CN102533268A - Blue light-emitting material and preparation method thereof - Google Patents

Blue light-emitting material and preparation method thereof Download PDF

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Publication number
CN102533268A
CN102533268A CN2012100117073A CN201210011707A CN102533268A CN 102533268 A CN102533268 A CN 102533268A CN 2012100117073 A CN2012100117073 A CN 2012100117073A CN 201210011707 A CN201210011707 A CN 201210011707A CN 102533268 A CN102533268 A CN 102533268A
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hydrogen
carbonate
emitting material
mixture
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梁宏斌
侯得健
苏锵
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Sun Yat Sen University
National Sun Yat Sen University
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National Sun Yat Sen University
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Abstract

The invention discloses a blue light-emitting material and a preparation method thereof. The blue light-emitting material has a chemical composition expression formula of Ba1-xEuxCa2MgSi2O8, wherein Eu<2+> ( bivalent rare earth europium ion) is an active ion, and x is the molar percentage coefficient of the active ion Eu<2+> relative to alkaline earth metal ion Ba<2+> and is not less than 0.001 and not more than 0.10. According to the invention, the preparation method is simple; and the prepared novel rare earth light-emitting material can emit blue light under the excitation of ultraviolet, has stronger light intensity than traditional commercial blue fluorescent powder BaMgAl10O17:Eu<2+> (BAM), and also has relatively better luminance intensity under the vacuum ultraviolet excitation.

Description

A kind of blue emitting material and preparation method thereof
Technical field
The present invention relates to a kind of blue emitting material and preparation method thereof.
Background technology
The trichromatic energy saving lamp is present most widely used set lights, and its principle is to utilize mercury vapor discharge to produce UV-light and a spot of 185 nm vacuum-ultraviolet lights of 254 nm, thereby the fluorescent material in the exciter lamp reaches illumination purposes.1974, synthesized blue emitting material magnesium aluminate barium, green luminescent material magnesium aluminate cerium and red illuminating material yttrium oxide first by Dutch scientist, process the trichromatic energy saving lamp.With traditional luminescent lamp ratio, the trichromatic energy saving light fixture has luminous efficiency high, and color developing is good, advantages such as long service life.
Plasma panel display (PDP) is the device that utilizes the luminous demonstration of noble gas discharge excitated fluorescent powder.VUV (VUV) light that the basic rare gas mixed gas plasma of the xenon (Xe) that the PDP device extensively adopts produces, mainly in 147 nanometers (nm) and 172 nanometers (nm) as excitaton source, excitated fluorescent powder is luminous.
The used blue colour fluorescent powder of trichromatic energy saving lamp and plasma panel display (PDP) mainly is BaMgAl 10O 17: Eu 2+But BAM exists less stable and the VUV optical excitation issues optical efficiency and the lower problem of luminous efficiency (BAM).Working long hours down, BAM powder luminous quantum efficiency reduces significantly, also skew to some extent of emmission spectrum simultaneously, influence illumination and display effect.
Rare earth blue emitting material of the present invention is synthetic simple, good stability, and luminosity is high, and especially under 254 nm optical excitation, its optimal luminescent intensity is about BaMgAl 10O 17: Eu 2+(BAM) 1.1 times.
     
Summary of the invention
The purpose of this invention is to provide a kind of under ultraviolet excitation luminous stronger blue emitting material.
Another object of the present invention provides the preparation method of above-mentioned luminescent material.
Blue emitting material of the present invention, its chemical constitution expression is:
Ba 1-xEu xCa 2MgSi 2O 8(abbreviating BCMSO as)
Wherein, x is active ions Eu 2+The molar percentage coefficient that relative alkaline earth metal ion Ba accounts for, span: 0.001≤x≤0.1.
The selected substrate material of the present invention is BaCa 2MgSi 2O 8Luminescence center is the bivalent rare earth europium ion.Under ultraviolet excitation, bivalent rare earth europium ion Eu 2+Blue light-emitting in matrix.
The preparation method of above-mentioned luminescent material comprises the steps: accurately to take by weighing raw material according to the chemical constitution expression of above-mentioned fluorescent material, and fully ground and mixed is even; With mixture roasting in hydrogen and nitrogen mixture body, naturally cool to room temperature then; Last products therefrom takes out to grind and promptly obtains the finished product.
In above-mentioned preparation method, said hydrogen and nitrogen volume ratio are 1:3.
In above-mentioned preparation method, described raw material is: the mixture of one or more in rare earth oxide, rare-earth oxalate, rare earth carbonate, the rare earth nitrate; The mixture of one or more of alkaline earth metal carbonate, alkine earth metal nitrate; Natural manganese dioxide, magnesium basic carbonate, Marinco H, the mixture of one or more of magnesium nitrate; Silicon-dioxide, ammonium chloride.
In above-mentioned preparation method, said sintering temperature is the 1100-1200 degree; Calcination time is 4-hour.
Compared with prior art, the present invention has following beneficial effect: luminescent material of the present invention and existing fluorescent material BaMgAl 10O 17(BAM) compare under 254 nm optical excitation luminous byer force, be about present commercial fluorescent material BaMgAl 10O 17(BAM) 110%, simultaneously, this fluorescent material excites at vacuum-ultraviolet light (147 nm, 172 nm) also has down luminosity preferably.
Luminescent material of the present invention adopts traditional high temperature solid-state method synthetic, and preparation technology is simple, easy handling, and equipment is easy to get, operational safety, condition is controlled easily.
Description of drawings
Fig. 1 a is the emmission spectrum of blue emitting material under 147 nm optical excitation of embodiment 8.
Fig. 1 b is the emmission spectrum of blue emitting material under 172 nm optical excitation of embodiment 8.
Fig. 1 c is the emmission spectrum of blue emitting material under 254 nm optical excitation of embodiment 8.
Fig. 2 is luminescent material Ba of the present invention 1-xEu xCa 2MgSi 2O 8(BCMSO) (embodiment 8) and commercial blue colour fluorescent powder BaMgAl 10O 17(BAM) chromaticity coordinates figure (1:Ba 1-xEu xCa 2MgSi 2O 8(BCMSO); 2:BaMgAl 10O 17(BAM)).
Fig. 3 is BaMgAl 10O 17(BAM) and Ba 1-xEu xCa 2MgSi 2O 8(BCMSO) (embodiment 8) respectively 147,172, the luminous photo when 254nm excites.
(active ions refer to bivalent rare earth Eu to the different active ions of the serial blue emitting material that obtains for the present invention 2+Ion) the concentration sample has similar spectral quality, so other similar composition materials do not provide spectrum and chromaticity coordinates thereof at accompanying drawing.
Embodiment
Embodiment 1:
Take by weighing europium sesquioxide (Eu 2O 3) 0.0004 g, barium carbonate (BaCO 3) 0.4140 g, lime carbonate (CaCO 3) 0.4204 g, magnesium basic carbonate (Mg (OH) 24MgCO 36H 2O) 0.2115 g silicon-dioxide (SiO 2) 0.2523 g, after ammonium chloride (NH4Cl) 0.0260g fully grinds in agate mortar and mixes, roasting in hydrogen and nitrogen (hydrogen and nitrogen volume ratio are 1:3) the mixed gas reducing atmosphere, 1200 ℃ of following sintering 4 hours.Naturally cool to room temperature.Sample is taken out grinding, finally obtain product.
Embodiment 2:
Take by weighing europium sesquioxide (Eu 2O 3) 0.0007 g, barium carbonate (BaCO 3) 0.4136 g, lime carbonate (CaCO 3) 0.4204 g, magnesium basic carbonate (Mg (OH) 24MgCO 36H 2O) 0.2115 g silicon-dioxide (SiO 2) 0.2523 g, after ammonium chloride (NH4Cl) 0.0260 g fully grinds in agate mortar and mixes, roasting in hydrogen and nitrogen (hydrogen and nitrogen volume ratio are 1:3) the mixed gas reducing atmosphere, 1200 ℃ of following sintering 4 hours.Naturally cool to room temperature.Sample is taken out grinding, finally obtain product.
Embodiment 3:
Take by weighing europium sesquioxide (Eu 2O 3) 0.0011 g, barium carbonate (BaCO 3) 0.4132 g, lime carbonate (CaCO 3) 0.4204 g, magnesium basic carbonate (Mg (OH) 24MgCO 36H 2O) 0.2115 g silicon-dioxide (SiO 2) 0.2523 g, after ammonium chloride (NH4Cl) 0.0260g fully grinds in agate mortar and mixes, roasting in hydrogen and nitrogen (hydrogen and nitrogen volume ratio are 1:3) the mixed gas reducing atmosphere, 1200 ℃ of following sintering 4 hours.Naturally cool to room temperature.Sample is taken out grinding, finally obtain product.
Embodiment 4:
Take by weighing europium sesquioxide (Eu 2O 3) 0.0018 g, barium carbonate (BaCO 3) 0.4123 g, lime carbonate (CaCO 3) 0.4204 g, magnesium basic carbonate (Mg (OH) 24MgCO 36H 2O) 0.2115 g silicon-dioxide (SiO 2) 0.2523 g, after ammonium chloride (NH4Cl) 0.0260g fully grinds in agate mortar and mixes, roasting in hydrogen and nitrogen (hydrogen and nitrogen volume ratio are 1:3) the mixed gas reducing atmosphere, 1200 ℃ of following sintering 4 hours.Naturally cool to room temperature.Sample is taken out grinding, finally obtain product.
Embodiment 5:
Take by weighing europium sesquioxide (Eu 2O 3) 0.0030 g, barium carbonate (BaCO 3) 0.4111 g, lime carbonate (CaCO 3) 0.4204 g, magnesium basic carbonate (Mg (OH) 24MgCO 36H 2O) 0.2115 g silicon-dioxide (SiO 2) 0.2523 g, after ammonium chloride (NH4Cl) 0.0260g fully grinds in agate mortar and mixes, roasting in hydrogen and nitrogen (hydrogen and nitrogen volume ratio are 1:3) the mixed gas reducing atmosphere, 1200 ℃ of following sintering 4 hours.Naturally cool to room temperature.Sample is taken out grinding, finally obtain product.
Embodiment 6:
Take by weighing europium sesquioxide (Eu 2O 3) 0.0037 g, barium carbonate (BaCO 3) 0.4103 g, lime carbonate (CaCO 3) 0.4204 g, magnesium basic carbonate (Mg (OH) 24MgCO 36H 2O) 0.2115 g silicon-dioxide (SiO 2) 0.2523 g, after ammonium chloride (NH4Cl) 0.0260g fully grinds in agate mortar and mixes, roasting in hydrogen and nitrogen (hydrogen and nitrogen volume ratio are 1:3) the mixed gas reducing atmosphere, 1200 ℃ of following sintering 4 hours.Naturally cool to room temperature.Sample is taken out grinding, finally obtain product.
Embodiment 7:
Take by weighing europium sesquioxide (Eu 2O 3) 0.0074 g, barium carbonate (BaCO 3) 0.4061 g, lime carbonate (CaCO 3) 0.4204 g, magnesium basic carbonate (Mg (OH) 24MgCO 36H 2O) 0.2115 g silicon-dioxide (SiO 2) 0.2523 g, after ammonium chloride (NH4Cl) 0.0260g fully grinds in agate mortar and mixes, roasting in hydrogen and nitrogen (hydrogen and nitrogen volume ratio are 1:3) the mixed gas reducing atmosphere, 1200 ℃ of following sintering 4 hours.Naturally cool to room temperature.Sample is taken out grinding, finally obtain product.
Embodiment 8:
Take by weighing europium sesquioxide (Eu 2O 3) 0.0111 g, barium carbonate (BaCO 3) 0.4020 g, lime carbonate (CaCO 3) 0.4204 g, magnesium basic carbonate (Mg (OH) 24MgCO 36H 2O) 0.2115 g silicon-dioxide (SiO 2) 0.2523 g, after ammonium chloride (NH4Cl) 0.0260g fully grinds in agate mortar and mixes, roasting in hydrogen and nitrogen (hydrogen and nitrogen volume ratio are 1:3) the mixed gas reducing atmosphere, 1200 ℃ of following sintering 4 hours.Naturally cool to room temperature.Sample is taken out grinding, finally obtain product.
Embodiment 9:
Take by weighing europium sesquioxide (Eu 2O 3) 0.0148 g, barium carbonate (BaCO 3) 0.3978 g, lime carbonate (CaCO 3) 0.4204 g, magnesium basic carbonate (Mg (OH) 24MgCO 36H 2O) 0.2115 g silicon-dioxide (SiO 2) 0.2523 g, after ammonium chloride (NH4Cl) 0.0260g fully grinds in agate mortar and mixes, roasting in hydrogen and nitrogen (hydrogen and nitrogen volume ratio are 1:3) the mixed gas reducing atmosphere, 1200 ℃ of following sintering 4 hours.Naturally cool to room temperature.Sample is taken out grinding, finally obtain product.
Embodiment 10:
Take by weighing europium sesquioxide (Eu 2O 3) 0.0185 g, barium carbonate (BaCO 3) 0.3937 g, lime carbonate (CaCO 3) 0.4204 g, magnesium basic carbonate (Mg (OH) 24MgCO 36H 2O) 0.2115 g silicon-dioxide (SiO 2) 0.2523 g, after ammonium chloride (NH4Cl) 0.0260g fully grinds in agate mortar and mixes, roasting in hydrogen and nitrogen (hydrogen and nitrogen volume ratio are 1:3) the mixed gas reducing atmosphere, 1200 ℃ of following sintering 4 hours.Naturally cool to room temperature.Sample is taken out grinding, finally obtain product.
Embodiment 11:
Take by weighing europium sesquioxide (Eu 2O 3) 0.0222 g, barium carbonate (BaCO 3) 0.3895 g, lime carbonate (CaCO 3) 0.4204 g, magnesium basic carbonate (Mg (OH) 24MgCO 36H 2O) 0.2115 g silicon-dioxide (SiO 2) 0.2523 g, after ammonium chloride (NH4Cl) 0.0260g fully grinds in agate mortar and mixes, roasting in hydrogen and nitrogen (hydrogen and nitrogen volume ratio are 1:3) the mixed gas reducing atmosphere, 1200 ℃ of following sintering 4 hours.Naturally cool to room temperature.Sample is taken out grinding, finally obtain product.
Embodiment 12:
Take by weighing europium sesquioxide (Eu 2O 3) 0.0259 g, barium carbonate (BaCO 3) 0.3854 g, lime carbonate (CaCO 3) 0.4204 g, magnesium basic carbonate (Mg (OH) 24MgCO 36H 2O) 0.2115 g silicon-dioxide (SiO 2) 0.2523 g, after ammonium chloride (NH4Cl) 0.0260g fully grinds in agate mortar and mixes, roasting in hydrogen and nitrogen (hydrogen and nitrogen volume ratio are 1:3) the mixed gas reducing atmosphere, 1200 ℃ of following sintering 4 hours.Naturally cool to room temperature.Sample is taken out grinding, finally obtain product.
Embodiment 13:
Take by weighing europium sesquioxide (Eu 2O 3) 0.0296 g, barium carbonate (BaCO 3) 0.3813 g, lime carbonate (CaCO 3) 0.4204 g, magnesium basic carbonate (Mg (OH) 24MgCO 36H 2O) 0.2115 g silicon-dioxide (SiO 2) 0.2523 g, after ammonium chloride (NH4Cl) 0.0260g fully grinds in agate mortar and mixes, roasting in hydrogen and nitrogen (hydrogen and nitrogen volume ratio are 1:3) the mixed gas reducing atmosphere, 1200 ℃ of following sintering 4 hours.Naturally cool to room temperature.Sample is taken out grinding, finally obtain product.
Embodiment 14:
Take by weighing europium sesquioxide (Eu 2O 3) 0.0370 g, barium carbonate (BaCO 3) 0.3730 g, lime carbonate (CaCO 3) 0.4204 g, magnesium basic carbonate (Mg (OH) 24MgCO 36H 2O) 0.2115 g silicon-dioxide (SiO 2) 0.2523 g, after ammonium chloride (NH4Cl) 0.0260g fully grinds in agate mortar and mixes, roasting in hydrogen and nitrogen (hydrogen and nitrogen volume ratio are 1:3) the mixed gas reducing atmosphere, 1200 ℃ of following sintering 4 hours.Naturally cool to room temperature.Sample is taken out grinding, finally obtain product.
 
Blue emitting material of the present invention excites down the emmission spectrum that records them at UV-light (254 nm) vacuum-ultraviolet light (147 nm, 172 nm), and is shown among Fig. 1.Can observe: Ba 1-xEu xCa 2MgSi 2O 8Series luminescent material (embodiment 1-14) blue light-emitting, the emission figure (Fig. 1) of representative sample (embodiment 8) shows that emission wavelength is about 430 nanometers; Series phosphor powder of the present invention and commercial blue colour fluorescent powder BaMgAl 10O 17(BAM) chromaticity coordinates is (embodiment 8) in Fig. 2, and wherein 1,2 is respectively Ba 1-xEu xCa 2MgSi 2O 8(BCMSO) and BaMgAl 10O 17(BAM) chromaticity coordinates.
The chromaticity coordinates of contrast blue colour fluorescent powder can be seen, blue colour fluorescent powder of the present invention and commercial at present blue powder BaMgAl 10O 17(BAM) chromaticity coordinates is close, and excites down at 254 nm, and emissive porwer is about 1.1 times of BAM.

Claims (5)

1. blue emitting material, its chemical constitution expression is:
Ba 1-xEu xCa 2MgSi 2O 8
Wherein, x is active ions Eu 2+The molar percentage coefficient that relative alkaline earth metal ion Ba accounts for, span: 0.001≤x≤0.1.
2. the preparation method of the said luminescent material of claim 1 is characterized in that comprising the steps: that the chemical constitution expression according to above-mentioned fluorescent material accurately takes by weighing raw material, and fully ground and mixed is even; With mixture roasting in hydrogen and nitrogen mixture body, naturally cool to room temperature then; Last products therefrom takes out to grind and promptly obtains the finished product.
3. preparation method as claimed in claim 2 is characterized in that said hydrogen and nitrogen volume ratio are 1:3.
4. preparation method as claimed in claim 2 is characterized in that described raw material is: the mixture of one or more in rare earth oxide, rare-earth oxalate, rare earth carbonate, the rare earth nitrate; The mixture of one or more of alkaline earth metal carbonate, alkine earth metal nitrate; Natural manganese dioxide, magnesium basic carbonate, Marinco H, the mixture of one or more of magnesium nitrate; Silicon-dioxide, ammonium chloride.
5. the described preparation method of claim 2 is characterized in that, said sintering temperature is the 1100-1200 degree; Calcination time is 4 hours.
CN2012100117073A 2012-01-16 2012-01-16 Blue light-emitting material and preparation method thereof Pending CN102533268A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102925144A (en) * 2012-11-14 2013-02-13 合肥工业大学 White light LED (light emitting diode) blue fluorescent material applicable to near ultraviolet wavelength excitation and preparation method thereof
CN104073255A (en) * 2014-06-30 2014-10-01 苏州大学 Zirconium silicate salt blue fluorescent powder, preparation method and application thereof
CN106118635A (en) * 2016-06-24 2016-11-16 东台市天源荧光材料有限公司 A kind of white light LEDs silicate yellow fluorescent powder and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Y. YONESAKI, ET AL.: "Crystal structure of BaCa2MgSi2O8 and the photoluminescent properties activated by Eu2+", 《JOURNAL OF LUMINESCENCE》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102925144A (en) * 2012-11-14 2013-02-13 合肥工业大学 White light LED (light emitting diode) blue fluorescent material applicable to near ultraviolet wavelength excitation and preparation method thereof
CN104073255A (en) * 2014-06-30 2014-10-01 苏州大学 Zirconium silicate salt blue fluorescent powder, preparation method and application thereof
CN104073255B (en) * 2014-06-30 2015-12-09 苏州大学 A kind of silicic acid zirconates blue colour fluorescent powder, preparation method and application thereof
CN106118635A (en) * 2016-06-24 2016-11-16 东台市天源荧光材料有限公司 A kind of white light LEDs silicate yellow fluorescent powder and preparation method thereof

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Application publication date: 20120704