CN101698799B - Method for preparing porous spherical CaSi2O2N2:Eu2 plus fluorescent powder - Google Patents
Method for preparing porous spherical CaSi2O2N2:Eu2 plus fluorescent powder Download PDFInfo
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- CN101698799B CN101698799B CN200910198250XA CN200910198250A CN101698799B CN 101698799 B CN101698799 B CN 101698799B CN 200910198250X A CN200910198250X A CN 200910198250XA CN 200910198250 A CN200910198250 A CN 200910198250A CN 101698799 B CN101698799 B CN 101698799B
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Abstract
The invention relates to a method for preparing porous spherical CaSi2O2N2:Eu2 plus fluorescent powder, which comprises the following steps: (1) dissolving calcium chloride, europium chloride and polyethylene glycol into water to prepare solution A, dissolving sodium carbonate, polyethylene glycol 6,000 and sodium dodecyl sulfate into the water to prepare solution B, pouring the solution A into the solution B for stirring, standing, water-rinsing and drying, taking and dispersing (Eu, Ca)CO3 into the water, adding Na2SiO3 solution, adjusting a pH value of the solution to 7 to 8, and then stirring, water-rinsing and drying the mixed solution; and (2) under the air current of NH3, heating a product obtained by the treatment in the step (1) to 1,250 to 1,400 DEG C, preserving the temperature and then cooling the product to a room temperature to obtain the porous spherical CaSi2O2N2:Eu2 plus fluorescent powder. The method of the invention is characterized by simpleness, low cost, simple required production equipment, low nitriding temperature, short nitriding time, energy consumption reduction and easy realization of industrial production; and the obtained porous spherical CaSi2O2N2:Eu2 plus fluorescent powder is good in dispersity, is not easy to agglomerate and keeps porous spherical appearance.
Description
Technical field
The invention belongs to CaSi
2O
2N
2: Eu
2+The preparation field of fluorescent material particularly relates to a kind of porous spherical CaSi
2O
2N
2: Eu
2+The preparation method of fluorescent material.
Background technology
Since invented with InGaN be the blue-light excited white light emitting diode (White-LEDs) on basis since, the application of white light LEDs in electron device developed rapidly, like the backlight of mobile phone etc.; Along with the progress of the technology of semiconductor chips and the exploitation of high-efficiency fluorescence powder, the luminous efficiency of white light LEDs already and will obtain improving more significantly simultaneously.White light LEDs has shown the potentiality that replace the traditional lighting mode, and the luminous efficiency of white light LEDs has surpassed incandescent light at present, near luminescent lamp.Again owing to long lifetime of white light LEDs, save the energy, eco-friendly characteristic, just rapidly by the application extension of personal communication apparatus, LCD backlight source aspect to automotive lighting and family general lighting field.
White light emitting diode can utilize the diode and the fluorescent material of InGaN base to realize.At present commonly used is InGaN base blue-light LED chip (wavelength be 450～470nm) with the yellow fluorescent powder combination, fluorescent material sends gold-tinted after the blue light that led chip is sent carries out intense absorption, finally obtain white light through complementary colors.Yet present applied fluorescent material, major part can't satisfy above requirement fully, like YAG:Ce the most commonly used
3+The thermostability of fluorescent material is relatively poor, and colour rendering index is lower.In order to address this problem, excellent heat stability, the oxynitride fluorescent powder of high color rendering index (CRI) has received widely and having paid close attention to.Like we CaSi at " luminous journal " Vol.29 (2008) pp.689-694 report
2O
2N
2: Eu
2+Fluorescent material is exactly comparatively excellent a kind of of performance wherein.And we have reported Eu at Mater.Lett.Vol.63 (2009) pp.1448-1450 subsequently
2+, Y
3+Codoped improves CaSi
2O
2N
2: Eu
2+The luminous intensity of fluorescent material, and to cooperate the 460nmLED chip to obtain colour rendering index be 82 white light.Yet, prepare CaSi at present
2O
2N
2: Eu
2+The method of fluorescent material only limits to high temperature solid state reaction.All is with highly purified Si like above-mentioned two pieces of reports and Y.Q.Li in the preparation method of Chem.Mater.Vol.17 (2005) 3242-3248 report
3N
4, SiO
2, CaCO
3, Eu
2O
3Be raw material, under the soaking time of 1400 ℃ even higher temperature and 6～12h, be prepared from.And the product particle shape is irregular, and size is big, is prone to reunite.Therefore, it is lower to seek a kind of temperature, and reacting preparation approach faster becomes the severe challenge that we face.
Summary of the invention
Technical problem to be solved by this invention provides a kind of porous spherical CaSi
2O
2N
2: Eu
2+The preparation method of fluorescent material, this method is simple, and cost is low, and required production unit is simple, and nitriding temperature is low, and nitridation time is short, reduces energy consumption, is easy to realize suitability for industrialized production.
A kind of porous spherical CaSi of the present invention
2O
2N
2: Eu
2+The preparation method of fluorescent material comprises:
(1) preparation of nucleocapsid structure oxide compound precursor
With calcium chloride, Europium chloride and polyethylene glycol wiring solution-forming A soluble in water; With sodium carbonate, Macrogol 6000 and lauryl sodium sulfate wiring solution-forming B soluble in water; Solution A is poured in the solution B fast, stirs 1-5min and keep 20-25 ℃, the still aging 18-24h of pH 7-8 will precipitate washing 5-8 time, and 80-100 ℃ of oven dry 0.5-2h promptly obtains (Eu, Ca) CO
3Tiny balloon;
Get 1.0-1.2g (Eu, Ca) CO
3Tiny balloon is dispersed in the 200-300ml water, CaCO in molar ratio under the room temperature
3: SiO
2=1.0-1.2: 2 dropwise add 0.05-0.1M Na
2SiO
3Solution is regulated pH 7-8, is warming up to 60-80 ℃ of reaction 1-2h behind the stirring 12-24h and reacts completely with assurance, washes 3-5 time, and 80-100 ℃ of oven dry 1-2h obtains (Ca, Eu) CO
3SiO
2The nucleocapsid structure precursor;
(2) porous spherical CaSi
2O
2N
2: Eu
2+The preparation of fluorescent material
With above-mentioned precursor 200-300mL/min NH in the tubular type atmosphere furnace
3Under the air-flow, be warming up to 1250-1400 ℃, under identical atmosphere, reduce to room temperature behind the insulation 0.5-5h and obtain porous spherical CaSi with stove
2O
2N
2: Eu
2+Fluorescent material.
The mol ratio of Europium chloride and calcium chloride is 0.03-0.05 in the said step (1): 1.
The molecular weight of said step (1) polyoxyethylene glycol is 6000.
In the said step (1) in the solution A in calcium chloride concentration and the solution B concentration of sodium carbonate identical, be 0.1M-0.2M.
Solution A is identical with polyoxyethylene glycol concentration in the solution B in the said step (1), is 1.0g/L-1.5g/L.
The concentration of the sodium lauryl sulphate in the said step (1) in the solution B is 1-2 * 10
-2M.
Said step (1) uses 1-1.5wt% Hydrogen chloride to regulate pH.
The temperature rise rate of said step (2) is 60-150 ℃/min.
Said step (2) porous spherical CaSi
2O
2N
2: Eu
2+Fluorescent material effectively obtains the fluorescence of 555nm in 325～450nm interval.
The invention consists of calcium chloride, europium chloride, in the presence of sodium carbonate, sodium lauryl sulfate, polyethylene glycol, to form an aqueous solution of europium-doped precipitated calcium carbonate hollow ball; europium-doped calcium hollow ball as the template, calcium silicate hydrolysis uniformly formed on the surface layer of silicon dioxide shell; the aforementioned core-shell structure having an oxide precursor in a tubular reactor, the ammonia in the current conditions, the high temperature nitridation a porous spherical CaSi
2 O
2 N
2 : Eu
2 + phosphors.
Beneficial effect
(1) preparation method of the present invention is simple, and cost is low, and required production unit is simple, and nitriding temperature is low, and nitridation time is short, reduces energy consumption, is easy to realize suitability for industrialized production;
(2) gained CaSi of the present invention
2O
2N
2: Eu
2+Fluorescent material good dispersivity, the difficult reunion, and kept the porous spherical pattern.
Description of drawings
150 ℃/min of Fig. 1 heat-up rate, 1300 ℃ of nitrogenize 1h gained CaSi
2O
2N
2: Eu
2+The X-ray diffractogram of fluorescent material;
150 ℃/min of Fig. 2 heat-up rate, 1300 ℃ of nitrogenize 1h gained CaSi
2O
2N
2: Eu
2+The flying-spot microscope photo of fluorescent material;
150 ℃/min of Fig. 3 heat-up rate, 1300 ℃ of nitrogenize 1h gained CaSi
2O
2N
2: Eu
2+The fluorescence spectrum figure of fluorescent material;
150 ℃/min of Fig. 4 heat-up rate, 1400 ℃ of nitrogenize 0.5h gained CaSi
2O
2N
2: Eu
2+The X-ray diffractogram of fluorescent material;
150 ℃/min of Fig. 5 heat-up rate, 1400 ℃ of nitrogenize 0.5h gained CaSi
2O
2N
2: Eu
2+The fluorescence spectrum figure of fluorescent material.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Calcium chloride, europium chloride, polyethylene glycol dissolved in water to make a solution, 200mL A; the sodium carbonate, polyethylene glycol, sodium lauryl sulfate was dissolved in water to make 300mL B, maintaining the solution A, calcium chloride and sodium carbonate in the same concentration of solution B, are 0.1M; europium chloride and calcium chloride in a molar ratio of 0.03:1; solutions A and B in the same concentration of polyethylene glycol, are 1g / L; sodium dodecyl sulfate concentration of 1 × 10
-2 M; quickly with a good solution A was poured into solution B, stirring after 1min maintained 20 ℃ , pH? 7 then aged for 18h, the resulting precipitate was washed 5 times, 80 ℃ drying 2h is obtained (Eu, Ca) CO
3 hollow microspheres;
Get 1g (Eu, Ca) CO
3Tiny balloon is dispersed in the 200mL water, CaCO in molar ratio under the room temperature
3: SiO
2Dropwise add 0.05M Na at=1: 2
2SiO
3Solution drips 1.5wt% Hydrogen chloride simultaneously to keep pH 7, temperature is risen to 80 ℃ of reaction 1h after stirring 12h, with 80 ℃ of oven dry 2h after the product washing that obtains 3 times,
With (Ca, Eu) CO that obtain
3SiO
2The nucleocapsid structure precursor is put into the aluminum oxide porcelain boat, 300mL/min NH in the tubular type atmosphere furnace
3Rise to 1300 ℃ with 150 ℃/min of temperature rise rate under the air-flow, under identical atmosphere, reduce to room temperature behind the insulation 1h with stove.Fig. 1 is the CaSi of present embodiment preparation
2O
2N
2: Eu
2+The X-ray diffractogram of fluorescent material, through contrasting with standard card, thing is purified CaSi mutually
2O
2N
2Phase.Fig. 2 is the CaSi of present embodiment preparation
2O
2N
2: Eu
2+The stereoscan photograph of fluorescent material, the visible final pattern of product is the hollow ball with vesicular structure.Fig. 3 is the CaSi of present embodiment preparation
2O
2N
2: Eu
2+The fluorescence spectrum of fluorescent material is it is thus clear that can effectively obtain the fluorescence that wavelength is 555nm under the 400nm optical excitation.
Embodiment 2
Calcium chloride, europium chloride, polyethylene glycol dissolved in water to make a solution, 400mL A; the sodium carbonate, polyethylene glycol, sodium lauryl sulfate was dissolved in water to make 600mL B; maintaining the solution A, calcium chloride and sodium carbonate in the same concentration of solution B, are 0.1M; europium chloride and calcium chloride in a molar ratio of 0.03:1; solutions A and B in the same concentration of polyethylene glycol, are 1.5g / L; sodium dodecyl sulfate concentration of 2 × 10
-2 M; quickly with a good solution A was poured into solution B, stirring after 5min remain 25 ℃, pH? 8 then aged for 24h, the resulting precipitate was washed 5 times, 80 ℃ drying 2h is obtained (Eu, Ca) CO
3 hollow microspheres;
Get 1.2g (Eu, Ca) CO
3Tiny balloon is dispersed in the 300mL water, CaCO in molar ratio under the room temperature
3: SiO
2Dropwise add 0.1M Na at=1.2: 2
2SiO
3Solution drips 1.5wt% Hydrogen chloride simultaneously to keep pH 8, temperature is risen to 60 ℃ of reaction 2h after stirring 24h, with 80 ℃ of oven dry 2h after the product washing that obtains 3 times;
With (Ca, Eu) CO that obtain
3SiO
2The nucleocapsid structure precursor is put into the aluminum oxide porcelain boat, 200mL/min NH in the tubular type atmosphere furnace
3Rise to 1250 ℃ with 60 ℃/min of temperature rise rate under the air-flow, under identical atmosphere, reduce to room temperature behind the insulation 5h with stove.X-ray diffraction shows that product is mainly CaSi
2O
2N
2Phase.Fluorescence spectrum is illustrated under the 400nm optical excitation can effectively obtain the fluorescence that wavelength is 545nm.
Embodiment 3
Calcium chloride, europium chloride, polyethylene glycol 6000 was dissolved in water to make 400mL A; the sodium carbonate, polyethylene glycol 6000, sodium lauryl sulfate was dissolved in water to make 600mL B; maintaining the solution a calcium chloride concentration of the sodium carbonate solution B in the same concentration, both 0.2M; europium chloride and calcium chloride in a molar ratio of 0.05:1; solutions A and B in the same concentration of polyethylene glycol, are 1.5g / L; sodium dodecyl sulfate concentration of 2 × 10
-2 M, with a good solution A solution B was poured into rapidly stirring after 1min maintained 20 ℃, pH? 8 then aged for 24h, the resulting precipitate was washed 8 times, 100 ℃ 0.5h drying is obtained (Eu, Ca) CO
3 hollow microspheres ball;
Get 1.2g (Eu, Ca) CO
3Tiny balloon is dispersed in the 300mL water, CaCO in molar ratio under the room temperature
3: SiO
2Dropwise add 0.1M Na at=1.2: 2
2SiO
3Solution drips 1wt% Hydrogen chloride simultaneously to keep pH 8, is warming up to 60 ℃ of reaction 2h behind the stirring 24h.With 100 ℃ of oven dry 1h after the product that the obtains washing 5 times;
With (Ca, Eu) CO that obtain
3SiO
2The nucleocapsid structure precursor is put into the aluminum oxide porcelain boat, 300mL/min NH in the tubular type atmosphere furnace
3Rise to 1400 ℃ with 150 ℃/min of temperature rise rate under the air-flow, under identical atmosphere, reduce to room temperature behind the insulation 0.5h with stove.Fig. 4 is the CaSi of present embodiment preparation
2O
2N
2: Eu
2+The X-ray diffractogram of fluorescent material is through being CaSi with the standard card contrast
2O
2N
2Phase.Fig. 5 is the fluorescence spectrum of the fluorescent material of present embodiment preparation, the visible fluorescence that in 325～450nm interval, effectively obtains 555nm.
Claims (8)
1. porous spherical CaSi
2O
2N
2: Eu
2+The preparation method of fluorescent material comprises:
(1) with calcium chloride, Europium trichloride and polyoxyethylene glycol wiring solution-forming A soluble in water; With yellow soda ash, polyethylene glycol 6000 and sodium lauryl sulphate wiring solution-forming B soluble in water; Solution A is poured in the solution B fast, stirs 1-5min and keep 20-25 ℃, the still aging 18-24h of pH 7-8 will precipitate washing 5-8 time, and 80-100 ℃ of oven dry 0.5-2h promptly obtains (Eu, Ca) CO
3Tiny balloon; Wherein, the mol ratio of Europium trichloride and calcium chloride is 0.03-0.05:1;
Get 1.0-1.2g (Eu, Ca) CO
3Tiny balloon is dispersed in the 200-300ml water, CaCO in molar ratio under the room temperature
3: SiO
2=1.0-1.2:2 dropwise adds 0.05-0.1M Na
2SiO
3Solution is regulated pH 7-8, is warming up to 60-80 ℃ of reaction 1-2h behind the stirring 12-24h and reacts completely with assurance, washes 3-5 time, and 80-100 ℃ of oven dry 1-2h obtains (Ca, Eu) CO
3/ SiO
2The nucleocapsid structure precursor;
(2) with above-mentioned precursor 200-300mL/minNH in the tubular type atmosphere furnace
3Under the air-flow, be warming up to 1250-1400 ℃, under identical atmosphere, reduce to room temperature behind the insulation 0.5-5h and obtain porous spherical CaSi with stove
2O
2N
2: Eu
2+Fluorescent material.
2. a kind of porous spherical CaSi according to claim 1
2O
2N
2: Eu
2+The preparation method of fluorescent material is characterized in that: the molecular weight of said step (1) polyoxyethylene glycol is 6000.
3. a kind of porous spherical CaSi according to claim 1
2O
2N
2: Eu
2+The preparation method of fluorescent material is characterized in that: in the said step (1) in the solution A in calcium chloride concentration and the solution B concentration of sodium carbonate identical, be 0.1M-0.2M.
4. a kind of porous spherical CaSi according to claim 1
2O
2N
2: Eu
2+The preparation method of fluorescent material is characterized in that: solution A is identical with polyoxyethylene glycol concentration in the solution B in the said step (1), is 1.0g/L-1.5g/L.
5. a kind of porous spherical CaSi according to claim 1
2O
2N
2: Eu
2+The preparation method of fluorescent material is characterized in that: the concentration of the sodium lauryl sulphate in the said step (1) in the solution B is 1-2 * 10
-2M.
6. a kind of porous spherical CaSi according to claim 1
2O
2N
2: Eu
2+The preparation method of fluorescent material is characterized in that: said step (1) uses 1-1.5wt% Hydrogen chloride to regulate pH.
7. a kind of porous spherical CaSi according to claim 1
2O
2N
2: Eu
2+The preparation method of fluorescent material is characterized in that: the temperature rise rate of said step (2) is 60-150 ℃/min.
8. a kind of porous spherical CaSi according to claim 1
2O
2N
2: Eu
2+The preparation method of fluorescent material is characterized in that: said step (2) porous spherical CaSi
2O
2N
2: Eu
2+Fluorescent material effectively obtains the fluorescence of 555nm in 325～450nm interval.
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| CN102559173B (en) * | 2011-12-27 | 2013-12-11 | 江苏博睿光电有限公司 | Core-surface layer gradient nitrogen oxide fluorescent powder, manufacturing method thereof and light-emitting device adopting fluorescent powder |
| CN102533260A (en) * | 2011-12-29 | 2012-07-04 | 彩虹集团公司 | nitrogen oxide yellowgreen fluorescent powder for LED and preparation method for nitrogen oxide yellowgreen fluorescent powder |
| CN104278363B (en) * | 2014-08-29 | 2016-08-17 | 东华大学 | A kind of Ca-α-SiAlON:Eu2+the preparation method of fluorescence nano band fiber |
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|---|---|---|---|---|
| CN101525536A (en) * | 2009-04-08 | 2009-09-09 | 东华大学 | A preparation method of CaSi2O2N2: eu2+, Y3+phosphor |
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