CN102260502A - A (Ca, mg) Si2O2N2: eu2+phosphor and its prepn - Google Patents
A (Ca, mg) Si2O2N2: eu2+phosphor and its prepn Download PDFInfo
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- CN102260502A CN102260502A CN2011101454224A CN201110145422A CN102260502A CN 102260502 A CN102260502 A CN 102260502A CN 2011101454224 A CN2011101454224 A CN 2011101454224A CN 201110145422 A CN201110145422 A CN 201110145422A CN 102260502 A CN102260502 A CN 102260502A
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Abstract
The invention relates to (Ca, Mg)Si2O2N2:Eu2<+> fluorescent powder and a preparation method thereof. The stoichiometric ratio of Ca, Mg, Si, O, N and Eu is (0.7-0.895):01:2:2:2:(0.005-0.2). The preparation method comprises the following steps of: uniformly mixing, drying and screening raw materials; calcining at 1,400-1,500 DEG C for 5-8 hours at the atmosphere of nitrogen; and pulverizing, washing and drying the calcined product to obtain the (Ca, Mg)Si2O2N2:Eu2<+> fluorescent powder. The luminous intensity of the (Ca, Mg)Si2O2N2:Eu2<+> fluorescent powder is obviously improved compared with the CaSi2O2N2:Eu2<+> fluorescent powder under the same ion concentration stimulating condition; and the invention has the advantages of simple preparation process and simple needed production equipment, is easy to realize industrialized production and has favorable application prospect.
Description
Technical field
The invention belongs to oxygen nitrogen systems fluorescent material field, particularly a kind of (Ca, Mg) Si
2O
2N
2: Eu
2+Fluorescent material and preparation method thereof.
Background technology
White light emitting diode (LED) has distinguishing features such as volume is little, current consumption is low, long service life, environmental protection, is to have one of new and high technology of development prospect in recent years most.Along with development of technology, be expected to replace incandescent light, luminescent lamp becomes lighting source of new generation.
Light conversion hysteria white light LEDs is at present the most frequently used also proven technique comparatively, sees first commercial white light LEDs of Japanese Ri Ya chemical company in 1996 invention the earliest, and its ultimate principle is to utilize InGaN base blue-light LED chip and YAG:Ce
3+Yellow fluorescent powder makes up and the realization white light.Yet, because YAG:Ce
3+Lack red wave band in the emmission spectrum of fluorescent material, be difficult to make the white light LEDs of high color rendering index (CRI), low colour temperature, therefore limited its Application Areas.
(oxygen) nitrogen systems fluorescent material structurally has rich diversity, so characteristics of luminescence regulation and control have than large space.MSi wherein
2O
2N
2: Eu
2+(Ba) the fluorescent material preparation condition is loose for M=Ca, Sr, and the luminescent properties excellence receives increasing concern in recent years.CaSi
2O
2N
2: Eu
2+As a kind of novel yellow-green fluorescence powder, can be by changing Eu
2+At CaSi
2O
2N
2: Eu
2+Doping in the fluorescent material is regulated the emission wavelength of fluorescent material, increases Eu simultaneously within the specific limits
2+Doping can also improve the luminous intensity of fluorescent material., reported in 033103 (2009) and worked as Eu at J.Appl.Phys.106 as X.F.Song etc.
2+Doping content when 0.5at% is increased to 20at%, CaSi
2O
2N
2: Eu
2+The emission wavelength of fluorescent material from the 499nm red shift to 550nm; Meanwhile, work as Eu
2+Doping content when 0.5at% is increased to 2at%, the emissive porwer of fluorescent material strengthens gradually, yet works as Eu
2+Doping content when surpassing 2at% luminous intensity will significantly reduce because of concentration quenching.By changing Eu
2+Though doping can in a big way, regulate CaSi
2O
2N
2: Eu
2+The emission wavelength of fluorescent material, but Eu worked as
2+During high-concentration dopant, the luminous intensity of fluorescent material will significantly lower and can't practical requirement, thereby has limited the application of such fluorescent material.
Summary of the invention
Technical problem to be solved by this invention provides a kind of (Ca, Mg) Si
2O
2N
2: Eu
2+Fluorescent material and preparation method thereof, under the condition of identical excited ion concentration, the luminous strength ratio CaSi of this fluorescent material
2O
2N
2: Eu
2+Increasing significantly of fluorescent material; This preparation method's technology is simple, and required production unit is simple, is easy to realize suitability for industrialized production, has a good application prospect.
A kind of (Ca, Mg) Si of the present invention
2O
2N
2: Eu
2+Fluorescent material, the stoichiometric ratio of its Ca, Mg, Si, O, N and Eu are 0.7～0.895: 0.1: 2: 2: 2: 0.005～0.2.
The stoichiometric ratio of Ca, Mg, Si, O, N and Eu is 0.85: 0.1: 2: 2: 2: 0.05,0.895: 0.1: 2: 2: 2: 0.005 or 0.7: 0.1: 2: 2: 2: 0.2.
A kind of (Ca, Mg) Si of the present invention
2O
2N
2: Eu
2+The preparation method of fluorescent material comprises:
(1) be raw material with lime carbonate, silicon-dioxide, silicon nitride, magnesium basic carbonate and europium sesquioxide,
Mix in molar ratio 1.4～1.79: 1: 1: 0.04: 0.005～0.2, dry, sieve;
(2) said mixture is calcined 5～8h with 1400～1500 ℃ under nitrogen atmosphere;
(3) above-mentioned calcinate pulverized, washed, drying, promptly.
The concrete technology of mixing in the described step (1) is to add dehydrated alcohol to grind 1～4h, supersound process 5～10min then in raw material.
Crossing grit number in the described step (1) is 150～200 orders.
Stream of nitrogen gas amount in the described step (2) is 250～300ml/min, and the calcining temperature rise rate is 2～3 ℃/min, and at 800 ℃ of insulation 0.5～1h.
Washing in the described step (3) comprises pickling 1～2h, uses distilled water and absolute ethanol washing then respectively.
Described Acidwash solution is the hydrochloric acid soln of volumetric concentration 5%～10%.
Dry concrete technology in described step (1) and (3) is 60 ℃～80 ℃ of drying temperatures, time of drying 8～12h.
The present invention passes through Mg
2+Doping not only can improve CaSi
2O
2N
2: Eu
2+The luminous intensity of fluorescent material, what is more important is at (Ca, Mg) Si
2O
2N
2Can realize Eu in the host lattice
2+High-concentration dopant, thereby can guarantee that fluorescent material is having under the prerequisite of higher luminous intensity the effective adjusting that realizes the fluorescent material emission wavelength.
Beneficial effect
(1) under the condition of identical excited ion concentration, luminous strength ratio CaSi of the present invention
2O
2N
2: Eu
2+Increasing significantly of fluorescent material;
(2) the present invention is by changing Eu
2+Content, can regulate light-emitting phosphor intensity and emission wavelength;
(3) preparation method's technology of the present invention is simple, and required production unit is simple, is easy to realize suitability for industrialized production, has a good application prospect.
Description of drawings
Fig. 1 is Ca
0.95Si
2O
2N
2: Eu
2+ 0.05Fluorescence spectrum;
Fig. 2 is (Ca
0.85, Mg
0.1) Si
2O
2N
2: Eu
2+ 0.05With Ca
0.95Si
2O
2N
2: Eu
2+ 0.05Fluorescence spectrum;
Fig. 3 is (Ca
0.895, Mg
0.1) Si
2O
2N
2: Eu
2+ 0.005Fluorescence spectrum;
Fig. 4 is (Ca
0.7, Mg
0.1) Si
2O
2N
2: Eu
2+ 0.2With (Ca
0.895, Mg
0.1) Si
2O
2N
2: Eu
2+ 0.005Fluorescence spectrum.
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 and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications 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.
Embodiment 1
Get lime carbonate 1.70g (0.017mo1), silicon-dioxide 0.60g (0.01mol), silicon nitride 1.40g (0.01mol), magnesium basic carbonate 0.1936g (0.0004mol), europium sesquioxide 0.176g (0.0005mol), add a small amount of dehydrated alcohol wet-milling 1h in agate mortar, ultrasonic then 5min, after mixing with raw material in 70 ℃ of oven drying 10h.Put into the aluminum oxide porcelain boat after the batching that obtains sieved by 150 purpose standard sieves, place the tubular type atmosphere furnace, under nitrogen atmosphere, be warming up to 800 ℃, nitrogen flow is 300ml/min, heat-up rate is 2 ℃/min, under this temperature, be incubated 30min, be warming up to 1500 ℃ with identical heat-up rate again, insulation 5h; Then, naturally cool to room temperature, after in agate mortar, grinding powder is distributed to volumetric concentration and is in 5% the hydrochloric acid soln, magnetic agitation 2h, again with distilled water and each centrifugal washing 3 times of dehydrated alcohol, dry 12h promptly obtains (Ca in 60 ℃ baking oven at last
0.85, Mg
0.1) Si
2O
2N
2: Eu
2+ 0.05Fluorescent material.Fig. 2 is the prepared (Ca of present embodiment
0.85, Mg
0.1) Si
2O
2N
2: Eu
2+ 0.05The fluorescence spectrum of fluorescent material and Ca
0.95Si
2O
2N
2: Eu
2+ 0.05As seen the fluorescence spectrum of fluorescent material compares (Ca with Comparative Examples 1
0.85, Mg
0.1) Si
2O
2N
2: Eu
2+ 0.05The luminous strength ratio Ca of fluorescent material
0.95Si
2O
2N
2: Eu
2+ 0.05The raising of fluorescent material 13%.
Embodiment 2
Get lime carbonate 1.79g (0.0179mol), silicon-dioxide 0.60g (0.01mol), silicon nitride 1.40g (0.01mol), magnesium basic carbonate 0.19g (0.0004mol) europium sesquioxide 0.0176g (0.00005mol), add a small amount of dehydrated alcohol wet-milling 2h in agate mortar, ultrasonic then 10min, after mixing with raw material in 80 ℃ of oven drying 12h.Put into the aluminum oxide porcelain boat after the batching that obtains sieved by 200 purpose standard sieves, place the tubular type atmosphere furnace, under nitrogen atmosphere, be warming up to 800 ℃, nitrogen flow is 280ml/min, heat-up rate is 3 ℃/min, under this temperature, be incubated 1h, be warming up to 1400 ℃ with identical heat-up rate again, insulation 6h; Then, naturally cool to room temperature, after in agate mortar, grinding powder is distributed to volumetric concentration and is in 10% the hydrochloric acid soln, magnetic agitation 1h, again with distilled water and each centrifugal washing 3 times of dehydrated alcohol, dry 8h promptly obtains (Ca in 80 ℃ baking oven at last
0.895, Mg
0.1) Si
2O
2N
2: Eu
2+ 0.005Fluorescent material.Fig. 3 is the prepared (Ca of present embodiment
0.895, Mg
0.1) Si
2O
2N
2: Eu
2+ 0.005The fluorescence spectrum of fluorescent material.
Embodiment 3
Get lime carbonate 1.40g (0.014mol), silicon-dioxide 0.60g (0.01mol), silicon nitride 1.40g (0.01mol), magnesium basic carbonate 0.19g (0.0004mol), europium sesquioxide 0.70g (0.002mol), add a small amount of dehydrated alcohol wet-milling 4h in agate mortar, ultrasonic then 5min, after mixing with raw material in 80 ℃ of oven drying 12h.Put into the aluminum oxide porcelain boat after the batching that obtains sieved by 150 purpose standard sieves, place the tubular type atmosphere furnace, under nitrogen atmosphere, be warming up to 800 ℃, nitrogen flow is 250ml/min, heat-up rate is 2 ℃/min, under this temperature, be incubated 30min, be warming up to 1400 ℃ with identical heat-up rate again, insulation 8h; Then, naturally cool to room temperature, after in agate mortar, grinding powder is distributed to volumetric concentration and is in 8% the hydrochloric acid soln, magnetic agitation 2h, again with distilled water and each centrifugal washing 3 times of dehydrated alcohol, dry 12h promptly obtains (Ca in 80 ℃ baking oven at last
0.7, Mg
0.1) Si
2O
2N
2: Eu
2+ 0.2Fluorescent material.Fig. 4 is the prepared (Ca of present embodiment
0.7, Mg
0.1) Si
2O
2N
2: Eu
2+ 0.2The fluorescence spectrum of fluorescent material and (Ca
0.895, Mg
0.1) Si
2O
2N
2: Eu
2+ 0.005As seen the fluorescence spectrum of fluorescent material compares (Ca with embodiment 2
0.7, Mg
0.1) Si
2O
2N
2: Eu
2+ 0.2The maximum excitation wavelength of fluorescent material from the 350nm red shift to 442nm, the optimum transmit peak position from the 543nm red shift to 552nm; Simultaneously, (Ca under best excited state
0.7, Mg
0.1) Si
2O
2N
2: Eu
2+ 0.2Luminous strength ratio (the Ca of fluorescent material
0.895, Mg
0.1) Si
2O
2N
2: Eu
2+ 0.005The raising of fluorescent material 36%.
Comparative Examples 1
Get lime carbonate 1.90g (0.019mol), silicon-dioxide 0.60g (0.01mol), silicon nitride 1.40g (0.01mol), europium sesquioxide 0.176g (0.0005mol), add a small amount of dehydrated alcohol wet-milling 1h in agate mortar, ultrasonic then 10min, after mixing with raw material in 60 ℃ of oven drying 12h.Put into the aluminum oxide porcelain boat after the batching that obtains sieved by 150 purpose standard sieves, place the tubular type atmosphere furnace, under nitrogen atmosphere, be warming up to 800 ℃, nitrogen flow is 300ml/min, heat-up rate is 2 ℃/min, under this temperature, be incubated 30min, be warming up to 1400 ℃ with identical heat-up rate again, insulation 5h; Then, naturally cool to room temperature, take out, after in agate mortar, grinding powder is distributed to volumetric concentration and is in 5% the hydrochloric acid soln, magnetic agitation 2h, again with distilled water and each centrifugal washing 3 times of dehydrated alcohol, dry 8h promptly obtains Ca in 70 ℃ baking oven at last
0.95Si
2O
2N
2: Eu
2+ 0.05Fluorescent material.Fig. 1 is the prepared Ca of present embodiment
0.95Si
2O
2N
2: Eu
2+ 0.05The fluorescence spectrum of fluorescent material.
Claims (8)
1. (Ca, Mg) Si
2O
2N
2: Eu
2+Fluorescent material, the stoichiometric ratio of its Ca, Mg, Si, O, N and Eu are 0.7～0.895: 0.1: 2: 2: 2: 0.005～0.2.
2. (Ca, Mg) Si
2O
2N
2: Eu
2+The preparation method of fluorescent material comprises:
(1) be raw material with lime carbonate, silicon-dioxide, silicon nitride, magnesium basic carbonate and europium sesquioxide, mix in molar ratio 1.4～1.79: 1: 1: 0.04: 0.005～0.2, dry, sieve;
(2) said mixture is calcined 5～8h with 1400～1500 ℃ under nitrogen atmosphere;
(3) will pulverize through above-mentioned incinerating product, wash, drying, promptly.
3. a kind of (Ca, Mg) Si according to claim 2
2O
2N
2: Eu
2+The preparation method of fluorescent material is characterized in that: the concrete technology of mixing in the described step (1) is ground 1～4h, supersound process 5～10min then for add dehydrated alcohol in raw material.
4. a kind of (Ca, Mg) Si according to claim 2
2O
2N
2: Eu
2+The preparation method of fluorescent material is characterized in that: crossing grit number in the described step (1) is 150～200 orders.
5. a kind of (Ca, Mg) Si according to claim 2
2O
2N
2: Eu
2+The preparation method of fluorescent material is characterized in that: the stream of nitrogen gas amount in the described step (2) is 250～300ml/min, and the calcining temperature rise rate is 2～3 ℃/min, and at 800 ℃ of insulation 0.5～1h.
6. a kind of (Ca, Mg) Si according to claim 2
2O
2N
2: Eu
2+The preparation method of fluorescent material is characterized in that: the washing in the described step (3) comprises pickling 1～2h, uses distilled water and absolute ethanol washing then respectively.
7. a kind of (Ca, Mg) Si according to claim 6
2O
2N
2: Eu
2+The preparation method of fluorescent material is characterized in that: described Acidwash solution is the hydrochloric acid soln of volumetric concentration 5%～10%.
8. a kind of (Ca, Mg) Si according to claim 2
2O
2N
2: Eu
2+The preparation method of fluorescent material is characterized in that: the dry concrete technology in described step (1) and (3) is 60 ℃～80 ℃ of drying temperatures, time of drying 8～12h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232088A (en) * | 2014-09-03 | 2014-12-24 | 江门市科恒实业股份有限公司 | Nitric oxide fluorescent powder and preparation method of nitric oxide fluorescent powder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004036962A1 (en) * | 2002-10-14 | 2004-04-29 | Philips Intellectual Property & Standards Gmbh | Light-emitting device comprising an eu(ii)-activated phosphor |
| CN101029230A (en) * | 2007-04-03 | 2007-09-05 | 北京宇极科技发展有限公司 | Nitrogen oxide compound fluorescent material and illuminating or displaying light source therefrom |
| KR100958700B1 (en) * | 2009-09-21 | 2010-05-18 | 금호전기주식회사 | Oxynitride phosphor, method for manufacturing the same and light-emitting device comprising the same |
-
2011
- 2011-06-01 CN CN201110145422.4A patent/CN102260502B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004036962A1 (en) * | 2002-10-14 | 2004-04-29 | Philips Intellectual Property & Standards Gmbh | Light-emitting device comprising an eu(ii)-activated phosphor |
| CN101029230A (en) * | 2007-04-03 | 2007-09-05 | 北京宇极科技发展有限公司 | Nitrogen oxide compound fluorescent material and illuminating or displaying light source therefrom |
| KR100958700B1 (en) * | 2009-09-21 | 2010-05-18 | 금호전기주식회사 | Oxynitride phosphor, method for manufacturing the same and light-emitting device comprising the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232088A (en) * | 2014-09-03 | 2014-12-24 | 江门市科恒实业股份有限公司 | Nitric oxide fluorescent powder and preparation method of nitric oxide fluorescent powder |
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Granted publication date: 20140108 Termination date: 20160601 |