of hydrogen and nitrogen is the mixed gas of 1:0.2～85;
(2) CO gas;
(3) carbon granules or various gac are at air: the gas that middle burning is produced.
10. the application of a chlorine calsil fluorescent material as claimed in claim 1 is characterized in that: it is cooperated suitable blueness and red fluorescence powder, apply and be packaged in outside the InGaN diode, preparation White-light LED illumination device.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173225A (en) * | 2013-04-03 | 2013-06-26 | 苏州大学 | Blue fluosilicate fluorescent powder as well as preparation method and application |
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| CN101605867A (en) * | 2006-10-03 | 2009-12-16 | 渲染材料公司 | Metal silicate halide phosphors and the LED illuminating device that uses them |
| WO2011156971A1 (en) * | 2010-06-18 | 2011-12-22 | 海洋王照明科技股份有限公司 | Halosilicate luminescent materials and preparation methods and uses thereof |
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2012
- 2012-05-04 CN CN2012101363357A patent/CN102660263A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101336279A (en) * | 2005-12-02 | 2008-12-31 | 沙诺夫公司 | Metal silicate halide phosphors and led lighting devices using the same |
| CN101605867A (en) * | 2006-10-03 | 2009-12-16 | 渲染材料公司 | Metal silicate halide phosphors and the LED illuminating device that uses them |
| WO2011156971A1 (en) * | 2010-06-18 | 2011-12-22 | 海洋王照明科技股份有限公司 | Halosilicate luminescent materials and preparation methods and uses thereof |
Non-Patent Citations (3)
| Title |
|---|
| 宁青菊，等: "Ca10(Si2O7)3Cl2∶Eu3+荧光粉的发光特性研究", 《电子元件与材料》, vol. 31, no. 2, 31 January 2012 (2012-01-31), pages 55 - 58 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173225A (en) * | 2013-04-03 | 2013-06-26 | 苏州大学 | Blue fluosilicate fluorescent powder as well as preparation method and application |
| CN103173225B (en) * | 2013-04-03 | 2014-07-16 | 苏州大学 | Blue fluosilicate fluorescent powder as well as preparation method and application |
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Application publication date: 20120912 |