CN1412271A - Fluorescent powder for GaN base light-emitting diode - Google Patents
Fluorescent powder for GaN base light-emitting diode Download PDFInfo
- Publication number
- CN1412271A CN1412271A CN 02152035 CN02152035A CN1412271A CN 1412271 A CN1412271 A CN 1412271A CN 02152035 CN02152035 CN 02152035 CN 02152035 A CN02152035 A CN 02152035A CN 1412271 A CN1412271 A CN 1412271A
- Authority
- CN
- China
- Prior art keywords
- emitting diode
- fluorescent material
- light
- fluorescent powder
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000843 powder Substances 0.000 title abstract description 11
- 239000000463 material Substances 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000012216 screening Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000010431 corundum Substances 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 4
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 241000282693 Cercopithecidae Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Landscapes
- Luminescent Compositions (AREA)
Abstract
The present invention relates to a fluorescent powder for preparing GaN base light-emitting diode (LED). Said fluorescent powder is a composite sulfide. Said invention provides its general formula, and its raw material composition and preparation method. Said fluorescent powder can be excited by 300nm-500 nm (specially 400nm-470 nm) light so as to give out 510 nm-650 nm light, and can be used for preparing green or white GaN base LED light-emitting diode with high luminosity.
Description
Technical field
The present invention relates to fluorescent material that a kind of GaN based light-emitting diode uses and preparation method thereof.
Background technology
GaN based light-emitting diode LED (Light Emitting Diode) is a kind of novel luminescent device, it is little to have volume, long current consumption of life-span hangs down and does not need to use the advantages such as mercury of contaminate environment, can be widely used on the various lighting installations, comprise indoor lamp, traffic lights, stop-light, street lamp, automobile taillight, indicator, brake lamp, outdoor ultra-large type screen, display screen and billboard etc. replace the function of various bulb gradually.This novel green light source will become the lighting source of new generation of 21 century, to energy-saving and environmental protection, improve aspects such as people's quality of life and all be significant.The fluorescent material that can be used for GaN base LED at present is also few, as mixes yttrium aluminum garnet (YAG) the type fluorescent material of Ce, but because it is to utilize blue led and YAG type fluorescent material to make the white light LEDs of two primary colours, and energy conversion rate is lower, colour rendering index is not high yet.Existingly can be used for purple pipe (UV-LED) excited fluorescent powder, common as the high-pressure mercury lamp phosphor, but these fluorescent material can't satisfy the needs of UV-LED on excitation wavelength; And on working conditions, also to contain mercury different with temperature rather different when being applied to UV-LED because of it.
Summary of the invention
The purpose of this invention is to provide to excite at 300nm-500nm light and send down fluorescent material that GaN based light-emitting diode 510nm-650nm light, that be suitable for using in market uses and preparation method thereof, its method is simple, the energy conversion rate height.
Fluorescent material provided by the invention is a kind of complex sulfide, and general formula is (A
xR
1-xS) (B
2S
3)
yOr (A
xR
1-xS) (B
2S
3)
Y-z(C
2S
3)
zWherein A represents the combination (as Mg, Sr, Ca, Ba, Cd, Pd, Hg and Zn) of one or more divalent-metal ions; B represents at least a or multiple aluminium that is selected from, the element of gallium or indium; On behalf of one or more, C be selected from the element of Gd, Y and La; R represents the combination (as Mn, Cu, Ag, Sm, Tb, Tm, Yb, Pr, Ce, Dy, Ho and Er) of Eu or Eu and other activator ion; 0.001≤x≤1,1≤y≤5,0.01≤z≤1.
The method that the present invention relates to prepare this fluorescent material system is as follows:
1) by the mole proportioning of general formula expression requirement, compound or salt to contain A contain B metal or compound or salt, and the compound or the salt that contain C are raw material, and the compound or the salt that contain R are raw material, and by the proportioning weighing of general formula requirement, it is even to mix porphyrize.
2) mixture that preceding step is obtained adds hydrogen sulfide or carbon adds in the atmosphere of sulphur at hydrogen sulfide, dithiocarbonic anhydride, hydrogen, between temperature 800-1200 ℃, forms through the one or many calcining.
3) promptly get product behind the sintered compact crushing screening that preceding step is obtained.
Adopt the inventive method synthetic fluorescent material to send 510nm-650nm light under 300nm-500nm light excites, the GaN based light-emitting diode that is suitable for using in market uses, and can be complementary with blue-ray LED, prepares two novel primary colours white light LEDs; Also can be complementary, partly be used for the preparation of three primary colours white light LEDs, energy conversion rate height as green emitting phosphor with UV-LED; Its synthetic method is simple and convenient, has filled up the blank that existing market needs.
Description of drawings
Fig. 1 is embodiment 1[(Sr
0.99Eu
0.01) S] (Ga
2S
3) the X ray spectrogram.
Fig. 2 is embodiment 1[(Sr
0.99Eu
0.01) S] (Ga
2S
3) emmission spectrum figure (400nm excites).
Fig. 3 is embodiment 3[(Ca
0.9Eu
0.1) S] (Ga
2S
3)
1.25Emmission spectrum figure (470nm excites).
Fig. 4 is embodiment 5[(Ca
0.96Eu
0.04) S] (Ga
2S
3)
0.6(Y
2S
3)
0.4Emmission spectrum figure (470nm excites).
Embodiment
Embodiment one:
[(Sr
0.99Eu
0.01) S] (Ga
2S
3) fluorescent material synthetic:
SrCO
3(analytical pure) 4.3846 grams;
Ga
2O
3(4N) 5.6232 grams;
Eu
2O
3(4N) 0.0528 gram.
With above-mentioned material in agate mortar, grind be mixed after, in the corundum crucible of packing into, at H
2800 ℃ of following calcinations in the S atmosphere, calcination time is no less than 1 hour, and take out the cooling back, and crushing screening obtains the greeny powder of outward appearance, sends green light at 250nm under 500nm light excites.Its X-ray spectrogram is seen Fig. 1, and emmission spectrum figure sees Fig. 2.
Embodiment two:
[(Sr
0.96Eu
0.02Tm
0.02) S] (Ga
2S
3) fluorescent material synthetic:
SrCO
3(analytical pure) 1.4172 grams;
Ga
2O
3(4N) 1.8744 grams;
Eu
2O
3(4N) 0.0352 gram;
Tm
2O
3(4N) 0.0386 gram.
With above-mentioned material in agate mortar, grind be mixed after, in the corundum crucible of packing into, at H
2800 ℃ of following calcinations in the S atmosphere, calcination time is no less than 1 hour,, take out the cooling back, and crushing screening obtains the greeny powder of outward appearance, sends green light at 250nm under 500nm light excites.
Embodiment three:
[(Ca
0.9Eu
0.1) S] (Ga
2S
3)
1.25Synthesizing of fluorescent material:
CaCO
3(analytical pure) 3.6024 grams;
Ga
2O
3(4N) 9.3728 grams;
Eu
2O
3(4N) 0.7038 gram.
With above-mentioned material in agate mortar, grind be mixed after, in the corundum crucible of packing into, at H
2850 ℃ of following calcinations in the S atmosphere, calcination time is no less than 1 hour,, take out the cooling back, and crushing screening obtains outward appearance and is the xanchromatic powder, sends sodium yellow at 250nm under 520nm light excites.Its emmission spectrum figure sees Fig. 3.
Embodiment four:
[(Sr
0.45Ca
0.45Eu
0.1) S] [(Al
0.2Ga
1.8) S
3]
2Synthesizing of fluorescent material:
SrCO
3(analytical pure) 0.6643 gram;
CaCO
3(analytical pure) 0.4503 gram;
Ga
2O
3(4N) 3.3739 grams;
Al (OH)
3(4N) 0.3120 gram;
Eu
2O
3(4N) 0.1760 gram;
S (analytical pure) 2.56 grams.
With above-mentioned material in agate mortar, grind be mixed after, pack in the little corundum crucible, again monkey is put into the big crucible of carbon-point, cover the corundum lid, 900 ℃ of following calcinations in retort furnace, calcination time is no less than 1 hour, take out the cooling back, crushing screening obtains outward appearance and is yellowish green powder, excites luminous down to 500nm light at 250nm.
Embodiment five:
[(Ca
0.96Eu
0.04) S] (Ga
2S
3)
0.6(Y
2S
3)
0.4Synthesizing of fluorescent material:
CaCO
3(analytical pure) 4.803 grams;
Ga
2O
3(4N) 5.6232 grams;
Y
2O
3(4N) 4.5162 grams;
Eu
2O
3(4N) 0.3519 gram.
With above-mentioned material in agate mortar, grind be mixed after, in the quartz boat of packing into, at H
2950 ℃ of following calcinations in the S atmosphere, calcination time is no less than 1 hour,, take out the cooling back, and crushing screening obtains outward appearance and is the xanchromatic powder, and luminous under 250nm excites to 520nm light, emmission spectrum is seen Fig. 4.
Embodiment six:
[(Ca
0.96Eu
0.04) S] (Ga
2S
3)
1.5[(Y
1.4Gd
0.6) S
3]]
0.5Synthesizing of fluorescent material:
CaCO
3(analytical pure) 0.9607 gram;
Ga
2O
3(4N) 2.8116 grams;
Y
2O
3(4N) 0.7903 gram;
Gd
2O
3(4N) 0.5438 gram;
Eu
2O
3(4N) 0.0704 gram.
With above-mentioned material in agate mortar, grind be mixed after, in the quartz boat of packing into, at H
2900 ℃ of following calcinations in the S atmosphere, calcination time is no less than 1 hour, and take out the cooling back, and crushing screening obtains outward appearance and is the xanchromatic powder, excites luminous down to 520nm light at 250nm.
Claims (3)
1. fluorescent material that the GaN based light-emitting diode is used, the general formula that it is characterized in that this fluorescent material is (A
xR
1-xS) (B
2S
3)
yOr (A
xR
1-xS) (B
2S
3)
Y-z(C
2S
3)
z, wherein A is the combination of one or more divalent-metal ions, B is at least a or multiple aluminium that is selected from, the element of gallium or indium, C is selected from the element of Gd, Y and La for one or more, and R is the combination of Eu or Eu and other activator ion, 0.001≤x≤1,1≤y≤5,0.01≤z≤1.
2. GaN based light-emitting diode fluorescent material as claimed in claim 1 is characterized in that the R in the general formula of this fluorescent material is Eu.
3. method for preparing the fluorescent material that GaN based light-emitting diode as claimed in claim 1 uses, it is characterized in that expressing the mole proportioning of requirement by general formula, use simple substance or the compound or the salt of expressed element, through batching, behind the porphyrize mixing, add hydrogen sulfide or carbon adds in the atmosphere of sulphur at hydrogen sulfide, dithiocarbonic anhydride, hydrogen, between temperature 800-1200 ℃, form through the one or many calcining.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021520356A CN1162511C (en) | 2002-11-25 | 2002-11-25 | Fluorescent powder for GaN base light-emitting diode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021520356A CN1162511C (en) | 2002-11-25 | 2002-11-25 | Fluorescent powder for GaN base light-emitting diode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1412271A true CN1412271A (en) | 2003-04-23 |
| CN1162511C CN1162511C (en) | 2004-08-18 |
Family
ID=4752080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021520356A Expired - Fee Related CN1162511C (en) | 2002-11-25 | 2002-11-25 | Fluorescent powder for GaN base light-emitting diode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1162511C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105219381A (en) * | 2015-10-26 | 2016-01-06 | 陕西光电科技有限公司 | A kind of rear-earth-doped thiogallate phosphor material powder and preparation method |
-
2002
- 2002-11-25 CN CNB021520356A patent/CN1162511C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105219381A (en) * | 2015-10-26 | 2016-01-06 | 陕西光电科技有限公司 | A kind of rear-earth-doped thiogallate phosphor material powder and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1162511C (en) | 2004-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1180052C (en) | Wavelength-converting luminous material of white light for LED | |
| TWI424045B (en) | A phosphor, a phosphor sheet, and a phosphor, and a light-emitting device using the phosphor | |
| CN1452253A (en) | Phosphor for white-light emitting diode and white-light emitting diode | |
| CN1927996A (en) | Fluorescent powder material, preparation method thereof and white light LED electric light source | |
| JP2006241249A (en) | Phosphor mixture and light-emitting device | |
| WO2008058462A1 (en) | An aluminate phosphor containing bivalence metal elements, its preparation and the light emitting devices incorporating the same | |
| CN103173225B (en) | Blue fluosilicate fluorescent powder as well as preparation method and application | |
| CN103254895B (en) | Aluminosilicate green fluorescent powder and preparation method thereof | |
| CN101054520A (en) | Red luminescence phosphor | |
| CN1255506C (en) | Boron-containing luminescent powder for LED, preparing method thereof and electric light source therefrom | |
| CN101054521A (en) | Red luminescence phosphor | |
| CN102585831A (en) | Europium-ion-excited fluoromolybdate red fluorescent powder and preparation method and application thereof | |
| CN103468249B (en) | Eu<2+> activated sodium-calcium silicate green phosphor and preparation and application | |
| CN103396800B (en) | Boron aluminate-based blue fluorescent powder, preparation method and application | |
| KR101331302B1 (en) | Aluminate compound phosphor | |
| CN101054523A (en) | Red luminescence phosphor | |
| CN100595259C (en) | Phosphor for white light LED and its prepn process | |
| CN1162511C (en) | Fluorescent powder for GaN base light-emitting diode | |
| CN101608117B (en) | Chlorborate-base phosphor powder used in light-emitting diodes | |
| CN1246420C (en) | Luminescent powder in user for LED with GaN as base and preparing method | |
| JP2004161808A (en) | Nitride fluorescent sheet, light-emitting device and method for producing nitride fluorescent film | |
| CN101735803A (en) | Silicate blue fluorescent powder for white-light LED and preparation method thereof | |
| CN104804731A (en) | Eu<2+>-activated magnesium potassium silicate blue-green fluorescent powder as well as preparation method and application thereof | |
| CN111778022A (en) | Alkali metal enhanced orange light fluorescent powder and preparation method and application thereof | |
| CN1900215A (en) | Fluorescent material and its preparing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040818 |