CN101892052A - Red light luminescent material, manufacturing method thereof and white light emitting device - Google Patents
Red light luminescent material, manufacturing method thereof and white light emitting device Download PDFInfo
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- CN101892052A CN101892052A CN2009100514362A CN200910051436A CN101892052A CN 101892052 A CN101892052 A CN 101892052A CN 2009100514362 A CN2009100514362 A CN 2009100514362A CN 200910051436 A CN200910051436 A CN 200910051436A CN 101892052 A CN101892052 A CN 101892052A
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Abstract
The invention relates to a red light luminescent material which can be excited by a first ray to emit red light. The red light luminescent material is characterized by having a chemical formula as shown in the following formula (1): A2Eu(MO4)(PO4)-formula (1), wherein A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) or silver (Ag); and M represents molybdenum (Mo), tungsten (W) or a combination of molybdenum and tungsten (MoxW(1-x)). The red light luminescent material can provide red light with high luminance and fine color purity. Besides, since the components of the red light luminescent material are oxides, the red light luminescent material has favorable chemical stability and long service life.
Description
Technical field
The invention relates 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, and particularly relevant for a kind of purity of color height, briliancy is strong and chemical stability is good 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 Nichia company disclosed white light emitting device in 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 do not contain red composition owing in the white-light emitting frequency spectrum, so color rendering is poor, has the insufficient problem of color rendering during as illumination light source according to this.For example, present this white light red cognition weak orange.
The problems referred to above can see through the red composition of increase white-light emitting frequency spectrum to be improved.The patent international publication number WO 02/11173A1 that is delivered according to ORSAM company, it utilizes emission wavelength to arrive blue light (370～480nm) photodiode for UV-light, two fluorescent material systems of collocation red light fluorescent powder and yellow green light fluorescent material composition and produce white light, wherein, the chemical formula of red light fluorescent powder is MS:Eu
2+, M represents Ba, Sr, Ca, Mg or Zn; The chemical formula of yellow green light fluorescent material is M*N*
2S
4: Eu
2+, Ce
3+, M* represents Ba, Sr, Ca, Mg or Zn, and N* then represents Al, Ga, In, Y, La or Gd.
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
In view of this, the invention provides a kind of red light flourescent material, 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, obtains 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 suitable for being 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
2Eu (MO
4) (PO
4)-------Shi (1);
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs) or silver (Ag); 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 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), and brightness value is 1.5～1.9 (cd/m relatively
2).
The present invention proposes a kind of manufacture method of red light flourescent material again.At first, provide a mixture according to chemical dose, this mixture comprises europiumsesquioxide, diammonium hydrogen phosphate, and the combination of metal molybdate or metal tungstates or metal molybdate and metal tungstates.Continue it, mix and the grinding said mixture.Afterwards, the sintering said mixture is to obtain red light flourescent material.
In one embodiment of this invention, the time of above-mentioned mixing and grinding mixture is 30 minutes., the temperature of sintering mix is 600 ℃, the time of sintering mix is 6 to 10 hours.
In one embodiment of this invention, the above-mentioned red light flourescent material that obtains has the chemical formula of following formula (1),
A
2Eu (MO
4) (PO
4)-------Shi (1);
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs) or silver (Ag); M represents the combination (Mo of molybdenum (Mo), tungsten (W) or molybdenum and tungsten
xW
(1-x)).
In one embodiment of this invention, also comprise the CHARACTERISTICS IDENTIFICATION step, to identify the physics and the chemical property of red light flourescent material.This 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, comprises 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 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 also comprises: gold-tinted fluorescent material, blue-light fluorescent material or green glow fluorescent material.Above-mentioned red light flourescent material is suitable 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.
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;
Fig. 3 is the radiating light spectrogram of the red light flourescent material of preferred embodiment of the present invention;
Fig. 4 is the tristimulus coordinates synoptic diagram of the red light flourescent material of preferred embodiment of the present invention;
Fig. 5 is the X ray diffraction chart of the red light flourescent material of preferred embodiment of the present invention;
Fig. 6 is the synoptic diagram of a kind of white light emitting device of preferred embodiment of the present invention.
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.
Embodiment
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 suitable for being 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
2Eu (MO
4) (PO
4)-------Shi (1);
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs) or silver (Ag); M represents the combination (Mo of molybdenum (Mo), tungsten (W) or molybdenum and tungsten
xW
(1-x)).
Be noted that at this M that works as in the above-mentioned formula (1) represents the combination (Mo of molybdenum and tungsten
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), that is this red light flourescent material quite is fit to be excited by first light of UV-light～blue light and yellow green light wave band, and then sends ruddiness.
Particularly, this red light flourescent material is owing to have the chemical structure of above-mentioned formula (1), its light for specific wavelength has very strong absorption, wherein, three of preferable absorption wavelength regions 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 (being illustrated in follow-up Fig. 2).
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, that is the purity of color of ruddiness can level off to saturated red (being illustrated in follow-up Fig. 4).In addition, its relative brightness value more can reach 1.5～1.9 (cd/m
2) (being illustrated in follow-up table one).
In addition, 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, comprising: the mixture of europiumsesquioxide, diammonium hydrogen phosphate and metal molybdate or metal tungstates or metal molybdate and metal tungstates according to chemical dose.
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 molybdate for example is Sodium orthomolybdate (Na
2MoO
4), metal tungstates then for example is sodium wolframate (Na
2WO
4).
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 sintering about 6～10 hours, can obtain this red light flourescent material with 600 ℃ temperature.
Resulting red light flourescent material is an oxide form, and has the chemical formula of following formula (1), A
2Eu (MO
4) (PO
4)-------Shi (1); Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs) or silver (Ag); M represents the combination (Mo of molybdenum (Mo), tungsten (W) or molybdenum and tungsten
xW
(1-x)).
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: alkali metal molybdate, alkali tungstates, europiumsesquioxide and diammonium hydrogen phosphate, required sintering temperature only are about 600 ℃.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 three groups according to the prepared red light flourescent material of above-mentioned embodiment, and with Fig. 2～Fig. 5 that the results are shown in of CHARACTERISTICS IDENTIFICATION, wherein, Fig. 2 is the exciting light spectrogram of the red light flourescent material of preferred embodiment of the present invention.Fig. 3 is the radiating light spectrogram of the red light flourescent material of preferred embodiment of the present invention.Fig. 4 is the tristimulus coordinates synoptic diagram of the red light flourescent material of preferred embodiment of the present invention.Fig. 5 is the X ray diffraction spectrum figure 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, and then clear announcement effect of the present invention.
As shown in Figure 1, weigh sodium wolframate (Na according to chemical dose
2WO
4), europiumsesquioxide (Eu
2O
3) and diammonium hydrogen phosphate ((NH
4)
2HPO
4) formation one mixture; Then, this mixture is placed on the alumina crucible through grinding 30 minutes; Then, place High Temperature Furnaces Heating Apparatus after 8 hours, can obtain red light flourescent material Na this crucible with 600 ℃ of sintering
2Eu (WO
4) (PO
4).
Then, to Na
2Eu (WO
4) (PO
4) carry out UV-light-visible reflectance spectrum analysis, fluorescent spectroscopy, tristimulus coordinates analysis and X ray diffraction analysis, wherein, the fluorescent exciting spectrum analysis the results are shown in Fig. 2; The fluorescent radiation spectroscopic analysis the results are shown in Fig. 3; The tristimulus coordinates analysis the results are shown in Fig. 4; The X ray diffraction analysis the results are shown in Fig. 5.
Specifically, above-mentioned fluorescent spectroscopy for example can see through spectrofluorometer (Spex Fluorolog-3spectrofluorometer, Instruments S.A., Edison, N.J., U.S.A.) provide first light 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, Hamamatsu Photonics R928) again is absorbed or the intensity of second light that red light flourescent material inspired.Measurement as for tristimulus coordinates then is the coordinate system that adopts CIE1931, and in the present embodiment, tristimulus coordinates is to see through color analysis instrument (Color Analyzer) Laiko DT-100 to measure.
Please refer to Fig. 2, embodiment 1 (Na
2Eu (WO
4) (PO
4)) the absorption spectrum of red fluorescence material be shown as the absorption peak at the place of x=0 shown in the figure, the absorption 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.
Then, please refer to Fig. 3, embodiment 1 (Na
2Eu (WO
4) (PO
4)) the excitation spectrum of red fluorescence material be shown as the radiation peak at the place of x=0 shown in the figure, when the light with ultraviolet wavelength 394nm puts on the red light flourescent material of embodiment 1 and measures its excitation spectrum, wavelength region between 580nm～720nm, comprise a plurality of wire radiation areas (
5D
0→
7F
J, J=1,2,3,4), particularly,, have the highest excitation light generation of intensity being positioned at the wire radiation area at 614nm place.
Be noted that at this above-mentioned four wire radiation areas belong to europium trivalent ion (Eu
3+) from the excited state transition return ground state characteristic spectrum (
5D
0→
7F
J, J=1,2,3,4).In the characteristic spectrum of embodiment 1～3, comparatively tangible two the wire radiation areas of intensity are
5D
0→
7F
1With
5D
0→
7F
2, wherein, be positioned at the wire radiation area of 590nm
5D
0→
7F
1Intensity relevant with the magnetic dipole migrate attribute; And be positioned at the wire radiation area of 614nm
5D
0→
7F
2Intensity then relevant with electric dipole transition.
Since in red light-emitting material of the present invention, europium trivalent ion (Eu
3+) occupied the symmetric crystallographic site of non-counter-rotating in the crystal, therefore increased the possibility of 4f → 4f electric dipole transition, so the emissive porwer of eelctric dipole will grow, but relatively the emissive porwer of magnetic dipole will die down.In a word, in the red light flourescent material of embodiment 1, can be observed main radiation peak is to launch saturate ruddiness
5D
0→
7F
2Transition.
Come, please refer to Fig. 4, the tristimulus coordinates of this red light flourescent material can reach the position of (0.66,0.33) on the NTSC chromaticity coordinates, that is the purity of color of ruddiness can level off to saturated red.
In addition, please refer to Fig. 5, embodiment 1 (Na
2Eu (WO
4) (PO
4)) the X ray diffraction analysis of red fluorescence material be shown as the crest at the place of x=0 shown in the figure.The X ray diffraction analysis can be resolved the crystalline network of this red fluorescence material thus.
Embodiment 2
Be similar to embodiment 1,, weigh Sodium orthomolybdate (Na according to chemical dose according to manufacture method shown in Figure 1
2MoO
4), sodium wolframate (Na
2WO
4), europiumsesquioxide (Eu
2O
3) and diammonium hydrogen phosphate ((NH
4)
2HPO
4) formation one mixture; Behind grinding and this mixture of sintering, can get the red light flourescent material Na of embodiment 2
2Eu (WO
4)
0.5(MoO
4)
0.5(PO
4).
Similarly, the red light flourescent material to embodiment 2 carries out CHARACTERISTICS IDENTIFICATION and the results are shown in Fig. 2～Fig. 5.Red light flourescent material (the Na of embodiment 2
2Eu (WO
4)
0.5(MoO
4)
0.5(PO
4)) be shown as the x=0.5 place.
It should be noted that embodiment 2 is characterised in that, the metal molybdate in the composition and the molar ratio of metal tungstates are 0.5: 0.5.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.Particularly, in the emission spectrum of Fig. 3, embodiment 2 (Na
2Eu (WO
4)
0.5(MoO
4)
0.5(PO
4)) intensity of ruddiness (wavelength is the 614nm place) of radiation is for the highest.
Embodiment 3
Be similar to embodiment 1,, weigh Sodium orthomolybdate (Na according to chemical dose according to manufacture method shown in Figure 1
2MoO
4), europiumsesquioxide (Eu
2O
3) and diammonium hydrogen phosphate ((NH
4)
2HPO
4) formation one mixture; This mixture can be got the red light flourescent material Na of embodiment 3 behind grinding and sintering
2Eu (MoO
4) (PO
4).
Similarly, to the red light flourescent material (Na of embodiment 3
2Eu (MoO
4) (PO
4)) carry out CHARACTERISTICS IDENTIFICATION and with the result and the results are shown in Fig. 2～Fig. 5.Red light flourescent material (the Na of embodiment 3
2Eu (MoO
4) (PO
4)) be shown as the x=1 place.
The spectral response curve of the red light flourescent material of the red light flourescent material of embodiment 3 and embodiment 1 is similar, is not repeated at this, and both differences only are that peak intensity is slightly different.By the result of above-mentioned analysis, the red light flourescent material that can obviously find out experimental example 1～3 of the present invention all has strong absorption for the light of particular range of wavelengths and is the red light district of 614nm at wavelength, has very strong intensity of radioactivity.
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 with evidence now at the 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 it be the results are shown in the table one embodiment 1～3, reference examples with identical condition.
Table one
Please refer to table one, wherein, embodiment 1～3 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 embodiment 1～3 described red light flourescent material gained, 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 1～3 is all greater than reference examples 1～2, especially in embodiment 2, when the molar ratio of tungsten and molybdenum was 0.5: 0.5, its relative briliancy was 1.9 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. 6 is the synoptic diagram of a kind of white light emitting device of preferred embodiment of the present invention.Please refer to Fig. 6, 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 also comprise: gold-tinted fluorescent material (not illustrating), blue-light fluorescent material (not illustrating) or green glow fluorescent material (not illustrating).Above-mentioned red light flourescent material is suitable 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 can be 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, the second light L2 (ruddiness) that first light L1 (blue green light) that this moment, light-emitting diode chip for backlight unit 210 was sent and red light flourescent material are inspired, 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 can be selected blue light-emitting diode for use and send the first light L1 (blue light); 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 light-emitting diode chip for backlight unit 210 can be selected ultraviolet light-emitting diodes for use.At this moment, the first light L1 that light-emitting diode chip for backlight unit 210 is produced is a UV-light, and 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 see through 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.
Though the present invention discloses as above with embodiment; right its is not in order to limit the present invention; have in the technical field under any and know the knowledgeable usually; without departing from the spirit and scope of the present invention; when doing a little change and retouching, so protection scope of the present invention is as the criterion when looking the claim person of defining.
Claims (12)
1. red light flourescent material is suitable for being subjected to one first light and excites and radiate a ruddiness, it is characterized in that this red light flourescent material is characterised in that:
This red light flourescent material has the chemical formula of following formula (1),
A
2Eu (MO
4) (PO
4)-------Shi (1);
Wherein, A represents lithium, sodium, potassium, rubidium, caesium or silver; M represents the combination (Mo of molybdenum, tungsten 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 this first light is between 360 nanometers～550 nanometers.
3. red light flourescent material as claimed in claim 1, wherein, the wavelength region of this first light comprises: near-ultraviolet light wavelength 394 ± 10nm, blue light wavelength 465 ± 10nm or yellow green light wavelength 535 ± 10nm.
4. red light flourescent material as claimed in claim 1 is characterized in that, represents the combination (Mo of this molybdenum and tungsten as M
xW
(1-x)) time, x is a mole fraction, it is worth between 0～1.
5. red light flourescent material as claimed in claim 1, wherein, the chromaticity coordinates of this ruddiness can reach (0.66,0.33), and the relative brightness value of this ruddiness is 1.5cd/m
2～1.9cd/m
2
6. the manufacture method of a red light flourescent material is characterized in that, comprising:
Provide a mixture to comprise according to chemical dose: an europiumsesquioxide, a diammonium hydrogen phosphate, and the combination of a metal molybdate or a metal tungstates or this metal molybdate and this metal tungstates;
Mixing is also ground this mixture; And
This mixture of sintering is to obtain this red light flourescent material.
7. the manufacture method of red light flourescent material as claimed in claim 6 is characterized in that, mixes and time of grinding this mixture is 30 minutes, and the temperature of this mixture of sintering is 600 ℃, and the time of this 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, this red light flourescent material has the chemical formula of following formula (1),
A
2Eu (MO
4) (PO
4)-------Shi (1);
Wherein, A represents lithium, sodium, potassium, rubidium, caesium or silver; M represents the combination (Mo of molybdenum, tungsten or molybdenum and tungsten
xW
(1-x)).
9. the manufacture method of red light flourescent material as claimed in claim 6 is characterized in that, also comprises a CHARACTERISTICS IDENTIFICATION step, identifies the physics and the chemical property of this red light flourescent material, and this CHARACTERISTICS IDENTIFICATION step comprises:
X ray diffraction analysis, fluorescent spectroscopy, tristimulus coordinates analysis or UV-light-visible reflectance spectrum analysis.
10. 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, this photoluminescence fluor comprises red light flourescent material as claimed in claim 1 at least;
Wherein, this photoluminescence fluor is subjected to this first exciting of light and radiates one second light, and this first light and this second light mixed light are white light.
11. white light emitting device as claimed in claim 10 is characterized in that, the wavelength region of this first light comprises: near-ultraviolet light wavelength 394 ± 10nm, blue light wavelength 465 ± 10nm or yellow green light wavelength 535 ± 10nm.
12., it is characterized in that this photoluminescence fluor also comprises as claim 10 or 11 described white light emitting devices:
One gold-tinted fluorescent material, a blue-light fluorescent material or a green glow fluorescent material;
Wherein, this red light flourescent material is suitable for selecting collocation to use with this gold-tinted fluorescent material, this blue-light fluorescent material and this green glow fluorescent material.
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|---|---|---|---|
| CN2009100514362A CN101892052A (en) | 2009-05-18 | 2009-05-18 | Red light luminescent material, manufacturing method thereof and white light emitting device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100514362A CN101892052A (en) | 2009-05-18 | 2009-05-18 | Red light luminescent material, manufacturing method thereof and white light emitting device |
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| CN101892052A true CN101892052A (en) | 2010-11-24 |
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ID=43101403
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|---|---|---|---|
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| JP2010242051A (en) * | 2009-04-01 | 2010-10-28 | Chunghwa Picture Tubes Ltd | Red phosphor, method for producing the same, and white light emitting device |
| CN102041003A (en) * | 2010-12-03 | 2011-05-04 | 华映视讯（吴江）有限公司 | Fluorescent materials and white light emitting component |
| CN102559185A (en) * | 2010-12-20 | 2012-07-11 | 财团法人交大思源基金会 | Yellow luminescent material with voelckerite structure and preparation method thereof as well as white light-emitting diode device |
| CN106566551A (en) * | 2016-10-08 | 2017-04-19 | 中山大学 | Red fluorescent powder applied to white-light LED device and preparing method of red fluorescent powder |
| CN109233834A (en) * | 2018-10-25 | 2019-01-18 | 德州学院 | A kind of phosphate base red fluorescence powder of high quantum production rate and preparation method thereof of ultraviolet leds chip excitation |
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| JP2008069334A (en) * | 2006-09-12 | 2008-03-27 | Jiaotong Univ | HIGHLY SATURATED RED LIGHT EMITTING Mn(IV)-ACTIVATED FLUORESCENT AND ITS MANUFACTURING PROCESS |
| CN101343541A (en) * | 2008-08-26 | 2009-01-14 | 江苏技术师范学院 | Red fluorescent powder for white radiation LED and preparation thereof |
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| CN1948427A (en) * | 2005-10-14 | 2007-04-18 | 财团法人工业技术研究院 | Red light fluorescent powder |
| JP2008069334A (en) * | 2006-09-12 | 2008-03-27 | Jiaotong Univ | HIGHLY SATURATED RED LIGHT EMITTING Mn(IV)-ACTIVATED FLUORESCENT AND ITS MANUFACTURING PROCESS |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010242051A (en) * | 2009-04-01 | 2010-10-28 | Chunghwa Picture Tubes Ltd | Red phosphor, method for producing the same, and white light emitting device |
| CN102041003A (en) * | 2010-12-03 | 2011-05-04 | 华映视讯（吴江）有限公司 | Fluorescent materials and white light emitting component |
| CN102559185A (en) * | 2010-12-20 | 2012-07-11 | 财团法人交大思源基金会 | Yellow luminescent material with voelckerite structure and preparation method thereof as well as white light-emitting diode device |
| CN102559185B (en) * | 2010-12-20 | 2014-12-17 | 财团法人交大思源基金会 | Yellow luminescent material with voelckerite structure and preparation method thereof as well as white light-emitting diode device |
| CN106566551A (en) * | 2016-10-08 | 2017-04-19 | 中山大学 | Red fluorescent powder applied to white-light LED device and preparing method of red fluorescent powder |
| CN109233834A (en) * | 2018-10-25 | 2019-01-18 | 德州学院 | A kind of phosphate base red fluorescence powder of high quantum production rate and preparation method thereof of ultraviolet leds chip excitation |
| CN109233834B (en) * | 2018-10-25 | 2019-10-01 | 德州学院 | A kind of phosphate base red fluorescence powder of high quantum production rate and preparation method thereof of ultraviolet leds chip excitation |
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Application publication date: 20101124 |