CN101591534A - Red light flourescent material and manufacture method thereof, and white light emitting device - Google Patents
Red light flourescent material and manufacture method thereof, and white light emitting device Download PDFInfo
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Abstract
The present invention is applicable to lighting technical field, and a kind of red light flourescent material is provided, and is used to be subjected to first light and excites and radiate ruddiness.This red light flourescent material is characterised in that the chemical formula with following formula (1): A
3B
2C
3(MO
4)
8: Eu
3+, wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs) or silver (Ag); B represents magnesium (Mg), calcium (Ca), strontium (Sr) or barium (Ba); C represents yttrium (Y), gadolinium (Gd) or lanthanum (La); M represents the combination (Mo of molybdenum (Mo), tungsten (W) or molybdenum and tungsten
xW
(1-x)).This red light flourescent material can provide the ruddiness of high briliancy and good color purity.In addition, owing to the oxide compound that consists of of this red light flourescent material, so this red light flourescent material has good chemical stability and long work-ing life.
Description
Technical field
The invention belongs to lighting technical field, relate in particular to a kind of red light flourescent material and manufacture method thereof and have the white light emitting device of this red light flourescent material.
Background technology
In recent years, because green science and technology is flourish, have that power saving, volume are little, the white light emitting diode (White light emitting diode) of low voltage drive and advantage such as not mercurous, be widely used in fields such as the backlight module of flat-panel screens and general illumination.In order to promote the luminescent properties of white light emitting diode, very important role is being played the part of in the research and development of fluorescent material, and the fluorescent material of many novelties is also proposed successively.
According to disclosed white light emitting device among the United States Patent (USP) notification number US 5,998,925, it mainly is the garnet phosphor powder (Y with doped with cerium
3Al
5O
12: Ce
3+, YAG:Ce) blue light that blue light-emitting diode sent is converted to gold-tinted, and passes through the blue light gold-tinted to produce white light.Yet this exists the higher problem of colour temperature by the white light that the garnet fluorescent material of blue light-emitting diode and doped with cerium is produced always, and particularly when improving actuating current, the problem that colour temperature raises can more become serious.In addition, the white light that mode produced according to this owing to do not contain red composition in its luminous frequency spectrum, thus the color rendering of white light (Color Render Index CRI) has only 80 approximately, has the insufficient problem of color rendering during as illumination light source.For example, present this white light red cognition weak orange.
The problems referred to above can be by increasing the white-light emitting frequency spectrum red composition to be improved.In United States Patent (USP) notification number US 6,580,097, can utilize blue light-emitting diode, the two fluorescent material system that collocation red light flourescent material and green glow fluorescent material are formed is with the generation white light.This pair fluorescent material system is by the red light fluorescent powder (Y of sulfur-bearing
2O
2S:Eu
3+, Bi
3+SrS:Eu
2+SrY
2S
4: Eu
2+Or CaLa
2S
4: Ce
3+) the green glow fluorescent material of collocation doping with rare-earth ions uses, and with this pair fluorescent material system collocation white light that blue light-emitting diode was produced, has preferable color rendering.
Though the white light that the above-mentioned pair of fluorescent material system produced can improve the problem of colour temperature and color rendering, yet, owing to all contain sulfide in the composition of employed fluorescent material, this sulfide easily reacts with airborne aqueous vapor, makes that the chemical stability of this pair fluorescent material system is not good.And under UV-light was shone for a long time, this pair fluorescent material system decayed easily, and insufficient problem in work-ing life is also arranged.In addition, because the thermostability of sulfide is not good, make to be subject to many limitations with the application of sulfide as the fluorescent material of main component.
Summary of the invention
The purpose of the embodiment of the invention is to provide a kind of red light flourescent material, and the ruddiness that briliancy is strong and purity of color is high can be provided.
The present invention provides a kind of manufacture method of red light flourescent material again, can use lower sintering temperature to obtain the good red light flourescent material of chemical stability.
The present invention provides a kind of white light emitting device again, has above-mentioned red light flourescent material, and good white light of color rendering and long service life can be provided.
Based on above-mentioned, the present invention proposes a kind of red light flourescent material, is used to be subjected to first light and excites and radiate ruddiness, and this red light flourescent material is characterised in that the chemical formula with following formula (1),
A
3B
2C
3(MO
4)
8: Eu
3+-------Shi (1);
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs) or silver (Ag); B represents magnesium (Mg), calcium (Ca), strontium (Sr) or barium (Ba); C represents yttrium (Y), gadolinium (Gd) or lanthanum (La); M represents the combination (Mo of molybdenum (Mo), tungsten (W) or molybdenum and tungsten
xW
(1-x)).
In one embodiment of this invention, the wavelength region of above-mentioned first light is between 360 nanometers (nm), 550 nanometers (nm).
In one embodiment of this invention, the wavelength region of above-mentioned first light comprises: near-ultraviolet light wavelength 394 ± 10nm, blue light wavelength 465 ± 10nm or yellow green light wavelength 535 ± 10nm.
In one embodiment of this invention, the wavelength of above-mentioned ruddiness comprises 614nm.
In one embodiment of this invention, the above-mentioned combination (Mo that represents molybdenum and tungsten as M
xW
(1-x)) time, x is a mole fraction, it is worth between 0-1.
In one embodiment of this invention, the chromaticity coordinates of above-mentioned ruddiness can reach (0.66,0.33).
In one embodiment of this invention, the relative brightness value of above-mentioned ruddiness is 1.5～1.8 (cd/m
2).
In one embodiment of this invention, above-mentioned red light flourescent material is applicable to white light emitting diode.
The present invention proposes a kind of manufacture method of aforesaid red light flourescent material again, comprise: provide a mixture according to chemical dose, this mixture comprises metal carbonate, alkaline earth metal carbonate, trivalent metal oxide, rare earth oxide, and the combination of molybdic oxide or tungstic oxide or molybdic oxide and tungstic oxide; Mix and the grinding said mixture; And the mixture after above-mentioned mixing of sintering and the grinding, to obtain red light flourescent material.
In one embodiment of this invention, the manufacture method of above-mentioned red light flourescent material more comprises provides ammonium halide salt as fusing assistant, and wherein the weight percent of ammonium halide salt is 10wt%.
In one embodiment of this invention, the time of above-mentioned mixing and grinding mixture is 30 minutes.
In one embodiment of this invention, the temperature of above-mentioned sintering mix is 600 ℃～800 ℃.
In one embodiment of this invention, the time of above-mentioned sintering mix is 6 to 10 hours.
In one embodiment of this invention, more comprise the CHARACTERISTICS IDENTIFICATION step, identify the physics and the chemical property of red light flourescent material.
In one embodiment of this invention, above-mentioned CHARACTERISTICS IDENTIFICATION step comprises: X ray diffraction analysis, fluorescent spectroscopy, tristimulus coordinates analysis or UV-light-visible reflectance spectrum analysis.
The present invention reintroduces a kind of white light emitting device, comprising: light-emitting diode chip for backlight unit and photoluminescence fluor.Light-emitting diode chip for backlight unit radiates first light.The photoluminescence fluor comprises at least that as above-mentioned red light flourescent material wherein, the photoluminescence fluor is subjected to first the exciting of light and radiates second light, and first light and the second light mixed light are white light.
In one embodiment of this invention, the wavelength region of above-mentioned first light is between 360 nanometers (nm), 550 nanometers (nm).
In one embodiment of this invention, the wavelength region of above-mentioned first light comprises: near-ultraviolet light wavelength 394 ± 10nm, blue light wavelength 465 ± 10nm or yellow green light wavelength 535 ± 10nm.
In one embodiment of this invention, above-mentioned photoluminescence fluor more comprises: gold-tinted fluorescent material, blue-light fluorescent material or green glow fluorescent material.Red light flourescent material is used for selecting collocation to use with gold-tinted fluorescent material, blue-light fluorescent material and green glow fluorescent material.
Red light flourescent material of the present invention can provide purity of color height and briliancy strong ruddiness because of adopting novel chemical structure.Particularly, the manufacture method of red light flourescent material proposed by the invention, because the consisting of oxide compound and do not contain the sulfide of poor chemical stability of red light flourescent material, so have good chemical stability.Moreover temperature required during owing to sintering is quite low, can also reduce the usage quantity of the energy.In addition, white light emitting device of the present invention has been owing to used above-mentioned red light flourescent material, and can provide color rendering good white light, and long service life.
For above-mentioned feature and advantage of the present invention can be become apparent, embodiment cited below particularly, and cooperate appended graphic being described in detail below.
Description of drawings
Fig. 1 is the manufacture method schematic flow sheet of the red light flourescent material of preferred embodiment of the present invention.
Fig. 2 is the exciting light spectrogram of the red light flourescent material of preferred embodiment of the present invention, has wherein shown the excitation spectrum of embodiments of the invention 1～5.
Fig. 3 is the tristimulus coordinates synoptic diagram of the red light flourescent material of preferred embodiment of the present invention.
Fig. 4 is the synoptic diagram of a kind of white light emitting device of preferred embodiment of the present invention.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The present invention proposes a kind of red light flourescent material of novelty, and it has the unique chemical crystalline structure, can produce the strong ruddiness of purity of color height and briliancy.Except can improve known in the insufficient problem of color rendering, this novel red light flourescent material is the structure of sulfur compound not more, from the not good problem of basic solution chemical stability.Below will narrate this red light flourescent material and manufacture method thereof one by one, and the white light emitting device that uses this red light flourescent material.
Red light flourescent material
The red light flourescent material that the present invention proposes is used to be subjected to first light and excites and radiate ruddiness, and this red light flourescent material is characterised in that the chemical formula with following formula (1),
A
3B
2C
3(MO
4)
8: Eu
3+-------Shi (1);
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs) or silver (Ag); B represents magnesium (Mg), calcium (Ca), strontium (Sr) or barium (Ba); C represents yttrium (Y), gadolinium (Gd) or lanthanum (La); M represents the combination (Mo of molybdenum (Mo), tungsten (W) or molybdenum and tungsten
xW
(1-x)).
Be noted that the combination (Mo that represents molybdenum and tungsten as above-mentioned M at this
xW
(1-x)) time, x is a mole fraction, its value can be between 0-1, the wavelength region of first light is then between 360 nanometers (nm)-550 nanometers (nm), also promptly, this red light flourescent material quite is fit to be excited by first light of UV-light～blue wave band and yellow green light wave band, and then sends ruddiness.
In formula (1), A
3B
2C
3(MO
4)
8Be red light flourescent material agent structure of the present invention, and Eu
3+Then be adulterated europium trivalent ion (Eu in the red light flourescent material agent structure of the present invention
3+).Red light flourescent material proposed by the invention mainly is to form with above-mentioned atoms metal A, alkaline earth metal atom B and rare earth atom C to have eight coordinate MO
4Special crystal structure is again by europium trivalent ion (Eu
3+) doping and have energy that absorbs first light and the characteristic that radiates ruddiness.
This red light flourescent material has very strong absorption for the light of specific wavelength, and wherein, three wavelength regions of preferable absorption are: near-ultraviolet light wavelength 394 ± 10nm, blue light wavelength 465 ± 10nm or yellow green light wavelength 535 ± 10nm.After the light ray energy that absorbs above-mentioned specific wavelength, this red light flourescent material will discharge the energy that is absorbed with the form of ruddiness, and the wavelength of this ruddiness for example is 614nm.
In addition, the ruddiness that this red light flourescent material sent, its purity of color can reach the position of (0.66,0.33) on the NTSC chromaticity coordinates, also is that the purity of color of ruddiness can level off to saturated red (as shown in Figure 3).In addition, its relative brightness value more can reach 1.5～1.8 (cd/m
2) (as shown in Table 1).
Because this red light flourescent material can provide briliancy height and the good ruddiness of purity of color, so this red light flourescent material quite is fit to be applied in white light emitting diode.
The manufacture method of red light flourescent material
Fig. 1 is the manufacture method schematic flow sheet of the red light flourescent material of preferred embodiment of the present invention.Please refer to Fig. 1, at first, in step S1, provide a mixture according to chemical dose, comprise: metal carbonate, alkaline earth metal carbonate, trivalent metal oxide, rare earth oxide, and the combination of molybdic oxide or tungstic oxide or molybdic oxide and tungstic oxide.
More specifically, the manufacture method of above-mentioned red light flourescent material can be allocated each proportion of composing of forming of red light flourescent material according to the shown mole fraction of above-mentioned formula (1) (mole ratio), and wherein, metal carbonate for example is Quilonum Retard (Li
2CO
3), alkaline earth metal carbonate for example is barium carbonate (BaCO
3), trivalent metal oxide for example is europium sesquioxide (Eu
2O
3), rare earth oxide then for example is gadolinium sesquioxide (Gd
2O
3).
Then, in step S2, mix and the grinding said mixture.When step S2, more even in order to make mixture, approximately need 30 minutes time to carry out the mixing and the grinding of said mixture.
Come, shown in step S3, the mixture after above-mentioned mixing of sintering and the grinding is to form red light flourescent material again.And when step S3 carries out sintering, for example the above-mentioned mixture that mixes and ground can be placed alumina crucible, again this alumina crucible is inserted in the High Temperature Furnaces Heating Apparatus, carried out the about 6-10 of sintering hour, can obtain this red light flourescent material with 600 ℃-800 ℃ temperature.
Resulting red light flourescent material is an oxide form, and has the chemical formula of following formula (1), A
3B
2C
3(MO
4)
8: Eu
3+-------Shi (1); Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs) or silver (Ag); B represents magnesium (Mg), calcium (Ca), strontium (Sr) or barium (Ba); C represents yttrium (Y), gadolinium (Gd) or lanthanum (La); M represents the combination (Mo of molybdenum (Mo), tungsten (W) or molybdenum and tungsten
xW
(1-x)).
In addition, also can when sintering step S3, add weight percent be the ammonium halide salt of 10wt% as fusing assistant to help sintering.
Please continue with reference to Fig. 1, shown in step S4,, also can further carry out CHARACTERISTICS IDENTIFICATION step S4, to identify the physics and the chemical property of red light flourescent material via the prepared red light flourescent material of above-mentioned steps S1-S3.In detail, the CHARACTERISTICS IDENTIFICATION step can comprise: X ray diffraction analysis, fluorescent spectroscopy, tristimulus coordinates (chromaticity coordinates) are analyzed or UV-light-visible reflectance spectrum analysis, yet not as limit.
What deserves to be mentioned is, the manufacture method of red light flourescent material proposed by the invention, its employed main component is metal carbonate, alkaline earth metal carbonate, trivalent metal oxide, rare earth oxide, and the combination of molybdic oxide or tungstic oxide or molybdic oxide and tungstic oxide, required sintering temperature only is about 600 ℃-800 ℃.Garnet fluorescent material (sintering temperature need 1 compared to known described doped with cerium, 500 ℃), general silicate and germanic acid salt fluorescent material (sintering temperature need 1,000 ℃～1,200 ℃) and the red light flourescent material of sulfur-bearing (sintering temperature needs 1,100 ℃-1,200 ℃), the sintering temperature of the manufacture method of red light flourescent material of the present invention is lower, makes the required energy and manufacturing cost and can reduce.
In addition,, do not contain the sulfide of poor chemical stability, so this red light flourescent material has excellent chemical stability according to the oxide compound that consists of of red light flourescent material of the present invention.Even if using under the irradiation of UV-light or under the pyritous environment for a long time, red light flourescent material of the present invention all can have long work-ing life and be used widely.
Below will enumerate five groups according to the prepared red light flourescent material of above-mentioned embodiment, and CHARACTERISTICS IDENTIFICATION be the results are shown in Fig. 2 and Fig. 3, wherein, Fig. 2 is the exciting light spectrogram of the red light flourescent material of preferred embodiment of the present invention, has wherein shown the excitation spectrum of embodiments of the invention 1～5.Fig. 3 is the tristimulus coordinates synoptic diagram of the red light flourescent material of preferred embodiment of the present invention.In addition, more list two kinds of commercial red light flourescent materials in contrast, use the clear effect of the present invention that discloses.
Embodiment 1
As shown in Figure 1, weigh Quilonum Retard (Li according to chemical dose
2CO
3), barium carbonate (BaCO
3), europium sesquioxide (Eu
2O
3), gadolinium sesquioxide (Gd
2O
3) and tungstic oxide (WO
3) formation one mixture; Then, this mixture is placed on the alumina crucible through grinding 30 minutes; Then, place High Temperature Furnaces Heating Apparatus with 600 ℃ of sintering 6 to 8 hours this alumina crucible, can obtain red light flourescent material Li
3Ba
2Gd
3(WO
4)
8: Eu
3+
Then, to Li
3Ba
2Gd
3(WO
4)
8: Eu
3+Carry out UV-light-visible reflectance spectrum analysis, fluorescent spectroscopy and tristimulus coordinates analysis, wherein, fluorescent spectroscopy the results are shown in Fig. 2, this red light flourescent material (Li as shown in Figure 2
3Ba
2Gd
3(WO
4)
8: Eu
3+) a plurality of absorption crests; The fluorescent characteristic analysis the results are shown in table one, this red light flourescent material (Li as shown in Table 1
3Ba
2Gd
3(WO
4)
8: Eu
3+) the radiation crest be 614nm and relative briliancy thereof; The tristimulus coordinates analysis the results are shown in Fig. 3, this red light flourescent material (Li as shown in Figure 3
3Ba
2Gd
3(WO
4)
8: Eu
3+) chromaticity coordinate value of ruddiness of radiation.
Specifically, above-mentioned fluorescent spectroscopy for example can be passed through spectrofluorometer (SpexFluorolog-3spectrofluorometer, Instruments S.A., Edison, N.J., U.S.A.) provide the first light (not shown) of different wave length, and the wavelength region of first light contains 360 nanometers (nm)-550 nanometers (nm).After first light that spectrofluorometer is produced through red light flourescent material measurement, measuring first light with photomultiplier (photomultiplier, HamamatsuPhotonics R928) again is absorbed or the intensity of second light that red light flourescent material inspired.Measuring value as for tristimulus coordinates is the coordinate system that adopts CIE1931, and in the present embodiment, tristimulus coordinates is to measure by color analysis instrument (Color Analyzer) Laiko DT-100.
Please refer to Fig. 2, embodiment 1 (Li
3Ba
2Gd
3(WO
4)
8: Eu
3+) the excitation spectrum of red fluorescence material be shown as the absorption peak at the place of x=0 shown in the figure, the excitation spectrum of embodiment 1 all has tangible absorption intensity at near-ultraviolet light wavelength 394 ± 10nm, blue light wavelength 465 ± 10nm and yellow green light wavelength 535 ± 10nm, especially has the most tangible absorption intensity at ultraviolet wavelength 394nm place.In addition, the absorption peak at 250nm-350nm mainly is that (charge transfer band C.T.B) causes charge-transfer band.
After absorbing above-mentioned wavelength energy, this red light flourescent material radiates the ruddiness that wavelength is 614nm.Then, please refer to Fig. 3, the tristimulus coordinates of the ruddiness that this red light flourescent material is emitted can reach the position of (0.66,0.33) on the NTSC chromaticity coordinates, also is that the purity of color of ruddiness can level off to saturated red.
Embodiment 2
Be similar to embodiment 1,, weigh Quilonum Retard (Li according to chemical dose according to manufacture method shown in Figure 1
2CO
3), barium carbonate (BaCO
3), europium sesquioxide (Eu
2O
3), gadolinium sesquioxide (Gd
2O
3), tungstic oxide (WO
3) and molybdic oxide (MoO
3) formation one mixture; Behind grinding and sintering, can get red light flourescent material Li
3Ba
2Gd
3(WO
4)
6(MoO
4)
2: Eu
3+
Similarly, embodiment 2 is carried out CHARACTERISTICS IDENTIFICATION and the results are shown in Fig. 2 and Fig. 3.Red light flourescent material (the Li of embodiment 2
3Ba
2Gd
3(WO
4)
6(MoO
4)
2: Eu
3+) be shown as the x=2 place.
In the composition of embodiment 2, the molar ratio of metal molybdate and metal tungstates is 2: 6.The spectral response curve of the red light flourescent material of the red light flourescent material of embodiment 2 and embodiment 1 is similar, is not repeated at this, and both differences only are that peak intensity is slightly different.
Be similar to the manufacture method of embodiment 2, can get red light flourescent material Li
3Ba
2Gd
3(WO
4)
4(MoO
4)
4: Eu
3+Similarly, embodiment 3 is carried out CHARACTERISTICS IDENTIFICATION and the results are shown in Fig. 2 and Fig. 3.Red light flourescent material (the Li of embodiment 3
3Ba
2Gd
3(WO
4)
4(MoO
4)
4: Eu
3+) be shown as the x=4 place.
It should be noted that embodiment 3 is characterised in that, the metal molybdate in the composition and the molar ratio of metal tungstates are 4: 4.The spectral response curve of the red light flourescent material of the red light flourescent material of embodiment 3 and embodiment 1-2 is similar, is not repeated at this, and gained difference only is that peak intensity is slightly different.Particularly, in the excitation spectrum of Fig. 2, embodiment 3 (Li
3Ba
2Gd
3(WO
4)
4(MoO
4)
4: Eu
3+) intensity for the highest.
Embodiment 4
Be similar to the manufacture method of embodiment 2, can get red light flourescent material Li
3Ba
2Gd
3(WO
4)
2(MoO
4)
6: Eu
3+Similarly, embodiment 4 is carried out CHARACTERISTICS IDENTIFICATION and the results are shown in Fig. 2 and Fig. 3.Red light flourescent material (the Li of embodiment 4
3Ba
2Gd
3(WO
4)
2(MoO
4)
6: Eu
3+) be shown as the x=6 place.
Embodiment 4 is characterised in that the metal molybdate in the composition and the molar ratio of metal tungstates are 6: 2.The spectral response curve of the red light flourescent material of the red light flourescent material of embodiment 4 and embodiment 1-3 is similar, is not repeated at this, and gained difference only is that peak intensity is slightly different.
Embodiment 5
Be similar to embodiment 1,, weigh Quilonum Retard (Li according to chemical dose according to manufacture method shown in Figure 1
2CO
3), barium carbonate (BaCO
3), europium sesquioxide (Eu
2O
3), gadolinium sesquioxide (Gd
2O
3) and molybdic oxide (Mo
2O
3) form a mixture, behind grinding and sintering, can get red light flourescent material Li
3Ba
2Gd
3(MoO
4)
8: Eu
3+Similarly, embodiment 5 is carried out CHARACTERISTICS IDENTIFICATION and it be the results are shown in Fig. 2 and the table 1, in Fig. 2, embodiment 5 is the spectrum at x=8 place.
Embodiment 5 is that with the difference of embodiment 1 tungstic oxide in the composition is replaced by molybdic oxide fully.The spectral response curve of the red light flourescent material of the red light flourescent material of embodiment 5 and embodiment 1-4 is similar, is not repeated at this, and gained difference only is that peak intensity is slightly different.
Result by above-mentioned analysis, the red light flourescent material that can obviously find out embodiment of the invention 1-5 all has tangible absorption intensity for near-ultraviolet light wavelength 394 ± 10nm, blue light wavelength 465 ± 10nm and yellow green light wavelength 535 ± 10nm, especially have the most tangible absorption intensity at ultraviolet wavelength 394nm place, and can radiate the ruddiness that wavelength is 614nm.
Hold above-mentioned, proposed by the invention red light flourescent material high color purity, high briliancy and the good ruddiness of fullness of shade can be provided.Below will compare to prove at embodiment of the invention 1-3 and commercially available red light flourescent material (reference examples 1, reference examples 2).Surveying instrument via described in the embodiment 1 measures and shows the result in the table one embodiment 1-5, reference examples 1-2 with identical condition.
Table one
Please refer to table one, wherein, embodiment 1-5 is a red light flourescent material proposed by the invention; Reference examples 1 is commercially available red light flourescent material Kasei Optonix P22-RE3 (Y
2O
2S:Eu
3+); Reference examples 2 is commercially available red light flourescent material Kasei Optonix KX-681B, (La
2O
2S:Eu
3+).
Can find out obviously that by table one tristimulus coordinates of embodiment 1-3 is all identical with reference examples 1, is all (0.66,0.33).In other words, by the ruddiness of the described red light flourescent material gained of embodiment 1-3, its purity of color can be consistent with the commercialization product and levels off to pure red (0.67,0.33) of NTSC institute standard.
What deserves to be mentioned is that the relative briliancy of experimental example 1-5 is all greater than reference examples 1-2, especially in embodiment 3, when the molar ratio of tungsten and molybdenum was 4: 4, its relative briliancy was 1.8 the highest in the table one (cd/m
2).Via the comparison of table one, can learn red light flourescent material proposed by the invention, the ruddiness that it sent the not only good and relative briliancy of purity of color more is higher than existing commercial product.
White light emitting device
Fig. 4 is the synoptic diagram of a kind of white light emitting device of preferred embodiment of the present invention.Please refer to Fig. 4, white light emitting device 200 comprises: light-emitting diode chip for backlight unit 210 and photoluminescence fluor 220.Light-emitting diode chip for backlight unit 210 radiates the first light L1, and photoluminescence fluor 220 comprises above-mentioned red light flourescent material at least, wherein, photoluminescence fluor 220 is subjected to exciting of the first light L1 and radiates the second light L2, and the first light L1 and the second light L2 mixed light are white light.
The wavelength region of the above-mentioned first light L1 can be between 360 nanometers (nm)-550 nanometers (nm).When the wavelength region of the first light L1 is near-ultraviolet light wavelength 394 ± 10nm, blue light wavelength 465 ± 10nm or yellow green light wavelength 535 ± 10nm, exciting light photoluminescence fluor 220 (comprising above-mentioned red light flourescent material at least) preferably, and make this photoluminescence fluor 220 emit the second light L2.
In addition, above-mentioned photoluminescence fluor 220 can more comprise: gold-tinted fluorescent material (not shown), blue-light fluorescent material (not shown) or green glow fluorescent material (not shown).Above-mentioned red light flourescent material is used for selecting collocation to use with gold-tinted fluorescent material, blue-light fluorescent material and green glow fluorescent material.
More specifically, in white light emitting device 200, photoluminescence fluor 220 can be separately red light flourescent material proposed by the invention, also two fluorescent material systems or even multiple fluorescent material blended system.For example, when photoluminescence fluor 220 only is red light flourescent material proposed by the invention, light-emitting diode chip for backlight unit 210 for example can be selected blue-green light LED for use, at this moment, the first light L1 (blue green light) that light-emitting diode chip for backlight unit 210 is sent, the second light L2 (ruddiness) that is inspired with red light flourescent material, but mixed light is a white light.
When if photoluminescence fluor 220 be a pair fluorescent material system, photoluminescence fluor 220 for example is a red light flourescent material of the present invention and the mixing of another gold-tinted fluorescent material.At this moment, light-emitting diode chip for backlight unit 210 for example can be selected blue light-emitting diode for use and send the first light L1 (blue light), and the second light L2 is the mixed light of ruddiness and gold-tinted, behind the first light L1 and the second light L2 mixed light, can produce white light.
In addition, photoluminescence fluor 220 can also be that red light flourescent material of the present invention, green glow fluorescent material mix with blue-light fluorescent material, and this moment, light-emitting diode chip for backlight unit 210 can be selected ultraviolet light-emitting diodes for use, and the first light L1 that it produced is a UV-light.At this moment, the second light L2 that photoluminescence fluor 220 is produced is blue light, green glow and ruddiness, and then is mixed into white light by UV-light, blue light, green glow and ruddiness.
From the above, white light emitting device 200 can be by different fluorescent material systems and different light emitting diode combined to produce white light, and what have this area knows that usually the knowledgeable is when can be according to its purpose and consider to adjust the mode of collocation and combination.
In sum, red light flourescent material proposed by the invention and manufacture method thereof, white light emitting device have following advantage at least:
Because red light flourescent material has unique crystalline structure, and can produce the ruddiness of high briliancy and high color purity, to improve the color rendering of white light.In addition, because red light flourescent material of the present invention is an oxide compound, with respect to the fluorescent material of sulfur compound, the present invention has good chemical stability (water-fast gas, heat-resisting).Moreover red light flourescent material manufacture method proposed by the invention because its sintering temperature is lower, can reduce the usage quantity of the energy.In addition, the white light emitting device that the present invention proposes can increase the work-ing life and the augmentation range of application of white light emitting device owing to used above-mentioned red light flourescent material.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. red light flourescent material is used to be subjected to one first light and excites and radiate a ruddiness, described it is characterized in that:
Described red light flourescent material has the chemical formula of following formula (1),
A
3B
2C
3(MO
4)
8: Eu
3+-------Shi (1);
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs) or silver (Ag); B represents magnesium (Mg), calcium (Ca), strontium (Sr) or barium (Ba); C represents yttrium (Y), gadolinium (Gd) or lanthanum (La); M represents the combination (Mo of molybdenum (Mo), tungsten (W) or molybdenum and tungsten
xW
(1-x)).
2. red light flourescent material as claimed in claim 1 is characterized in that, the wavelength region of first light is between 360 nanometers (nm)-550 nanometers (nm);
The wavelength region of described first light comprises: near-ultraviolet light wavelength 394 ± 10nm, blue light wavelength 465 ± 10nm or yellow green light wavelength 535 ± 10nm;
The wavelength of described ruddiness comprises 614nm.
3. red light flourescent material as claimed in claim 1 is characterized in that, represents the combination (Mo of described molybdenum and tungsten as M
xW
(1-x)) time, x is a mole fraction, it is worth between 0-1.
4. red light flourescent material as claimed in claim 1 is characterized in that the chromaticity coordinates of described ruddiness can reach (0.66,0.33);
The relative brightness value of described ruddiness is 1.5～1.8 (cd/m
2);
5. as each described red light flourescent material in the claim 1 to 4, wherein, this red light flourescent material is applicable to white light emitting diode.
6. the manufacture method of a red light flourescent material as claimed in claim 1 is characterized in that, may further comprise the steps:
Provide a mixture according to chemical dose, comprise a metal carbonate, an alkaline earth metal carbonate, a trivalent metal oxide, a rare earth oxide, and the combination of a molybdic oxide or a tungstic oxide or described molybdic oxide and described tungstic oxide;
Mixing is also ground described mixture; And
Described mixture after sintered compound and the grinding is to form described red light flourescent material.
7. the manufacture method of red light flourescent material as claimed in claim 6 is characterized in that, further comprising provides the step of an ammonium halide salt as fusing assistant, and the weight percent of wherein said ammonium halide salt is 10wt%;
The time of mixing and grinding described mixture is 30 minutes;
The temperature of the described mixture of sintering is 600 ℃～800 ℃;
The time of the described mixture of sintering is 6 to 10 hours.
8. the manufacture method of red light flourescent material as claimed in claim 6 is characterized in that, further comprises a CHARACTERISTICS IDENTIFICATION step, is used to identify the physics and the chemical property of described red light flourescent material; Described CHARACTERISTICS IDENTIFICATION step comprises:
X ray diffraction analysis, fluorescent spectroscopy, tristimulus coordinates analysis or UV-light-visible reflectance spectrum analysis.
9. a white light emitting device is characterized in that, comprising:
One light-emitting diode chip for backlight unit radiates one first light; And
One photoluminescence fluor, described photoluminescence fluor comprises red light flourescent material as claimed in claim 1 at least;
Wherein, described photoluminescence fluor is subjected to described first the exciting of light and radiates one second light, and described first light and the described second light mixed light are white light.
10. white light emitting device as claimed in claim 9, wherein the wavelength region of first light is between 360 nanometers (nm)-550 nanometers (nm);
The wavelength region of wherein said first light comprises: near-ultraviolet light wavelength 394 ± 10nm, blue light wavelength 465 ± 10nm or yellow green light wavelength 535 ± 10nm;
Wherein, described photoluminescence fluor further comprises:
One gold-tinted fluorescent material, a blue-light fluorescent material or a green glow fluorescent material;
Wherein, described red light flourescent material is used for selecting collocation to use with described gold-tinted fluorescent material, described blue-light fluorescent material and described green glow fluorescent material.
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Cited By (7)
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| CN102277163A (en) * | 2011-06-14 | 2011-12-14 | 上海华明高技术（集团）有限公司 | Rare earth red fluorescent powder for white LED and preparation method thereof |
| CN102433119A (en) * | 2011-12-09 | 2012-05-02 | 常熟理工学院 | Tungsten molybdate red fluorescent powder for white light-emitting diode (LED) and preparation method of tungsten molybdate red fluorescent powder |
| CN102604632A (en) * | 2012-02-03 | 2012-07-25 | 上海华明高纳稀土新材料有限公司 | Rare earth luminescent material for white light LED (Light Emitting Diode) and preparation method thereof |
| CN102807864A (en) * | 2012-08-22 | 2012-12-05 | 常熟理工学院 | Europium-activated tungstate red fluorescent powder for white-light light-emitting diode (LED) and preparation method of europium-activated tungstate red fluorescent powder |
| CN104371719A (en) * | 2014-11-18 | 2015-02-25 | 安徽理工大学 | Double-perovskite tungsten molybdate red fluorescent powder for white light LED and preparation method of double-perovskite tungsten molybdate red fluorescent powder |
| CN107338051A (en) * | 2017-06-28 | 2017-11-10 | 陕西科技大学 | Samarium red fluorescence powder and preparation method thereof is mixed suitable for the molybdic acid alkali of white light LEDs |
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| CN101338194B (en) * | 2008-05-15 | 2011-09-21 | 沈阳化工学院 | Rare-earth red fluorescent material and method for preparing same |
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| CN102277163A (en) * | 2011-06-14 | 2011-12-14 | 上海华明高技术（集团）有限公司 | Rare earth red fluorescent powder for white LED and preparation method thereof |
| CN102433119A (en) * | 2011-12-09 | 2012-05-02 | 常熟理工学院 | Tungsten molybdate red fluorescent powder for white light-emitting diode (LED) and preparation method of tungsten molybdate red fluorescent powder |
| CN102604632A (en) * | 2012-02-03 | 2012-07-25 | 上海华明高纳稀土新材料有限公司 | Rare earth luminescent material for white light LED (Light Emitting Diode) and preparation method thereof |
| CN102807864A (en) * | 2012-08-22 | 2012-12-05 | 常熟理工学院 | Europium-activated tungstate red fluorescent powder for white-light light-emitting diode (LED) and preparation method of europium-activated tungstate red fluorescent powder |
| CN104371719A (en) * | 2014-11-18 | 2015-02-25 | 安徽理工大学 | Double-perovskite tungsten molybdate red fluorescent powder for white light LED and preparation method of double-perovskite tungsten molybdate red fluorescent powder |
| CN107338051A (en) * | 2017-06-28 | 2017-11-10 | 陕西科技大学 | Samarium red fluorescence powder and preparation method thereof is mixed suitable for the molybdic acid alkali of white light LEDs |
| CN107365582A (en) * | 2017-06-28 | 2017-11-21 | 陕西科技大学 | Europium red fluorescence powder and preparation method thereof is mixed suitable for the molybdic acid alkali of white light LEDs |
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| CN101591534B (en) | 2012-07-18 |
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