CN103045259A - Oxynitride fluorescent powder, preparation method thereof and LED light source including same - Google Patents
Oxynitride fluorescent powder, preparation method thereof and LED light source including same Download PDFInfo
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- CN103045259A CN103045259A CN2012105567315A CN201210556731A CN103045259A CN 103045259 A CN103045259 A CN 103045259A CN 2012105567315 A CN2012105567315 A CN 2012105567315A CN 201210556731 A CN201210556731 A CN 201210556731A CN 103045259 A CN103045259 A CN 103045259A
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Abstract
The invention discloses an oxynitride fluorescent powder, of which the structural formula is (M1-xRex) 3 (Al, Ga) 5-yByO12-yNy, wherein M is one or more elements of Y, Lu, Gd and Tb; Re is one or both elements of Ce and Pr, x is larger than 0 and smaller than or equal to 0.1, and y is larger than or equal to 0 and smaller than or equal to 1.0. The invention discloses a preparation method of the oxynitride fluorescent powder and further discloses a white-light light source including the oxynitride fluorescent powder. According to the invention, the luminescence property of YAG:Ce fluorescent powder is improved for the first time through introduction of BN, and the luminescence is enhanced while temperature rises, so that a higher luminous efficiency is provided within a larger temperature range.
Description
Technical field
The invention belongs to the fluorescent material technical field, be specifically related to a kind of oxynitride fluorescent powder and preparation method thereof and comprise the led light source of this fluorescent material.
Background technology
White light emitting diode is fast-developing in recent years a kind of New Solid lighting source, compare with traditional incandescent light and luminescent lamp, the advantages such as it has energy-saving and environmental protection, the life-span is long, volume is little, response is fast, shock-resistant, being described as is the 4th generation lighting source (S.Nakamura et al. after incandescent light, luminescent lamp and high-voltage gas discharging light, Appl.Phys.Lett., 64,1687 (1994)).
White light is to realize according to the photosynthetic reason proportioning of the principle of three primary colours by three kinds of colors of RGB RGB as a kind of mixed light.At present, the implementation that the most extensively adopts of white light LEDs is to apply one deck Ce at blue light InGaN chip
3+(the Y that mixes
1-aGd
a)
3(Al
1-bGa
b) O
12(being called for short YAG:Ce) yellow fluorescent powder (US Pat.5998925,6069440,7071616; S.Nakamura et al., Springer, Berlin, 1997).This structure has advantages of stable performance, production cost is low and be easy to realize.But, because the YAG:Ce fluorescent material that adopts lacks the red emission of long-wave band, cause the white LED light source colour rendering index CRI on the low side of this combination preparation＜75, the higher CCT＞5000K of colour temperature, the warm white LED device of general room illumination is satisfied in very difficult preparation.Therefore, in order to improve the optical property of above-mentioned white LED light source, in recent years, many investigators have carried out YAG:Ce
3+The study on the modification of fluorescent material.
Method one of the prior art is by the mutual replacement of cation position, that is: by other metal ion of different size or the Y of ion pair replacement dodecahedron position
3+The perhaps Al of octahedron or tetrahedral site
3+, change Ce
3+Crystal field on every side causes the crystal field splitting of its 5d excited state to increase or reduces, and then makes the emmission spectrum of this fluorescent material that to a certain degree red shift or blue shift occur, and its luminous intensity also changes simultaneously.(M.C.Maniquiz?et?al.，J.Electrochem.Soc.，157，H1135(2010)，US?pat.5,998,925，6,069,440，7,071,616，6,409,938；E.P.pat.1,116,418)。Method two: by the common replacement of zwitterion, both by the stronger Si of covalency
4+-N
3-Key or Al
3+-N
3-Key replaces the relatively weak Al of covalency
3+(tetrahedral site)-O
2-Key has strengthened Ce
3+Covalency on every side, cause the crystal field splitting of its 5d excited state to increase, and then make its emmission spectrum generation red shift to a certain degree, use this single-component phosphor in conjunction with the white light LED part of the led chip development of blue light InGaN, CCT can be reduced to below the 4000K, and CRI can bring up to 80.But simultaneously, luminous intensity and the thermostability of fluorescent material reduces (A.A.Setlur et al., Chem.Mater., 20:6277 (2008) greatly with it; US Pat.0,197,443, World Pat.WO2005/061659, WO2006/050645).This replacement is further analyzed, has both used equally Si
4+The Al that replaces tetrahedral site
3+, and use Ca
2+Or Mg
2+Carry out charge compensation, can not cause that then emmission spectrum similar long wave direction occurs and moves.
Summary of the invention
The present invention overcomes the above defective of prior art, and the led light source that has proposed first a kind of new oxynitride fluorescent powder and preparation method thereof and comprised this fluorescent material is used.The present invention proposes with B with innovating
3+-N
3-The mode of key (BN) is introduced N
3-, without Si
4+As charge compensation, both used B
3+-N
3-Key replaces Al
3+(tetrahedral site)-O
2-Key.After correspondingly replacing, how to affect structure and the luminescent properties of YAG:Ce fluorescent material? whether also can make its emmission spectrum produce certain red shift? how do luminous intensity and thermostability change? at present also not research report and the Patents of this aspect.
One of purpose of the present invention is N
3-Mode with BN is incorporated in the YAG:Ce lattice, in the situation that keep its original structure, has developed a kind of novel garnet-base oxynitride fluorescent powder.Use B
3+-N
3-Key replaces Al
3+(tetrahedral site)-O
2-Key is by changing Ce
3+Localised crystal's field environment on every side is optimized its luminescent properties, and when improving its luminous efficiency, thermostability strengthens greatly.This fluorescent material is used for white light LED part, can greatly improves the stability of photoluminescence under the LED device high temperature and prolong its work-ing life.
The invention provides a kind of oxynitride fluorescent powder, it adopts chemical general formula (M
1-xRe
x)
3(Al, Ga)
5-yB
yO
12-yN
yExpression, wherein M is one or more elements among Y, Lu, Gd, the Tb, and Re is one or both elements among Ce, the Pr, and each parameter satisfies 0＜x≤0.1,0≤y≤1.0.
Oxynitride fluorescent powder provided by the present invention is with N
3-Mode with BN is incorporated in the YAG:Ce lattice, namely uses B
3+-N
3-Key has replaced Al
3+-O
2-Key.
Oxynitride fluorescent powder provided by the present invention after adding BN, has still kept original garnet crystal lattice structure.
Oxynitride fluorescent powder provided by the present invention, the 5nm blue shift has occured in its luminescent spectrum after adding BN.
Oxynitride fluorescent powder provided by the present invention, its luminous intensity has improved 11% after adding BN.
Oxynitride fluorescent powder provided by the present invention, its luminous intensity increases along with the rising of temperature after adding BN, conventional temperature cancellation do not occur, and at 250 ℃, its luminous intensity has been brought up to 175% under the room temperature.
The present invention also provides a kind of preparation method of oxynitride fluorescent powder, and its initial feed that adopts comprises: the oxide compound of the oxide compound of pure M and pure Re, nanometer α-Al
2O
3, Ga
2O
3, nanometer BN and account for the sintering aid NH of the analytical pure level of initial feed weight 1wt%
4F.Wherein, described nanometer BN is the non-crystalline state BN of content＞99%, median size 20nm.
The preparation method of oxynitride fluorescent powder provided by the present invention may further comprise the steps:
(1) takes by weighing raw material; Described raw material comprises: the oxide compound of the oxide compound of pure M and pure Re, nanometer α-Al
2O
3, Ga
2O
3, nanometer BN and sintering aid NH
4F;
(2) preparation of oxide compound mixing presoma: described raw material is put into the tetrafluoroethylene ball grinder, add dehydrated alcohol and zirconia ball, to obtain precursor pulp drying, pulverizing after fully grinding, cross 200 eye mesh screens, both obtain required oxide compound precursor;
(3) high temperature solid-phase sintering: the Al that above-mentioned oxide precursor will be housed
2O
3Crucible places the high temperature sintering furnace take graphite as heating element, at 95%N
2/ 5%H
2Under the atmosphere, 1400-1650 ℃, be incubated thermal treatment in 4-10 hour, temperature rise rate is 300-600 ℃/h, synthetic fluorescent powder is with body water-cooling;
(4) pickling: above-mentioned fluorescent powder is put into the beaker that fills deionized water, adding concentration is the dilute hydrochloric acid of 36%-38%, wherein the volume ratio of deionized water and dilute hydrochloric acid is 10: 1, continuously stirring is 1 hour under the normal temperature, standing demix, filter supernatant liquid after, with washed with de-ionized water to solution PH=6.5-7.0, filtration, drying obtain described oxynitride fluorescent powder.
The present invention also provides a kind of white LED light source, and it comprises: the LED photophore, and be arranged on the luminescent layer that contains described oxynitride fluorescent powder on this LED photophore.
During the present invention used, for after being arranged on the luminescent layer of white light LEDs photophore, its luminous efficiency had improved 7.4% with oxynitride fluorescent powder.
Wherein, the luminescence chip in the described LED photophore is that emission wavelength is at the led chip of the InGaN of 440-470nm base.The structure of LED device is referring to another part Chinese invention patent application (application number: 201110407225.5) of applicant.
The present invention compared with prior art has following advantage: 1. first passage BN is with B
3+-N
3-The mode of key is introduced N in the YAG lattice
3-, without Si
4+As charge compensation, synthesized a kind of novel (M
1-xRe
x)
3(Al, Ga)
5-yB
yO
12-yN
yOxynitride fluorescent powder; 2. studied first the introducing of BN to the impact of YAG:Ce base fluorescent powder luminescent properties, B
3+-N
3-The introducing of key has increased the covalency around the light emitting ionic equally, but blue shift has to a certain degree appearred in its luminescent spectrum, and luminous intensity increases; 3. synthetic oxynitride fluorescent powder comprises very wide excitation and emission spectra, can effectively be excited by the blue light of 440-470nm, sends the peak wavelength scope at green glow or the gold-tinted of 505-550nm; 4. synthetic its luminous intensity of oxynitride fluorescent powder rises along with the increase of temperature, conventional temperature quenching phenomenon do not occur; 5. synthetic oxynitride fluorescent powder is coated on the LED chip of InGaN base, in conjunction with special optical texture design, the white LED light source that has prepared a kind of high-luminous-efficiency, its chromaticity coordinates, colour rendering index and colour temperature are adjustable in certain scope, can be satisfied with the application requiring of varying environment.
Be that 201110407225.5 patent is compared with the application number of application before the applicant, progress of the present invention and advantage comprise: (1) replaces Si with BN
3N
4With B
3+-N
3-The mode of key is introduced N in the YAG lattice
3-, without Si
4+As charge compensation, synthesized a kind of novel (M
1-xRe
x)
3(Al, Ga)
5-yB
yO
12-yN
yOxynitride fluorescent powder.(2) in application number is 201110407225.5 patent, Si
3N
4Introducing cause the emmission spectrum of YAG:Ce fluorescent material significantly red shift to occur, simultaneously luminous intensity and thermostability sharply descend.BN is incorporated into after the YAG:Ce fluorescent material in the present invention, the blue shift of 5nm has but appearred in its luminescent spectrum, and luminous intensity has increased by 11%, simultaneously, its thermostability strengthens greatly, conventional temperature quenching phenomenon do not occur, luminous intensity strengthens along with the increase of temperature, in the time of 250 ℃, its luminous intensity even reached 175% under the room temperature, the red shift of 15nm has appearred in luminescent spectrum simultaneously.(3) synthetic oxynitride fluorescent powder is coated on the led chip of InGaN base, in conjunction with special optical texture design, the white LED light source that has prepared a kind of high-luminous-efficiency, its chromaticity coordinates, colour rendering index and colour temperature are adjustable in certain scope, luminous efficiency has increased by 7.5%, can be satisfied with the application requiring of varying environment.
Description of drawings
Fig. 1 is the XRD figure spectrum of the oxynitride fluorescent powder of the garnet structure that embodiment 1-5 synthesizes among the present invention.
Fig. 2 is the excitation and emission spectra of embodiment 1-5 synthetizing phosphor powder among the present invention.
Fig. 3-1 is the SEM photo of the fluorescent material that embodiment 1 synthesizes among the present invention.
Fig. 3-2 is the SEM photo of the fluorescent material that embodiment 2 synthesizes among the present invention.
Fig. 3-3 is the SEM photo of the fluorescent material that embodiment 4 synthesizes among the present invention.
Fig. 3-4 is the SEM photo of the fluorescent material that embodiment 5 synthesizes among the present invention.
Fig. 4 is the luminescent spectrum of 3 synthetizing phosphor powders of embodiment under differing temps among the present invention.
Fig. 5 is for adopting the synthetic fluorescent material of embodiment 1-5, the electroluminescent spectrum of the white LED light source device of making by embodiment 6.
Embodiment
In conjunction with following specific embodiments and the drawings, the present invention is described in further detail.Implement process of the present invention, condition, reagent, experimental technique etc., except the following content of mentioning specially, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
Adopt the material prescription of prior art and the preparation process that is equipped with among the present invention to prepare, illustrate that as benchmark the interpolation of nanometer BN is on the impact of fluorescent material pattern, structural and optical properties.
Step (1) takes by weighing raw material.With Y
2O
3, nanometer α-Al
2O
3And CeO
2Press chemical formula Y
2.925Ce
0.075Al
5O
12Strict ratio batching, take by weighing the Y of 3.30g
2O
3, 2.55g α-Al
2O
3, 0.13g CeO
2With 0.06g solubility promoter NH
4F, the purity of above-mentioned raw materials is 99.99% or 99.9995%, i.e. 4N or 5N, solubility promoter NH
4F is analytical pure, chemical formula Y
2.925Ce
0.075Al
5O
12In Ce
3+=2.5at%.
Among the present invention, " pure M and the oxide compound of Re " refers to that purity is 99.99% or 99.9995% high pure oxide.
Step (2) is at first put into the tetrafluoroethylene ball grinder with above-mentioned four kinds of raw materials, adds the zirconia ball of 5ml dehydrated alcohol and 24.2g φ 3mm, fully grinds 3-5 hour; The precursor slurry that obtains was put in 80-120 ℃ the vacuum drying oven insulation 10-20 hour, obtained the dry oxide compound precursor that contains the part coacervate; Then the above-mentioned oxide compound precursor that contains the part coacervate is placed in the agate mortar and grinds gently, pulverize, cross 200 eye mesh screens, extracting screen underflow is the oxide compound precursor.
Step (3), high temperature solid-phase sintering is put into Al with above-mentioned oxide compound precursor
2O
3Crucible also places high temperature sintering furnace take graphite as heating element, 95%N
2/ 5%H
2Under the atmosphere, 1400-1650 ℃, be incubated thermal treatment in 4-10 hour, temperature rise rate is 300-600 ℃/h, synthetic fluorescent powder is with body water-cooling.
Step (4), pickling, fluorescent powder after taking out is put into the beaker that fills the 100ml deionized water, adding concentration is 36%～38% dilute hydrochloric acid 10ml, and continuously stirring is 1 hour under the normal temperature, standing demix, filter supernatant liquid, repeatedly clean to solution PH=6.5-7.0 with deionized water, filtered and put into the dry 10-20 of loft drier hour, obtain the yellow YAG:Ce fluorescent material that can effectively be excited to blue light by ultraviolet.
Adopt preparation process of the present invention can synthesize the YAG:Ce fluorescent material of pure phase, about median size 15 μ m, in ultraviolet or blue-light excited lower, send main peak at the gold-tinted of 530nm.
Following initial feed with 4N or 5N: Y
2O
3, nanometer α-Al
2O
3, CeO
2Amorphous BN presses chemical formula Y with nanometer
2.925Ce
0.075Al
4.7B
0.3O
11.7N
0.3Strict ratio batching, take by weighing the Y of 3.30g
2O
3, 2.40g α-Al
2O
3, 0.07g BN, 0.13g CeO
2NH with 0.06g
4F is as solubility promoter, wherein Ce
3+=2.5at%, the relative content of BN are 0.3mol.
Above-mentioned five kinds of initial feed are put into the tetrafluoroethylene ball grinder, and the zirconia ball 23.8g of the dehydrated alcohol 5ml of 0.8 times of initial feed weight of adding and the φ 3mm of 4 times of initial feed weight fully ground 3-5 hour; The precursor slurry that obtains was put in 80-120 ℃ the vacuum drying oven insulation 10-20 hour, obtained the dry oxide compound precursor that contains the part coacervate; Then the above-mentioned oxide compound precursor that contains the part coacervate is placed in the agate mortar and grinds gently, pulverize, cross 200 eye mesh screens, extracting screen underflow is the oxide compound precursor; At last above-mentioned oxide compound precursor is put into Al
2O
3Crucible also places high temperature sintering furnace take graphite as heating element, at 95%N
2/ 5%H
2Under the atmosphere, 1400-1650 ℃, be incubated thermal treatment in 4-6 hour, temperature rise rate is 300-600 ℃/h, synthetic fluorescent powder is with body water-cooling.Fluorescent powder after the taking-up is put into the beaker that fills the 100ml deionized water, adding concentration is the dilute hydrochloric acid 10ml of 36%-38%, under 100 ℃ of conditions, stirred 1 hour, standing demix, after filtering supernatant liquid, repeatedly clean to solution PH=6.5-7.0 with deionized water, filtered and put into the dry 10-20 of loft drier hour, obtain the yellow-green colour Y that can effectively be excited to blue light by ultraviolet
2.925Al
4.7B
0.3O
11.7N
0.3: Ce fluorescent material.
After adding the BN of relative content 0.3mol, do not change garnet crystalline network, still can obtain pure YAG phase, but crystal grain begins to grow up, average grain size is about 25 μ m.Blue-light excited lower, send predominant wavelength at the yellow green light of 528nm.Compare with the fluorescent material that embodiment 1 obtains, luminous intensity has improved 11%.
Following initial feed with 4N or 5N: Y
2O
3, nanometer α-Al
2O
3, CeO
2Amorphous BN presses chemical formula Y with nanometer
2.925Ce
0.075Al
4.5B
0.5O
11.5N
0.5Strict ratio batching, Ce wherein
3+=2.5at%, the relative content of BN are 0.5mol.Y with 3.30g
2O
3, 2.30g α-Al
2O
3, 0.12g BN, 0.13g CeO
2Solubility promoter NH with 0.06g
4F presses the technique preparation described in the embodiment 2, obtains the yellow-green colour Y that can effectively be excited to blue light by ultraviolet
2.925Al
4.5B
0.
5O
11.5N
0.5: Ce fluorescent material.
As shown in Figure 4, behind the BN of interpolation relative content 0.5mol, still can obtain the YAG phase of pure garnet structure, its crystal grain is further grown up, and average grain size is about 35 μ m.Blue-light excited lower, send predominant wavelength at the yellow green light of 527nm, the sample of the BN of luminous intensity and interpolation 0.3mol is suitable.This fluorescent material is characterized at the luminescent properties under the differing temps, find that conventional temperature quenching phenomenon does not appear in its luminous intensity, but along with the luminous continuous enhancing of rising from room temperature to 250 ℃, in the time of 250 ℃, its luminous intensity even reached 175% under the room temperature.Simultaneously, the red shift of 15nm has appearred in luminescent spectrum.
Following initial feed with 4N or 5N: Y
2O
3, nanometer α-Al
2O
3, CeO
2Amorphous BN presses chemical formula Y with nanometer
2.925Ce
0.075Al
4.3B
0.7O
11.3N
0.7Strict ratio batching, Ce wherein
3+=2.5at%, the relative content of the amorphous BN of nanometer are 0.7mol.Y with 3.30g
2O
3, 2.19g nanometer α-Al
2O
3, the amorphous BN of 0.17g nanometer, 0.13g CeO
2Solubility promoter NH with 0.06g
4F presses the technique preparation described in the embodiment 2, obtains the yellow-green colour Y that can effectively be excited to blue light by ultraviolet
2.925Al
4.3B
0.7O
11.3N
0.7: Ce fluorescent material.
After adding the BN of relative content 0.7mol, the XRD material phase analysis shows except principal crystalline phase YAG, impurity phase YBO
3Begin to occur, the solid solubility≤0.5mol of BN the best in the YAG lattice is described.Its crystal grain is further grown up, and largest grain size is about 60 μ m.Blue-light excited lower, send predominant wavelength at the yellow green light of 526nm, to compare with the fluorescent material that embodiment 1 obtains, luminous intensity has improved 7.5%.
Following initial feed with 4N or 5N: Y
2O
3, nanometer α-Al
2O
3, CeO
2, the amorphous BN of nanometer presses chemical formula Y
2.925Ce
0.075Al
4BO
11The strict ratio batching of N, wherein Ce
3+=2.5at%, the relative content of the amorphous BN of nanometer are 1.0mol.Y with 3.30g
2O
3, 2.04g α-Al
2O
3, the amorphous BN of 0.25g nanometer, 0.13g CeO
2And the NH of 0.06g
4F presses the technique preparation described in the embodiment 2, obtains the yellow-green colour Y that can effectively be excited to blue light by ultraviolet
2.925Al
4BO
11N:Ce fluorescent material.
After adding the BN of relative content 1.0mol, impurity phase YBO
3Content increases gradually, and its crystal grain is also further obviously grown up, and is suitable with the sample of interpolation 0.7molBN, illustrates that unnecessary BN does not enter in the YAG lattice, but formed YBO with the form of impurity phase
3Blue-light excited lower, send predominant wavelength at the yellow green light of 525nm, to compare with the fluorescent material that embodiment 1 obtains, luminous intensity has reduced by 7.5%.
Embodiment 6
The structure of white LED light source, the Chinese invention patent application of seeing application number 201110407225.5.Be provided with the luminescent layer that comprises the described fluorescent material of this patent at LED luminescent device upper surface, thereby improve its luminescent properties and the gold-tinted that its blue light that sends and blue chip are sent is compounded to form white light.
Embodiment 7-10
Following initial feed with 4N or 5N: Y
2O
3, Lu
2O
3, Gd
2O
3, Tb
4O
7, nanometer α-Al
2O
3, Ga
2O
3, CeO
2, Pr
6O
11, the amorphous BN of nanometer and NH
4F is respectively in the strict ratio batching of each chemical formula shown in the table 1, wherein Ce
3+=2.5at%, Pr
3+=0.5at%, the relative content of the amorphous BN of nanometer are 0.5mol.Each initial feed content shown in the table 1 is pressed the technique preparation described in the embodiment 2, obtain effectively to be excited and containing to blue light by ultraviolet (the M of green, yellow and red wave band
1-xRe
x)
3(Al, Ga)
4.5B
0.5O
11.5N
0.5Fluorescent material.
The chemical constitution of synthetizing phosphor powder and corresponding proportioning raw materials among the table 1 embodiment 7-10
Comparing embodiment 1-5 can draw, and adds among a small amount of BN to YAG:Ce of relative content≤0.5mol, does not change the crystalline network of YAG, referring to accompanying drawing 1, still can obtain the YAG:Ce fluorescent material of pure phase; When the relative addition of BN reaches 0.7mol above 0.5mol, impurity phase YBO
3Begin to occur, the solid solubility≤0.5mol of BN the best in the YAG lattice is described.
Comparing embodiment 1-5 prepares the luminescent spectrum (accompanying drawing 3) of fluorescent material and finds, add in nano-scale amorphous BN to the YAG:Ce lattice, blue shift has a little appearred in emmission spectrum, and emission peak is blue shifted to 525nm from 530nm.Simultaneously, the trend that reduces has afterwards appearred increasing first in luminous intensity, and is when the addition of BN is 0.5-0.7mol, luminous the strongest.Microstructure referring to accompanying drawing 3-1 to 3-4 can find out, add BN after, the crystal grain of fluorescent material is grown up gradually, crystallinity is better, is 0.7mol at the addition of BN, crystal grain is 60 μ m to the maximum, continues to increase the content of BN, crystal grain is no longer grown up.
Oxynitride fluorescent powder synthetic among the embodiment 3 is characterized at the luminescent spectrum under the differing temps, referring to accompanying drawing 4, can find out, add the oxynitride fluorescent powder that a small amount of BN makes, its luminous intensity strengthens along with the increase of temperature, in the time of 250 ℃, its luminous intensity even reached 175% under the room temperature.Simultaneously, the red shift of 15nm has appearred in luminescent spectrum.
Adopt the in conjunction with the embodiments white LED light source device of the technique preparation in 6 of any single oxynitride fluorescent powder synthetic among the embodiment 1-5, under the forward current of 20mA, provided bright white light emission, referring to accompanying drawing 5; Its chromaticity coordinates is positioned at white portion: 0.29≤x≤0.32,0.30≤y≤0.35, colour temperature: CCT 〉=6000K, colour rendering index: CRI 〉=75, luminous efficiency:＞125lm/W, be satisfied with the application demand of general room illumination, be expected to replace incandescent light and luminescent lamp, become the main product of following interior lighting.
Comparing embodiment 7-10 can draw, and behind the interpolation BN, can cause equally the increase of luminous intensity and the blue shift of emmission spectrum.Comparing embodiment 3 and and 7 find, add the Pr of 0.5at%
3+After, the red emission peak of its emmission spectrum a little less than the 638nm place occurs one can remedy the deficiency that YAG:Ce fluorescent material lacks red emission, improves the colour rendering index of white light LEDs.Comparing embodiment 3 and 8 is found, after Y element is replaced by Lu, sends main peak at the green glow of 505nm, the blue shift of 25nm occurred, and luminous intensity improves 20%.Comparing embodiment 3 and 9 is found, after the Y of 25at% is replaced by Gd, sends main peak at the orange light of 545nm, the red shift of 15nm occurred, and luminous intensity has improved 5% simultaneously.Comparing embodiment 3 and 9 is found, after the Y of 27at% is replaced by Ga by 25at%Gd, 1at%Lu, 1at%Tb and 10at%Al respectively, sends main peak at the gold-tinted of 540nm, the red shift of 10nm occurred, and luminous intensity improves 10% simultaneously.
Protection content of the present invention is not limited to above embodiment.Under the spirit and scope that do not deviate from inventive concept, variation and advantage that those skilled in the art can expect all are included in the present invention, and take appending claims as protection domain.
Claims (9)
1. an oxynitride fluorescent powder is characterized in that, it adopts chemical general formula (M
1-xRe
x)
3(Al, Ga)
5-yB
yO
12-yN
yExpression, wherein, M is one or more elements among Y, Lu, Gd, the Tb, Re is one or both elements among Ce, the Pr, 0＜x≤0.1,0≤y≤1.0.
2. oxynitride fluorescent powder as claimed in claim 1 is characterized in that, its structure is the garnet crystal lattice structure.
3. oxynitride fluorescent powder as claimed in claim 1 is characterized in that, the 5nm blue shift occurs its luminescent spectrum.
4. oxynitride fluorescent powder claimed in claim 1 is characterized in that, its luminous intensity increases along with the rising of temperature, the temperature cancellation do not occur.
5. the preparation method of an oxynitride fluorescent powder as claimed in claim 1 is characterized in that, may further comprise the steps:
(1) takes by weighing raw material; Described raw material comprises: the oxide compound of the oxide compound of pure M and pure Re, nanometer α-Al
2O
3, Ga
2O
3, nanometer BN and sintering aid NH
4F;
(2) preparation of oxide compound mixing presoma: after described raw material weighed by stoichiometric, put into the tetrafluoroethylene ball grinder, add dehydrated alcohol and zirconia ball, grind rear drying, pulverize, cross 200 eye mesh screens, namely obtain required oxide compound precursor;
(3) high temperature solid-phase sintering: the Al that above-mentioned oxide precursor will be housed
2O
3Crucible places the high temperature sintering furnace take graphite as heating element, at 95%N
2/ 5%H
2Under the atmosphere, 1400-1650 ℃, be incubated thermal treatment in 4-10 hour, temperature rise rate is 300-600 ℃/h, synthetic fluorescent powder is with body water-cooling;
(4) pickling: above-mentioned fluorescent powder is put into the beaker that fills deionized water, adding concentration is the dilute hydrochloric acid of 36%-38%, wherein the volume ratio of deionized water and dilute hydrochloric acid is 10: 1, continuously stirring is 1 hour under the normal temperature, standing demix, filter supernatant liquid after, with washed with de-ionized water to solution PH=6.5-7.0, filtration, drying obtain described oxynitride fluorescent powder.
6. the preparation method of oxynitride fluorescent powder as claimed in claim 5 is characterized in that, described nanometer BN is the non-crystalline state BN of content＞99%, median size 20nm.
7. a white LED light source is characterized in that, comprises the LED photophore, and is arranged on the luminescent layer that contains oxynitride fluorescent powder as claimed in claim 1 on this LED photophore.
8. white LED light source as claimed in claim 7 is characterized in that, the luminescence chip in the described LED photophore is that emission wavelength is at the led chip of the InGaN of 440-470nm base.
9. the application of oxynitride fluorescent powder as claimed in claim 1 is characterized in that, described oxynitride fluorescent powder is used for being arranged on the luminescent layer of white light LEDs photophore.
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Cited By (3)
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| CN104629759A (en) * | 2015-02-12 | 2015-05-20 | 杭州电子科技大学 | Method for enhancing emission intensity of strontium aluminate fluorescent powder |
| CN109592978A (en) * | 2018-12-03 | 2019-04-09 | 江苏师范大学 | High-capacity LED/LD illumination refers to fluorescence ceramics and the preparation method and application thereof with warm white height is aobvious |
| WO2020135303A1 (en) * | 2018-12-26 | 2020-07-02 | 深圳光峰科技股份有限公司 | Light-emitting device with high red light brightness and high reliability |
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