CN103059843A - Orange-red rear-earth phosphors and preparation method thereof - Google Patents
Orange-red rear-earth phosphors and preparation method thereof Download PDFInfo
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- CN103059843A CN103059843A CN201310012418XA CN201310012418A CN103059843A CN 103059843 A CN103059843 A CN 103059843A CN 201310012418X A CN201310012418X A CN 201310012418XA CN 201310012418 A CN201310012418 A CN 201310012418A CN 103059843 A CN103059843 A CN 103059843A
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Abstract
The invention relates to orange-red rear-earth phosphors and a preparation method thereof. The orange-red rear-earth phosphors are prepared from strontium carbonate, calcium chloride, strontium chloride hexahydrate, strontium fluoride, strontium bromide, aluminum hydroxide, boric acid and europium oxide serving as raw materials by adopting a high-temperature solid state method. The preparation method comprises the following steps of: uniformly mixing the raw materials according to proportions, pre-sintering for 3-6 hours at 400-500 DEG C, cooling to a room temperature, taking out the raw materials and uniformly grinding again, reducing and sintering at a CO atmosphere for 4-10 hours at 1000-1200 DEG C, and grinding fine obtained sinters to obtain final products. The orange-red rear-earth phosphors have high luminous efficiency, good stability and very high quenching temperature and are suitable for InGaN chips giving out ultraviolet lights with about 400nm wavelength.
Description
Technical field
The present invention relates to a kind of orange red fluorescent RE powder and preparation method thereof, specifically, is orange red fluorescent RE powder of a kind of high thermal quenching temperature that is applicable to 400 nm left and right sides near ultraviolet excitations and preparation method thereof.Belong to the rare earth material preparation field.
Background technology
White light emitting diode (W-LED, white-light-emitting diode) solid state lighting has a lot of significantly advantages with respect to traditional lighting engineering (such as incandescent light, luminescent lamp etc.), has become people's study hotspot at present.White light LEDs is mainly realized white light by two kinds of approach at present: a kind of is fluorescent conversion type, namely uses single led chip and phosphor combination luminous; Another kind method is to adopt red, green, blue three-color LED chip portfolio luminous, i.e. the multi-chip white light LEDs.
Known business-like white light LEDs still obtains by first method (fluorescent conversion type).Business-like white light LEDs is that the blue light (approximately 450 nm) that Japanese Nichia company uses the GaN base LED chip to be sent out comes excitation rare-earth fluorescent material YAG:Ce the earliest
3+Yellow light-emitting low temperature, but this class white light LEDs cause its colour rendering index bad, and its luminous efficiency is low because it lacks the spectrum in ruddiness zone.The emission wavelength of current I nGaN chip blue shift can provide higher excitation energy for fluorescent material to the near ultraviolet region.
Be applied at present about 400 nm on the purple pipe InGaN chip the main or traditional fluorescent material of three primary colors fluorescent powder as: blue powder is BaMgAl
10O
17: Eu
2+, green powder is ZnS:(Cu
+, Al
3+), rouge and powder then is Y
2O
2S:Eu
3+Deng.These fluorescent material excite not strong in the near ultraviolet region, efficient is not high, and are minimum with red light emitting phosphor efficient again in the middle of this, and unstable, so that the white light LEDs luminous efficiency can not promote up.
Mainly concentrate on the series phosphor powder that the trivalent europium excites for current white light LEDs with rouge and powder, be disclosed a kind of europkium-activated red fluorescent powder for light-emitting diodes and preparation method thereof among the CN 102191048A such as China Patent Publication No., and China Patent Publication No. is disclosed a kind of europkium-activated molybdate red phosphor and preparation method thereof among the CN102212364A, utilizes exactly Eu
3+Red emission.Because Eu
3+To excite be 4
f-4
fTransition, assimilated efficiency is low in the near-ultraviolet light district, causes its red light-emitting efficient also low.They all do not study the thermal quenching temperature of fluorescent material in addition.Because the problem of packaging process, the working temperature of white light LEDs can reach 100 ℃, and this requires our fluorescent material must have very high thermal quenching temperature.Therefore the research rare earth red fluorescent powder tool that can be appropriate to the high thermal quenching temperature that 400 nm left and right sides near ultraviolet excitation light conversion hysteria LED use has very important significance.
Summary of the invention
The purpose of this invention is to provide a kind of orange red fluorescent RE powder and preparation method thereof, it is the deficiency that exists with red fluorescence powder for the existing InGaN chip of sending out 400 nm left and right sides near-ultraviolet lights, provide that a kind of luminous efficiency is high, good stability, have very high quenching temperature, be suitable for sending out the rare earth orange red fluorescent powder that the InGaN chip of 400 nm left and right sides near-ultraviolet lights is used.Another object of the present invention provides the preparation method of the orange red luminescent phosphor of above-mentioned rare earth.
The present invention implements by following technical scheme
The InGaN chip of of the present invention 400 nm left and right sides near-ultraviolet lights with the chemical constitution of the orange red luminescent phosphor of rare earth is: Sr
3-x-yCa
yAl
2-zB-
zO
5Cl
2-x '-y 'F
X 'Br
Y ': xEu
2+
Wherein: x, y, z, x ', y ' are the mole coefficient ratio, 0.0＜x≤1.0,0.0≤y≤3.0,0.0＜z≤2.0,0.0＜x '≤2.0,0.0＜y '≤2.0.The quality percentage composition of raw material type used in the present invention and each raw material is respectively: Strontium carbonate powder (SrCO
3): 40.58 % ~ 51.70 %; Calcium chloride (CaCl
2): 0 ~ 19.86 %; Six water strontium chloride (SrCl
26H
2O): 0 ~ 39.20 %; Strontium fluoride (SrF
2): 0 ~ 22.58 %; Strontium bromide (SrBr
2): 0 ~ 35.28 %; Aluminium hydroxide [Al (OH)
3]: 0 ~ 27.90 %; Boric acid (H
3BO
3): 0 ~ 23.37 %; Europiumsesquioxide (Eu
2O
3): 0 ~ 0.57 %.Total amount is 100%.
Near-ultraviolet light of the present invention refers to send out the near-ultraviolet light of 380～410 nm.
The preparation method of the orange red luminescent phosphor of above-mentioned rare earth, adopt high temperature solid-state method, comprise the steps: various raw materials are mixed in proportion, 400～500 ℃ of lower pre-burnings 3～6 hours, be chilled to room temperature, take out and again grind evenly, the reduction sintering is 4～10 hours in 1000～1200 ℃ of CO atmosphere, with the levigate the finished product that get of gained sinter.
Advantage of the present invention and positively effect
Rare earth orange red fluorescent powder of the present invention very strong excite and has very strong orange red light emission (emission peak is positioned at about 600 nm) having about 400 nm, and luminous efficiency is high, Heat stability is good.
Description of drawings
Fig. 1 is excitation spectrum (the monitoring wavelength is 600 nm) and the emmission spectrum (excitation wavelength is 400 nm) of fluorescent material of the present invention;
Fig. 2 is the alternating temperature spectrogram of fluorescent material of the present invention;
Fig. 3 is the luminescent spectrum figure of InGaN LED under 20 mA electric currents excite of coating orange red fluorescent powder of the present invention.
Embodiment
Embodiment 1:
Take by weighing Strontium carbonate powder (SrCO
3): 2.89 g (51.70%), calcium chloride (CaCl
2): 1.11 g(19.86%), aluminium hydroxide [Al (OH)
3]: 1.56 g(27.90 %), europiumsesquioxide (Eu
2O
3): 0.03 g(0.54 %), after in agate mortar, fully grinding and mixing, 500 ℃ of lower pre-burnings 4 hours, be chilled to room temperature, take out and again to grind evenly, the reduction sintering is 4 hours in 1200 ℃ of CO atmosphere, gets the finished product to 350-400 nm with the gained sinter is levigate.
The luminescent properties of this fluorescent material as shown in Figure 1, it has the very strong broadband excitation that excites in the near-ultraviolet light district, the emmission spectrum under 400 nm optical excitation as shown in Figure 1, the emission of sample is that orange red light emission take about 600 nm is as main.
The emmission spectrum of this fluorescent material under differing temps as shown in Figure 2.Along with the rising of temperature, light-emitting phosphor intensity is descending, but spectral shape does not change.When temperature was raised to 100 ℃, the emissive porwer of sample was about 80 % of Emission at Room Temperature intensity, and this sample that shows that we synthesize has fine thermal quenching effect, is conducive to be applied on the white light LEDs.
Be coated with the emmission spectrum of InGaN LED under 20 mA electric currents excite of orange red fluorescent powder of the present invention as shown in Figure 3.380 nm are that the InGaN chip sends and the royal purple light that do not absorbed by fluorescent material to the emission peak between 410 nm among the figure, and the emission of fluorescent material is positioned at 600 nm.The red emission of this LED is very strong.
Embodiment 2:
Take by weighing Strontium carbonate powder: 2.89 g(41.40%), six water strontium chlorides: 2.67 g(38.25%), aluminium hydroxide: 0.78 g(11.17%), boric acid 0.61 g(8.74%), europiumsesquioxide: 0.03 g(0.44%), after in agate mortar, grinding and mixing, 400 ℃ of lower pre-burnings 6 hours, be chilled to room temperature, take out and again grind evenly, the reduction sintering is 7 hours in 1100 ℃ of CO atmosphere, with the levigate the finished product that get of gained sinter.
Embodiment 3:
Take by weighing Strontium carbonate powder: 2.91 g(45.75%), strontium fluoride: 0.63 g(9.90%), strontium bromide: 1.24 g(19.50%), aluminium hydroxide: 1.56 g(24.53%), europiumsesquioxide: 0.02 g (0.32%), after in agate mortar, fully grinding and mixing, 500 ℃ of lower pre-burnings 3 hours, be chilled to room temperature, take out and again grind evenly, the reduction sintering is 8 hours in 1000 ℃ of CO atmosphere, with the levigate the finished product that get of gained sinter.
Claims (4)
1. orange red fluorescent RE powder, it is characterized in that: its chemical constitution is:
Sr
3-x-yCa
yAl
2-zB-
zO
5Cl
2-x’-y’F
x’Br
y’:?xEu
2+
Wherein: x, y, z, x ', y ' are the mole coefficient ratio, 0.0＜x≤1.0,0.0≤y≤3.0,0.0＜z≤2.0,0.0＜x '≤2.0,0.0＜y '≤2.0.
2. according to the preparation method of the described orange red fluorescent RE powder of claim art, it is characterized in that: finish according to the following steps,
1) the quality percentage composition of raw material type and each raw material is respectively: Strontium carbonate powder (SrCO
3): 40.58 % ~ 51.70 %; Calcium chloride (CaCl2): 0 ~ 19.86 %; Six water strontium chlorides (SrCl26H2O): 0 ~ 39.20 %; Strontium fluoride (SrF2): 0 ~ 22.58 %; Strontium bromide (SrBr2): 0 ~ 35.28 %; Aluminium hydroxide [Al (OH) 3]: 0 ~ 27.90 %; Boric acid (H3BO3): 0 ~ 23.37 %; Europiumsesquioxide (Eu2O3): 0 ~ 0.57 %, total amount is 100%;
2) preparation method comprises the steps: various raw materials are mixed in proportion, and 400～500 ℃ of lower pre-burnings 3～6 hours, is chilled to room temperature, take out and again grind evenly, under 1000～1200 ℃ of temperature, the reduction sintering is 4～10 hours in the CO atmosphere, with the levigate the finished product that get of gained sinter.
3. the preparation method of claim art 2 described orange red fluorescent RE powders, it is characterized in that: composition of raw materials and quality percentage composition are: Strontium carbonate powder 51.70%, calcium chloride 19.86%, aluminium hydroxide 27.90 %, europiumsesquioxide 0.54 %.
4. the preparation method of claim art 2 described orange red fluorescent RE powders, it is characterized in that: composition of raw materials and quality percentage composition are: Strontium carbonate powder 45.75%, strontium fluoride 9.90%, strontium bromide 19.50%, aluminium hydroxide 24.53%, europiumsesquioxide 0.32%.
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Citations (8)
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|---|---|---|---|---|
| CN101270286A (en) * | 2008-05-21 | 2008-09-24 | 中国科学院长春应用化学研究所 | White radiation fluorescent powder for LED excitated with ultraviolet and near ultraviolet and preparation method thereof |
| US20100019262A1 (en) * | 2008-07-24 | 2010-01-28 | Teng-Ming Chen | White-emitting phosphors and lighting apparatus using the same |
| TW201032355A (en) * | 2009-02-25 | 2010-09-01 | Epistar Corp | Light-emitting device with narrow dominant wavelength distribution and method of making the same |
| CN101818058A (en) * | 2010-04-13 | 2010-09-01 | 中国科学院长春光学精密机械与物理研究所 | Orange long-afterglow fluorescent powder and preparation method thereof |
| CN101864315A (en) * | 2010-06-13 | 2010-10-20 | 中山大学 | Cerium-ion activated flashing light-emitting material for X-ray detection and method for preparing the same |
| CN101899297A (en) * | 2010-07-15 | 2010-12-01 | 兰州大学 | Orange-yellow long-afterglow luminescent material and preparation method thereof |
| WO2010136411A1 (en) * | 2009-05-25 | 2010-12-02 | Osram Opto Semiconductors Gmbh | Chloroaluminate compound, process for the preparation thereof, radiation-emitting device comprising the chloroaluminate compound and process for producing the radiation-emitting device |
| US20110095676A1 (en) * | 2009-10-27 | 2011-04-28 | General Electric Company | Orange-red persistent phosphors |
-
2013
- 2013-01-14 CN CN201310012418XA patent/CN103059843A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101270286A (en) * | 2008-05-21 | 2008-09-24 | 中国科学院长春应用化学研究所 | White radiation fluorescent powder for LED excitated with ultraviolet and near ultraviolet and preparation method thereof |
| US20100019262A1 (en) * | 2008-07-24 | 2010-01-28 | Teng-Ming Chen | White-emitting phosphors and lighting apparatus using the same |
| TW201032355A (en) * | 2009-02-25 | 2010-09-01 | Epistar Corp | Light-emitting device with narrow dominant wavelength distribution and method of making the same |
| WO2010136411A1 (en) * | 2009-05-25 | 2010-12-02 | Osram Opto Semiconductors Gmbh | Chloroaluminate compound, process for the preparation thereof, radiation-emitting device comprising the chloroaluminate compound and process for producing the radiation-emitting device |
| US20110095676A1 (en) * | 2009-10-27 | 2011-04-28 | General Electric Company | Orange-red persistent phosphors |
| CN101818058A (en) * | 2010-04-13 | 2010-09-01 | 中国科学院长春光学精密机械与物理研究所 | Orange long-afterglow fluorescent powder and preparation method thereof |
| CN101864315A (en) * | 2010-06-13 | 2010-10-20 | 中山大学 | Cerium-ion activated flashing light-emitting material for X-ray detection and method for preparing the same |
| CN101899297A (en) * | 2010-07-15 | 2010-12-01 | 兰州大学 | Orange-yellow long-afterglow luminescent material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| XINMIN ZHANG，ET AL: "Orange emission enhancement by energy transfer in Sr3Al2O5Cl2:Ce3+,Eu2+ phosphor for solid-state lighting", 《JOURNAL OF LUMINESCENCE》, vol. 130, 7 August 2009 (2009-08-07), pages 117 - 120 * |
| XINMIN ZHANG，ET AL: "Orange emissive Sr3Al2O5Cl2:Eu2+ phosphor for warm-white light-emitting diodes", 《SOLID STATE COMMUNICATIONS》, vol. 149, 14 April 2009 (2009-04-14), pages 1017 - 1020 * |
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Application publication date: 20130424 |