CN102304360A - Red divalent bismuth ion doping calcium phosphate fluorescent material and preparation method thereof - Google Patents
Red divalent bismuth ion doping calcium phosphate fluorescent material and preparation method thereof Download PDFInfo
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- CN102304360A CN102304360A CN201110185679A CN201110185679A CN102304360A CN 102304360 A CN102304360 A CN 102304360A CN 201110185679 A CN201110185679 A CN 201110185679A CN 201110185679 A CN201110185679 A CN 201110185679A CN 102304360 A CN102304360 A CN 102304360A
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Abstract
The invention relates to a preparation method of a red divalent bismuth ion doping calcium phosphate fluorescent material, which comprises the following steps of: taking a compound raw material containing calcium, phosphorus and bismuth, wherein the molar ratio of calcium: phosphorus: bismuth: 2 (1-x): 2: 2x, wherein X is larger than or equal to 0.00001 and is less than or equal to 0.08; grinding, uniformly mixing and then presintering, and controlling the temperature to be in the range of 900 to 1200 DEG C; after presintering, grinding again, uniformly mixing and then burning at high temperature, controlling the temperature to be in the range of 800-1000 DEG C; and finally placing a sample at the reducing atmosphere of 900-1200 DEGC for reacting for 15 minutes to 10 hours. The fluorescent material prepared by the method has the ultraviolet and blue light spectral region absorption function, has red fluorescent lights covering 600nm-750nm sections under the excitation of ultraviolet or blue lights; the fluorescence lifetime of the fluorescent material is about 10 microseconds; the fluorescence light of the fluorescent material has good heat resistance hardening characteristic; when the temperature is risen from 10k to the room temperature, the fluorescent intensity of the fluorescent material is reduced by less than 10%, and the fluorescence lifetime of the fluorescent material is shortened by less than 5%.
Description
Technical field
The present invention relates to the luminescent material research field, specifically is a kind of divalence bismuth ion doping phosphoric acid calred look fluorescent material and preparation method thereof.
Background technology
The solid state LED lighting engineering has that energy consumption is low, luminous efficiency is high, long service life, not mercurous, volume is little, advantage such as cracky not, thereby is widely used in general lighting, automobile, traffic, imaging, agricultural, medicine and other fields gradually.The research in St Babara branch school, University of California shows, if replace traditional bulb with the white light LEDs (WLED) of 150 lumens/watt, is only the U.S. to 2025 and just can saves 1,150 hundred million dollars at lighting field, so just can build 133 power house less, few emission greenhouse CO
225,800 ten thousand tons of gases.Given this, recently in the ascendant for the research of LED especially WLED.Obtain based on LED and fluorescent material coupling in schemes of WLED at all, the most simply be with a kind of blue-ray LED with have the coupling of blue light absorption yellow fluorescent powder.Commercial at present WLED product, blue light InGaN LED and Y
3Al
5O
12: Ce
3+(YAG:Ce) combination (after this, abbreviating BLED+YAG:Ce as) just is being based on this scheme.The efficient of this BLED+YAG:Ce product is better than compact fluorescent lamp, but compares with incandescent light, halogen lamp (colour temperature is usually located at 2500-3200K, and colour rendering index CRI is 100), and its inferior position is that colour temperature is higher, is usually located at 4500-6500K; CRI is lower, usually less than 80.In order suitably to reduce the BLED+YAG:Ce colour temperature, improve its colour rendering index CRI, obtain the warm tones white light LEDs, need to introduce the fluorescent material of another long wavelength emission usually, for example red.The new luminescent material that adds has absorption in blue region usually.
In view of this consideration, some Eu
2+, Ce
3+Or Mn
2+Novel fluorescent materials such as adulterated nitride, oxynitride, silicate, aluminate are reported in succession.Wherein nitride or oxynitride have especially excellent spectral quality, and quantum yield surpasses 70%, are considered to the fluorescent material of tool potentiality, thereby recently more active to the research of these compounds.But synthetic these materials need compare exacting terms, for example Eu usually
2+Doping β-SiAlON need be 1900
oC, 10 normal atmosphere nitrogen atmospheres are synthetic down.This High Temperature High Pressure is very high to the requirement of equipment.In addition, these researchs mostly concentrate on rare earth ion or doped transition metal ions, divalence bismuth ion Bi
2+Adulterated report is very few.
Summary of the invention
The objective of the invention is to the deficiency to prior art, a kind of divalence bismuth ion doping phosphoric acid calcium fluorescent material and preparation method thereof is provided, the present invention can be at lesser temps (≤1200
oC) down preparation adopts that the lower bismuth of price is adulterated to have go out a calcium phosphate red fluorescence powder of ability of good resistance hot-quenching.
Realize that the technical scheme that the object of the invention adopted comprises:
A kind of divalence bismuth ion doping phosphoric acid calred look Preparation of Fluorescent Material method comprises the steps:
(1) take by weighing the raw materials of compound of calcic, phosphorus and bismuth, its mol ratio is pressed calcium: phosphorus: bismuth=2 (1-x): 2: 2x, wherein 0.00001≤x≤0.08;
(2) the above-mentioned raw material that weighs up after grinding mixing, carries out pre-burning, controlled temperature 900～1200
oC; (3) sample after the pre-burning is taken out, behind the regrinding mixing, carry out high-temperature firing, controlled temperature 800-1000
oC;
(4) sample after will firing is put in 900～1200
oReaction is 15 minutes～10 hours under the C reducing atmosphere, can make required red fluorescence material.
Said calcareous raw materials of compound is a lime carbonate, Calcium hydrogen carbonate, calcium oxide, nitrocalcite, any in caoxalate and the calcium acetate; Said phosphorated raw materials of compound is a primary ammonium phosphate, ammonium hydrogen phosphate, any in phosphoric acid and the Vanadium Pentoxide in FLAKES; Said bismuthiferous raw materials of compound is a bismuthous oxide bismuth trioxide, bismuth meal, any in Bismuth Subcarbonate and the bismuth chloride.
The carbon monoxide that said reducing atmosphere produces for the Graphite Powder 99 incomplete combustion, the mixed gas of hydrogen or nitrogen and hydrogen.
Compared with prior art, the present invention has following advantage and beneficial effect: the characteristic of the fluorescent material of the inventive method preparation is: (230～330nm) excite down and have covering 600nm～red fluorescence in 750nm interval (1) UV-light; Has the interval red fluorescence of covering 600nm～750nm under (2) 350～520nm optical excitation; (3) the red fluorescence life-span is about 10 microseconds; (4) its fluorescence has good heat resistanceheat resistant cancellation characteristic, and temperature rises to room temperature by 10K, and fluorescence intensity reduces less than 10%, and fluorescence lifetime shortens less than 5%.
Description of drawings
Fig. 1 is the blue-light excited fluorescence spectrum of bismuth doping phosphoric acid calcium down of different wave length of the present invention: the corresponding excitation wavelength 465nm of solid line, the corresponding excitation wavelength 412nm of dotted line;
Fig. 2 is the ultraviolet region excitation spectrum of bismuth doping phosphoric acid calcium of the present invention: the corresponding emission wavelength 652nm of solid line, the corresponding emission wavelength 682nm of dotted line;
Fig. 3 is the blue light region excitation spectrum of bismuth doping phosphoric acid calcium of the present invention: the corresponding emission wavelength 652nm of solid line, the corresponding emission wavelength 682nm of dotted line;
Fig. 4 is the fluorescence decay curve of bismuth doping phosphoric acid calcium of the present invention; Wherein symbol zero is represented emission wavelength 652nm, the experimental result of excitation wavelength 465nm, and the black line on this symbol is a single index attenuation equation fitting result; Both degrees of correlation 99.71%, match obtains fluorescence lifetime 8112ns; Symbol ● represent emission wavelength 682nm, the experimental result of excitation wavelength 412nm, the black line on this symbol is a single index attenuation equation fitting result, both degrees of correlation 99.93%, match obtains fluorescence lifetime 12498ns;
Fig. 5 is that temperature of the present invention is to the fluorescence intensity of bismuth doping phosphoric acid calcium and the influence in life-span;
Fig. 6 is the fluorescence spectrum of bismuth doping phosphoric acid calcium under the differing temps of the present invention.
Embodiment
Below in conjunction with specific embodiment the present invention is done further concrete detailed description the in detail, but embodiment of the present invention is not limited thereto, the processing parameter for not indicating especially can carry out with reference to routine techniques.
Embodiment 1
Choose lime carbonate, primary ammonium phosphate and bismuthous oxide bismuth trioxide are made starting raw material, press Ca
2 (1-x)P
2O
7: mol ratio, i.e. Ca: P: Bi shown in the 2xBi (x=0.05)=1.9: 2: 0.1, take by weighing three kinds of raw materials respectively, the control mixture total weight is 100 grams.100 gram mixtures are put into corundum crucible after milling mixing, then crucible is put into high-temperature electric resistance furnace.Accurately the control temperature rise rate is controlled the phosphorus compound decomposition reaction velocity, prevents that mixture from overflowing from crucible, and sample is 500
oC pre-burning 10 hours.Sample after the pre-burning is taken out, behind the regrinding mixing, put into crucible, 1100
oC fired 10 hours twice, and the centre is ground even once more.Fired sample is put in 1100
oC H
2The middle processing 15 minutes promptly makes divalence bismuth doping red fluorescence material.X-ray diffraction analysis shows that it is Ca
2P
2O
7Pure phase.As shown in Figure 1, this fluorescent material excites down at 465nm can produce the red fluorescence that peak position is positioned at 652nm, excites down at 412nm to produce the fluorescence that peak position is positioned at 682nm.These fluorescence cover the 600-750nm spectral region.Like Fig. 2 and shown in Figure 3, the excitation spectrum of corresponding 652nm fluorescence is by 258nm, 280nm, and four excitation peaks of 412nm and 465nm are formed, and wherein 280nm is a highest peak; The excitation spectrum of corresponding 682nm fluorescence is by 258nm, and three excitation peaks of 280nm and 465nm are formed, and wherein 258nm is a highest peak.The life-span of 652nm and 682nm fluorescence is respectively 8112ns and 12498ns, as shown in Figure 4.As shown in Figure 5, raise with temperature, fluorescence lifetime shortens slightly, and fluorescence intensity has slightly and weakens, and fluorescence peak has the red shift (see figure 6) slightly.Rise to 300K by 10K, the lost of life 5.7%, strength reduction 8.1%, this shows that this luminescent material has the property of heat resistanceheat resistant cancellation preferably.
Embodiment 2
Choose Calcium hydrogen carbonate, primary ammonium phosphate and bismuth meal are made starting raw material, press Ca
2 (1-x)P
2O
7: mol ratio, i.e. Ca: P: Bi shown in the 2xBi (x=0.00001)=1.99998: 2: 0.00002, take by weighing three kinds of raw materials respectively, the control mixture total weight is 100 grams.100 gram mixtures are put into platinum crucible after milling mixing, then crucible is put into high-temperature electric resistance furnace.Accurately the control temperature rise rate is controlled the phosphorus compound decomposition reaction velocity, prevents that mixture from overflowing from crucible, and sample is 400
oC pre-burning 10 hours.Sample after the pre-burning is taken out, behind the regrinding mixing, put into crucible, 1200
oC fired 5 hours twice, and the centre is ground even once more.Fired sample is put in 1200 degrees centigrade of N
2+ H
2The middle processing 1 hour promptly makes divalence bismuth doping red fluorescence material.X-ray diffraction analysis shows that it is Ca
2P
2O
7Pure phase.The spectral quality of fluorescent material and heat resistanceheat resistant cancellation performance are with similar among the embodiment 1.
Embodiment 3
Choose calcium oxide, ammonium hydrogen phosphate and Bismuth Subcarbonate are made starting raw material, press Ca
2 (1-x)P
2O
7: mol ratio, i.e. Ca: P: Bi shown in the 2xBi (x=0.08)=1.84: 2: 0.16, take by weighing three kinds of raw materials respectively, the control mixture total weight is 100 grams.100 gram mixtures are put into platinum crucible after milling mixing, then crucible is put into high-temperature electric resistance furnace.Accurately the control temperature rise rate is controlled the phosphorus compound decomposition reaction velocity, prevents that mixture from overflowing from crucible, and sample is 800
oC pre-burning 5 hours.Sample after the pre-burning is taken out, behind the regrinding mixing, put into crucible, 1100
oC fired 20 hours twice, and the centre is ground even once more.Fired sample is put in 1100 degrees centigrade of imperfect combustion Graphite Powder 99s and handled 1 hour, promptly makes divalence bismuth doping red fluorescence material.X-ray diffraction analysis shows that its principal phase is Ca
2P
2O
7The spectral quality of fluorescent material and heat resistanceheat resistant cancellation performance are with similar among the embodiment 1.
Embodiment 4
Choose caoxalate, phosphoric acid and bismuth chloride are made starting raw material, press Ca
2 (1-x)P
2O
7: mol ratio, i.e. Ca: P: Bi shown in the 2xBi (x=0.05)=1.90: 2: 0.10, take by weighing three kinds of raw materials respectively, the control mixture total weight is 100 grams.100 gram mixtures are put into platinum crucible after milling mixing, then crucible is put into high-temperature electric resistance furnace.Accurately the control temperature rise rate is controlled the phosphorus compound decomposition reaction velocity, prevents that mixture from overflowing from crucible, and sample is 600
oC pre-burning 8 hours.Sample after the pre-burning is taken out, behind the regrinding mixing, put into crucible, 1100
oC fired 15 hours twice, and the centre is ground even once more.Fired sample is put among 1100 degrees centigrade of CO and handled 4 hours, promptly makes divalence bismuth doping red fluorescence material.X-ray diffraction analysis shows that its principal phase is Ca
2P
2O
7The spectral quality of fluorescent material and heat resistanceheat resistant cancellation performance are with similar among the embodiment 1.
Embodiment 5
Choose calcium acetate, Vanadium Pentoxide in FLAKES and bismuthous oxide bismuth trioxide are made starting raw material, press Ca
2 (1-x)P
2O
7: mol ratio, i.e. Ca: P: Bi shown in the 2xBi (x=0.01)=1.98: 2: 0.02, take by weighing three kinds of raw materials respectively, the control mixture total weight is 100 grams.100 gram mixtures are put into platinum crucible after milling mixing, then crucible is put into high-temperature electric resistance furnace.Accurately the control temperature rise rate is controlled the phosphorus compound decomposition reaction velocity, prevents that mixture from overflowing from crucible, and sample is 700
oC pre-burning 10 hours.Sample after the pre-burning is taken out, behind the regrinding mixing, put into crucible, 1100
oC fired 5 hours twice, and the centre is ground even once more.Fired sample is put in 1100 degrees centigrade of nitrogen and hydrogen mixtures and handled 10 hours, promptly makes divalence bismuth doping red fluorescence material.X-ray diffraction analysis shows that it is Ca
2P
2O
7Pure phase.The spectral quality of fluorescent material and heat resistanceheat resistant cancellation performance are with similar among the embodiment 1.
Embodiment 6
Choose nitrocalcite, Vanadium Pentoxide in FLAKES and bismuth meal are made starting raw material, press Ca
2 (1-x)P
2O
7: mol ratio, i.e. Ca: P: Bi shown in the 2xBi (x=0.01)=1.98: 2: 0.02, take by weighing three kinds of raw materials respectively, the control mixture total weight is 100 grams.100 gram mixtures are put into platinum crucible after milling mixing, then crucible is put into high-temperature electric resistance furnace.Accurately the control temperature rise rate is controlled the phosphorus compound decomposition reaction velocity, prevents that mixture from overflowing from crucible, and sample is 500
oC pre-burning 10 hours.Sample after the pre-burning is taken out, behind the regrinding mixing, put into crucible, 1100
oC fired 10 hours twice, and the centre is ground even once more.Fired sample is put among the CO that 1100 degrees centigrade of carbon dusts produce and handled 0.5 hour, promptly makes divalence bismuth doping red fluorescence material.X-ray diffraction analysis shows that it is Ca
2P
2O
7Pure phase.The spectral quality of fluorescent material and heat resistanceheat resistant cancellation performance are with similar among the embodiment 1.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (3)
1. a divalence bismuth ion doping phosphoric acid calred look Preparation of Fluorescent Material method is characterized in that, comprises the steps:
(1) take by weighing the raw materials of compound of calcic, phosphorus and bismuth, its mol ratio is pressed calcium: phosphorus: bismuth=2 (1-x): 2: 2x, wherein 0.00001≤x≤0.08;
The above-mentioned raw material that weighs up after grinding mixing, carries out pre-burning, controlled temperature 900～1200
oC; (3) sample after the pre-burning is taken out, behind the regrinding mixing, carry out high-temperature firing, controlled temperature 800～1000
oC;
(4) sample after will firing is put in 900～1200
oReaction is 15 minutes～10 hours under the C reducing atmosphere, can make required red fluorescence material.
2. preparation method according to claim 1 is characterized in that, said calcareous raw materials of compound is a lime carbonate, Calcium hydrogen carbonate, calcium oxide, nitrocalcite, any in caoxalate and the calcium acetate; Said phosphorated raw materials of compound is a primary ammonium phosphate, ammonium hydrogen phosphate, any in phosphoric acid and the Vanadium Pentoxide in FLAKES; Said bismuthiferous raw materials of compound is a bismuthous oxide bismuth trioxide, bismuth meal, any in Bismuth Subcarbonate and the bismuth chloride.
3. preparation method according to claim 1 is characterized in that, the carbon monoxide that said reducing atmosphere produces for the Graphite Powder 99 incomplete combustion, the mixed gas of hydrogen or nitrogen and hydrogen.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586871A (en) * | 2012-03-29 | 2012-07-18 | 华南理工大学 | Luminous crystal containing bismuth and with ultra wide band of 1-3 micrometers and preparation method thereof |
| CN104371716A (en) * | 2014-11-18 | 2015-02-25 | 井冈山大学 | Divalent bismuth ion doped red fluorescent material and preparation method thereof |
-
2011
- 2011-07-05 CN CN201110185679A patent/CN102304360A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| MINGYING PENG ET AL.: "Broadband NIR photoluminescence from Bi-doped Ba2P2O7 crystals: Insights into the nature of NIR-emitting Bismuth centers", 《OPTICS EXPRESS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586871A (en) * | 2012-03-29 | 2012-07-18 | 华南理工大学 | Luminous crystal containing bismuth and with ultra wide band of 1-3 micrometers and preparation method thereof |
| CN104371716A (en) * | 2014-11-18 | 2015-02-25 | 井冈山大学 | Divalent bismuth ion doped red fluorescent material and preparation method thereof |
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Application publication date: 20120104 |