CN103173217A - Temperature-resisting nitride fluorescent material and light-emitting device comprising same - Google Patents
Temperature-resisting nitride fluorescent material and light-emitting device comprising same Download PDFInfo
- Publication number
- CN103173217A CN103173217A CN2011104374490A CN201110437449A CN103173217A CN 103173217 A CN103173217 A CN 103173217A CN 2011104374490 A CN2011104374490 A CN 2011104374490A CN 201110437449 A CN201110437449 A CN 201110437449A CN 103173217 A CN103173217 A CN 103173217A
- Authority
- CN
- China
- Prior art keywords
- fluorescent material
- light
- heatproof
- nitride fluorescent
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention relates to a temperature-resisting nitride fluorescent material and a light-emitting device containing the same. The temperature-resisting nitride fluorescent material has the chemical formula (I): M<1>yM<2>5OzNx: M<3>w (I), wherein M<1>, M<2>, the M<3>, x, y, w and z in the formula (I) are defined in the range shown as the specification and the patent application. The invention also provides the light-emitting device comprising a light-emitting diode material element which can emit a light source and the temperature-resisting nitride fluorescent material arranged on the light-emitting diode material element, wherein the temperature-resisting nitride fluorescent material emits light through absorbing at least a part of the light source. The temperature-resisting nitride fluorescent material disclosed by the invention has good heat-resisting stability and can emit natural and not-dazzling light when applied to the light-emitting device.
Description
Technical field
The present invention relates to a kind of fluorescent material, particularly relate to a kind of heatproof nitride fluorescent material.
Background technology
Day, inferior chemical industry was produced white light LEDs since 1996.United States Patent (USP) 5,998,925 disclose a kind of blue light-emitting diodes that adopt wavelength 450nm to 470nm as luminescence unit, and with the yttrium-aluminium garnet fluorescent substance (Y of cerium as active center
3Al
5O
12: Ce
3+, claim again YAG:Ce
3+) make up, and acquisition produces the luminescent system of white light.The part blue light that luminescence unit sends is absorbed by fluorescent substance and converts gold-tinted to is that main wider spectrum (spectral centroid is 580nm) is emitted, due to ruddiness and the green glow acceptor in a large amount of gold-tinted radiating capacity stimulation human eyes, add original a small amount of blue ray radiation has stimulated blue light receptor, seems similarly to be to have produced white light.
But the shortcoming that has in essence that is combined in of blue-ray LED and YAG fluorescent material is: cause color rendering not good because lacking ruddiness, luminous efficiency can increase and reduces with use temperature, and excites lower light of emitting at high power light source, and its temperature stability is not good.
For improving the shortcoming of YAG, many researchs improve towards adding Si or S.Because silicon or silicate substrate have higher thermostability and chemical stability, at ultraviolet region, stronger absorption is arranged, and highly purified silicon or earth silicon material is cheap easily obtains again, therefore with Si
4+Substitute for Al
3+Rare-earth ion activated siliceous luminescent material cause the height attention.
US 2010/0142182 discloses a kind of lighting system, and comprise one and contain the luminaire of the first luminous element, and the second luminous element that separates with luminaire.This first luminous element is provided with fluorescent material, can for example comprise Si and N with the yttrium-aluminium garnet fluorescent substance of cerium as activator, this fluorescent substance has following general molecular formula:
(Y
1-α-β-a-bLu
αGd
β)
3(Al
5-u-vGa
uSi
v)O
12-vN
v:Ce
a 3+
Wherein, 0≤α＜1,0≤β＜1,0＜(alpha+beta+a+b)≤1,0≤u≤1,0＜v＜1,0＜a≤0.2.
The structure that this fluorescent substance is based on YAG improves, but the inherent defect that contains Si fluorescent material is that tolerable temperature is lower and more unstable, and emit photochromic comparatively gorgeous, easily can cause overstimulation to human eye.If life-time service easily causes people's visual fatigue.Though this fluorescent material adds the higher nitrogen element of sintering temperature, but its sintering temperature is 1500 ℃, tolerable temperature is lower and stable deficiency still, it is similar to the YAG material of upgrading not that it drills colour index (Ra value), all be no more than 80%, and this type of fluorescent material when being used for light-emitting device required deal more.
From the above, research and develop that a kind of tolerable temperature is high, color rendering and good thermal stability, and photochromic naturally not dazzling fluorescent material is the present important topic of technique.
This shows, above-mentioned existing fluorescent material obviously still has inconvenience and defective, and demands urgently further being improved in method, product structure and use.In order to solve the problem of above-mentioned existence, relevant manufacturer there's no one who doesn't or isn't seeks solution painstakingly, but have no for a long time applicable design is completed by development always, and general method and product do not have appropriate method and structure to address the above problem, and this is obviously the problem that the anxious wish of relevant dealer solves.Therefore how to found a kind of new heatproof nitride fluorescent material and contain its light-emitting device, real one of the current important research and development problem that belongs to, also becoming the current industry utmost point needs improved target.
Summary of the invention
The object of the invention is to, overcome the defective that existing fluorescent material exists, and provide a kind of new heatproof nitride fluorescent material, technical problem to be solved is that the method that improves in the past YAG mainly replaces Al with Si, the inventor is more unstable and photochromic comparatively gorgeous dazzling under high temperature in view of the fluorescent material that contains Si, therefore develop and a kind ofly replace part 0 to add N, and do not contain the fluorescent material of Si.Therefore, the first purpose of the present invention namely providing a kind of heat-resisting stability high and photochromic natural heatproof nitride fluorescent material, is very suitable for practicality.
Another object of the present invention is to, a kind of light-emitting device is provided, comprise one and can send the light-emitting diodes material elements of a light source, and be arranged at the aforementioned heatproof nitride fluorescent material on this light-emitting diodes material elements; This heatproof nitride fluorescent material is luminous by absorbing this light source of at least a portion, thereby more is suitable for practicality.
The object of the invention to solve the technical problems realizes by the following technical solutions.Its that proposes according to the present invention has the chemical formula of following formula (I):
M
1 yM
2 5O
zN
x:M
3 w (I)
M
1To be selected from Sc
3+, Y
3+, La
3+, Sm
3+, Gd
3+, Pm
3+, Er
3+, Lu
3+, or an aforesaid combination; M
2Be selected from Al
3+, In
3+, Ga
3+, or an aforesaid combination; M
3To be selected from Tm
3+, Bi
3+, Tb
3+, Ce
3+, Eu
3+, Mn
3+, Er
3+, Yb
3+, Ho
3+, Gd
3+, Pr
3+, Dy
3+, Nd
3+, or an aforesaid combination; Reaching x is the integer of 3-8,2.7≤y≤3,0＜w≤0.3, and 0≤z≤7.5.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Aforesaid heatproof nitride fluorescent material, wherein said in 0.01≤w≤0.06.
Aforesaid heatproof nitride fluorescent material, wherein said this heatproof nitride fluorescent material is to be selected from Y
2.98Al
5O
7.5N
3: Tm
0.02,
Y
2.95Al
5O
6N
4:Bi
0.05、
Y
2.94Al
5O
6N
4:Tb
0.06、
Y
2.95Al
5O
7.5N
3:Ce
0.05、
Y
2.95Al
5O
6N
4:Ce
0.05、
Y
2.95Al
5O
4.5N
5:Ce
0.05、
Y
2.95Al
5O
6N
4:Mn
0.05、
Y
2.75GaAl
4O
6N
4:Mn
0.25、
Y
2.94Al
5N
8:Bi
0.06、
Y
2.94Al
5N
8:Tm
0.06、
Y
2.95Al
5N
8:Ce
0.05、
Y
2.95Al
5N
8:Mn
0.05、
Y
2.95Ga
5N
8:Mn
0.05、
Y
2.94Al
5O
6N
4:Bi
0.06、
Y
2.94Al
5O
6N
4:Mn
0.06、
Y
2.94Al
5O
6N
4:Ce
0.06、
Lu
1.72Gd
1.2Al
5O
6N
4:Ce
0.05Pr
0.03、
Lu
1.72Er
1Ga
5O
4.5N
5:Mn
0.25Dy
0.03、
Lu
1.92Sc
1Al
5O
6N
4:Ce
0.05Yb
0.03、
Sm
1.92La
1Al
5O
6N
4:Ce
0.05Ho
0.03、
Y
2.32Gd
0.6In
1Al
4O
6N
4:Ce
0.05Nd
0.03，
Or Lu
1.95Pm
1Al
5O
6N
4: Ce
0.05
Aforesaid heatproof nitride fluorescent material, the radiation wavelength region of wherein said this heatproof nitride fluorescent material is 380-700nm.
Aforesaid heatproof nitride fluorescent material, the excitation wavelength range of wherein said this heatproof nitride fluorescent material are 250-500nm.
The object of the invention to solve the technical problems also realizes by the following technical solutions.According to a kind of light-emitting device that the present invention proposes, it comprises: a light-emitting diodes material elements, can send a light source; Reaching one by the described heatproof nitride fluorescent material of any one in claim the 1-5 item, is to be arranged on this light-emitting diodes material elements; This heatproof nitride fluorescent material is luminous by absorbing this light source of at least a portion.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Aforesaid light-emitting device, the radiation wavelength region of wherein said this heatproof nitride fluorescent material is 380-700nm.
By technique scheme, heatproof nitride fluorescent material of the present invention and the light-emitting device that contains it have following advantages and beneficial effect at least: this heatproof nitride fluorescent material makes this heatproof nitride fluorescent material emit required coloured light via the various different elements of collocation; Compared take the material that YAG improves as the basis with the past, the present invention does not contain S or Si, but replaces part or all of O with N, by the covalent bond structure that N has, this nitride fluorescent material thermostability is promoted, and tolerable temperature is higher; When this heatproof nitride fluorescent material was applied to light-emitting device, after light source activation, that emits was photochromic more naturally not dazzling, and color rendering is better.
In sum, heatproof nitride fluorescent material of the present invention and contain its light-emitting device, its a kind of heatproof nitride fluorescent material has the chemical formula of following formula (I):
M
1 yM
2 5O
zN
x:M
3 w (I)
The M of formula (I)
1, M
2, M
3, x, y, w and z be as the definien of institute in specification sheets and claim.The present invention separately provides a kind of light-emitting device, comprise a light-emitting diodes material elements that can send a light source, and being arranged at aforementioned heatproof nitride fluorescent material on this light-emitting diodes material elements, this heatproof nitride fluorescent material is luminous by absorbing this light source of at least a portion.Heatproof nitride fluorescent material of the present invention possesses good heat-resistant stability, and when being applied to light-emitting device, that emits is photochromic naturally not dazzling.The present invention is a significant progress in technology, and has obvious positively effect, is really a new and innovative, progressive, practical new design.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, for can clearer understanding technique means of the present invention, and can be implemented according to the content of specification sheets, and for above and other objects of the present invention, feature and advantage can be become apparent, below especially exemplified by preferred embodiment, and the cooperation accompanying drawing, be described in detail as follows.
Description of drawings
Fig. 1 is a relative spectral power distribution plan, and the relative spectral power of embodiment 13 and comparative example 2 is described; (a) be the analytical results of embodiment 13 and (b) be the analytical results of comparative example 2;
Fig. 2 is a radiating light spectrogram;
Fig. 3 is a radiating light spectrogram;
Fig. 4 is a CIE chromaticity coordinate figure;
Fig. 5 is a CIE chromaticity coordinate figure; And
Fig. 6 is a light decay graphic representation, and the light decay curve of embodiment 5 and comparative example 1 is described; (a) be the analytical results of embodiment 5 and (b) be the analytical results of comparative example 1.
Embodiment
Reach for further setting forth the present invention technique means and the effect that predetermined goal of the invention is taked, below in conjunction with accompanying drawing and preferred embodiment, the heatproof nitride fluorescent material that foundation the present invention is proposed and its embodiment of light-emitting device, method, step, structure, feature and the effect thereof that contains it are described in detail as follows.
Heatproof nitride fluorescent material of the present invention has the chemical formula of following formula (I):
M
1 yM
2 5O
zN
x:M
3 w (I)
M
1For the active center metallic element, be trivalent rare earth element.M
1To be selected from Sc
3+, Y
3+, La
3+, Sm
3+, Gd
3+, Pm
3+, Er
3+, Lu
3+, or an aforesaid combination.
This M
2Being anion lattice, is to be selected from Al
3+, In
3+, Ga
3+, or an aforesaid combination.
This M
3Be the active center metallic element, or be the element that adds lustre to, have the fine setting effect, help to promote the brightness of this heatproof nitride fluorescent material.M
3To be selected from Tm
3+, Bi
3+, Tb
3+, Ce
3+, Eu
3+, Mn
3+, Er
3+, Yb
3+, Ho
3+, Gd
3+, Pr
3+, Dy
3+, Nd
3+, or an aforesaid combination.
In formula (I), 3≤x≤8,2.7≤y≤3,0＜w≤0.3, and 0≤z≤7.5.
The present invention makes this heatproof nitride fluorescent material emit required coloured light via the various different elements of collocation; And the present invention replaces part or all of 0 with N, because N has covalent bond structure, this heatproof nitride fluorescent material bond strength enhancing is easy fracture not, and tolerable temperature improves, and sintering temperature is at 1800 ℃, and good thermal stability.
Separately, as active center metallic element M
3Comprise Tm
3+Or Bi
3+The time, this heatproof fluorescent material is subjected to emit blue light after light source activation, as active center metallic element M
3Comprise Tb
3+Or Ce
3+The time, this heatproof fluorescent material is subjected to emit yellow green light after light source activation, as active center metallic element M
3Comprise Eu
3+Or Mn
3+The time, this heatproof fluorescent material is subjected to emit ruddiness after light source activation.This active center metallic element (or claim add lustre to element) except with the radiating light wavelength mutually outside the Pass, also help to promote the intensity of giving out light of this heatproof nitride fluorescent material.
Preferably, 0.01≤w≤0.06.As w less than 0.01 the time, the luminance shortage of this heatproof nitride fluorescent material; Greater than 0.06 the time, the radiation wavelength of this heatproof nitride fluorescent material can increase as this w, and causes brightness to descend.It is more preferably 0.01≤w≤0.03.
Preferably, this heatproof nitride fluorescent material is to be selected from
Y
2.98Al
5O
7.5N
3:Tm
0.02、
Y
2.95Al
5O
6N
4:Bi
0.05、
Y
2.94Al
5O
6N
4:Tb
0.06、
Y
2.95Al
5O
7.5N
3:Ce
0.05、
Y
2.95Al
5O
6N
4:Ce
0.05、
Y
2.95Al
5O
4.5N
5:Ce
0.05、
Y
2.95Al
5O
6N
4:Mn
0.05、
Y
2.75GaAl
4O
6N
4:Mn
0.25、
Y
2.94Al
5N
8:Bi
0.06、
Y
2.94Al
5N
8:Tm
0.06、
Y
2.95Al
5N
8:Ce
0.05、
Y
2.95Al
5N
8:Mn
0.05、
Y
2.95Ga
5N
8:Mn
0.05、
Y
2.94Al
5O
6N
4:Bi
0.06、
Y
2.94Al
5O
6N
4:Mn
0.06、
Y
2.94Al
5O
6N
4:Ce
0.06、
Lu
1.72Gd
1.2Al
5O
6N
4:Ce
0.05Pr
0.03、
Lu
1.72Er
1Ga
5O
4.5N
5:Mn
0.25Dy
0.03、
Lu
1.92Sc
1Al
5O
6N
4:Ce
0.05Yb
0.03、
Sm
1.92La
1Al
5O
6N
4:Ce
0.05Ho
0.03、
Y
2.32Gd
0.6In
1Al
4O
6N
4:Ce
0.05Nd
0.03，
Or Lu
1.95Pm
1Al
5O
6N
4: Ce
0.05
Preferably, the radiation wavelength region of this heatproof nitride fluorescent material is 380-700nm.Work as M
3Comprise the element T b that adds lustre to
3+, Er
3+, Yb
3+Or Ho
3+, the radiation wavelength region of this heatproof nitride fluorescent material is 380-530nm; Work as M
3Comprise the element Gd that adds lustre to
3+, Pr
3+, Dy
3+Or Nd
3+, the radiation wavelength region of this heatproof nitride fluorescent material is at 530-700nm.
Preferably, the excitation wavelength range of this heatproof nitride fluorescent material is 250-500nm.
Preferably, the particle size range of this heatproof Nitride phosphor is between 50nm-10 μ m.
The preparation method of this heatproof Nitride phosphor can be solid state process (solid-state method), Citrate trianion gel method, and coprecipitation method, is not limited to single kind of method preparation.
Preferably, this heatproof Nitride phosphor is prepared by solid state process.The advantage of solid state process is that method for making is simple, is conducive to a large amount of productions, therefore has the industry using value.More preferably, the sintering temperature of solid state process is 1800 ℃, and reduction temperature is 1500 ℃.
Light-emitting device of the present invention comprises: a light-emitting diodes material elements, can send a light source; And an aforementioned heatproof nitride fluorescent material, this heatproof nitride fluorescent material is arranged on this light-emitting diodes material elements; This heatproof nitride fluorescent material is luminous by absorbing this light source of at least a portion.
Preferably, this light-emitting diodes material elements can be such as but not limited to containing aluminium, gallium, nitrogen, phosphorus, or the chip of an aforesaid combination.More preferably, this light-emitting diodes material elements is the LED chip that is selected from blue light, blue light or green glow.
Preferably, the main peak value scope of the luminescent spectrum of this light source is 350-500nm.
Preferably, this heatproof nitride fluorescent material is to be arranged on this light-emitting diodes material elements by evaporation or vapour deposition.More preferably, this heatproof nitride fluorescent material forms a film by evaporation or vapour deposition on this light-emitting diodes material elements, and this film has as level and smooth high-quality surface as minute surface.
The present invention will be described further with regard to following examples, but will be appreciated that, this embodiment is only for illustrating use, and should not be interpreted as restriction of the invention process.
＜chemical source 〉
Bismuth oxide (Bi
2O
3): available from ACROS company, purity 99.9%, reagent level.
Barium fluoride (BaF
2): available from ACROS company, purity 99.9%, reagent level.
Trioxide (Tm
2O
3): available from ACROS company, purity 99.9%, reagent level.
Cerium oxide (CeO
2): available from ACROS company, purity 99.9%, reagent level.
Bicarbonate of ammonia (NH
4HCO
3): available from ACROS company, purity 99.9%, reagent level.
Manganese oxide (MnO
2): available from ACROS company, purity 99.9%, reagent level.
Yttrium oxide (Y
2O
3): available from ACROS company, purity 99.9%, reagent level.
Aluminum oxide (Al
2O
3): available from ACROS company, purity 99.9%, reagent level.
Bismuth dioxide (BiO
2): available from ACROS company, purity 99.9%, reagent level.
Terbium sesquioxide (Tb
4O
7): available from ACROS company, purity 99.9%, reagent level.
Gallium oxide (Ga
2O
3): available from ACROS company, purity 99.9%, reagent level.
Gadolinium sesquioxide (Gd
2O
3): available from ACROS company, purity 99.9%, reagent level.
Lutecium oxide (Lu
2O
3): available from ACROS company, purity 99.9%, reagent level.
Erbium trioxide (Er
2O
3): available from ACROS company, purity 99.9%, reagent level.
Dysprosium oxide (Dy
2O
3): available from ACROS company, purity 99.9%, reagent level.
Praseodymium trioxide (Pr
6O
11): available from ACROS company, purity 99.9%, reagent level.
Scium trioxide (Sc
2O
3): available from ACROS company, purity 99.9%, reagent level.
Ytterbium oxide (Yb
2O
3): available from ACROS company, purity 99.9%, reagent level.
Samarium trioxide (Sm
2O
3): available from ACROS company, purity 99.9%, reagent level.
Holmium trioxide (Ho
2O
3): available from ACROS company, purity 99.9%, reagent level.
Neodymium trioxide (Nd
2O
3): available from ACROS company, purity 99.9%, reagent level.
Promethium oxide (Pm
2O
3): available from ACROS company, purity 99.9%, reagent level.
Barium magnesium aluminate (Barium magnesium aluminate, BaMgAl
10O
17, be called for short BAM): available from the basic chemical company of Japan.
Cerium: yttrium-aluminium garnet (be called for short YAG:Ce): available from the basic chemical company of Japan.
Erbium: yttrium-aluminium garnet (be called for short YAG:Er): available from the basic chemical company of Japan.
YN: by YCl
3And Li
3N is synthetic under 1800 ℃ of nitrogen environments.
AlN: by AlCl
3And Li
3N is synthetic under 1800 ℃ of nitrogen environments.
CeN: by CeCl
3And Li
3N is synthetic under 1800 ℃ of nitrogen environments.
GaN: by GaCl
3And Li
3N is synthetic under 1800 ℃ of nitrogen environments.
＜embodiment 1-25 〉
[embodiment 1]
Preparation heatproof nitride fluorescent material
According to chemical dosage ratio, weigh 33.65g Y
2O
3, 0.39g Tm
2O
3, 20.39g Al
2O
3, 4.10g AlN, with aforementioned base materials and 2.9g fusing assistant BaF
2Be uniformly mixed to form a mixture.The required chemical kind of Preparation Example 1 is recorded in table 1 in detail.
This mixture is inserted in crucible, and be warming up to 1650 ℃ with the temperature rise rate of 5 ℃/min carried out calcination 24 hours in nitrogen, then be cooled to room temperature with the speed of 5 ℃/min, obtain the powder through calcination.
Grind this through the powder of calcination, then after cleaning and drying, sieve with 400 order mesh screens.
The powder that will be somebody's turn to do again through grinding is placed in N
2/ H
2Be in 85%/15% reducing atmosphere, reduction is 12 hours under 1500 ℃, makes the heatproof Nitride phosphor of embodiment 1.
Luminous test
Purple light excited with embodiment 1 heatproof Nitride phosphor sample with 400nm, the radiation wavelength that measures this embodiment 1 sample by electroluminescence (PhotoLuminesecence is called for short PL) phenomenon is the blue light of 460nm.The luminous test result of embodiment 1 is recorded in table 2.
[embodiment 2-25]
Preparation process, preparation condition and the testing method of the heatproof nitride fluorescent material of embodiment 2-25 are identical with embodiment 1, and difference is in the kind of feed chemicals and consumption, and embodiment 2-25 raw material type used is recorded in table 1 in detail.
The heatproof nitride fluorescent material sample of embodiment 2-25 is carried out luminous test, and excitation wavelength and measured radiation wavelength and radiating light color are recorded in table 2.
＜comparative example 1-4 〉
The fluorescent material of comparative example 1-3 is the commercially available material, is respectively YAG:Ce, YAG:Er and BAM.
Comparative example 4 is Y
3Al
2O
7.5: Ce is according to chemical dosage ratio, weighs raw material Y
2O
3, Al
2O
3, and CeO
2, with aforementioned base materials and fusing assistant BaF
2Be uniformly mixed to form a mixture.The required chemical kind of preparation comparative example 4 is recorded in table 1 in detail.
The fluorescent material sample of comparative example 1-4 is carried out luminous test, and excitation wavelength and measured radiating light wavelength and radiating light color are recorded in table 2.
Table 2
As shown in Table 2, the YAG:Ce material of comparative example 1 is subjected to blue-light excited, and radiating light is the sodium yellow of wavelength 530nm; Comparative example 2 is YAG:Er, the red light of purple light excited rear emit wavelength 620nm.Hence one can see that, and active center is different, and excitation wavelength and radiation wavelength are also different.
The heatproof nitride fluorescent material of embodiment 1-23 does not contain Si or S, replaces partly or entirely 0 with N, and by collocation different component and active center, making the radiation wavelength region is the heatproof nitride fluorescent material of all kinds of 450-675nm.
By the excitation wavelength of embodiment 4-6 and radiating light wavelength as can be known, the rising of N content and the relative reduce of oxygen level can't impact the radiating light wavelength.The radiation wavelength of each embodiment is mainly and active center metallic element M
3Kind relevant: M
3Comprise Tm
3+Or Bi
3+The time, this heatproof nitride fluorescent material is subjected to emit blue light after light source activation, as active center metallic element M
3Comprise Tb
3+Or Ce
3+The time, this heatproof nitride fluorescent material is subjected to emit yellow-green light after light source activation, as active center metallic element M
3Comprise Eu
3+Or Mn
3+The time, this heatproof nitride fluorescent material is subjected to emit ruddiness after light source activation.Work as M
3Comprise the element T b that adds lustre to
3+, Er
3+, Yb
3+Or Ho
3+, the radiation wavelength region of this heatproof nitride fluorescent material is 380-530nm; Work as M
3Comprise the element Gd that adds lustre to
3+, Pr
3+, Dy
3+Or Nd
3+
See also Fig. 1, by (a) embodiment 13 and (b) comparative example 2 relative spectral power distribution figure as can be known, as comparative example 2 (YAG:Er) sample and embodiment 13 (Y
2.95Al
5N
8: Mn
0.05) sample be subject to equally 460nm when blue-light excited, embodiment 13 has better luminous intensity.
See also Fig. 2 and Fig. 3.Fig. 2 is the fluorescence spectrum figure of comparative example 3 (BAM), is the purple light excited of 400nm when comparative example 3 is subject to wavelength, and emit wavelength is the blue light of 450nm, and spectrum average frequently is 446.9.Fig. 3 is embodiment 15 (Y
2.94Al
5O
6N
4: Bi
0.06) to be subject to wavelength be following purple light excited of 400nm, emit wavelength is the spectrogram of 450nm blue light, spectrum average frequently is 701.1, shows that the luminous efficacy of embodiment 15 is better than comparative example 3.
See also Fig. 4 and Fig. 5.What need to specify is, comparative example 4 (Y
3Al
2O
7.5: outward appearance Ce) is white powder, structurally with yttrium-aluminium garnet (structure is Y
3Al
3-5O
9-12) difference.As shown in Figure 4, when the blue-light excited comparative example 4 attempted take wavelength as 450nm, its CIE (chromaticity coordinates) chromaticity coordinate is shown in region of blue light, shows that comparative example 4 is not excited by blue-light source, do not have fluorescence to emit, do not have fluorescence phenomenon.
Embodiment 4 is Y
2.95Al
5O
7.5N
3: Ce
0.05, structurally the difference with comparative example 4 is (AlN)
3As shown in Figure 5, when the blue-light excited embodiment 4 take wavelength as 450nm, its CIE chromaticity coordinate is positioned at white portion, shows that embodiment 4 is subjected to blue-light excited and radiates yellow fluorescence, and yellow fluorescence forms white light with the blue light that is partly absorbed.The difference of the present invention and existing fluorescent material has been on structure many (AlN)
m, 3≤m≤8, and can produce fluorescence phenomenon.
See also Fig. 6, by (a) comparative example 1 (YAG) and (b) embodiment 5 (Y
2.95Al
5O
6N
4: Ce
0.05) the light decay curve as can be known, in destructive test, when temperature raise, the situation that the intensity of giving out light of fluorescent material has decay occured.The anti-light decay performance of embodiment 5 is better than comparative example 1, and supposition is because embodiment 5 has the covalent bond structure of N, makes this heatproof nitride fluorescent material more stable under hot environment, and the strength retrogression's that gives out light degree is little, has good thermostability.
Aspect color rendering, the color rendering (Ra value) of general YAG material is 80%.Past replaces with Si or S the fluorescent material that Al carries out upgrading YAG, and owing to not breaking away from essence the structure of yttrium-aluminium garnet (YAG), so color rendering do not have considerable change, and the Ra value is also in 80% left and right; And heatproof nitride fluorescent material of the present invention has the color rendering that is better than current material, and the Ra value can reach more than 85%.
In sum, heatproof nitride fluorescent material of the present invention is via the various different elements of collocation, makes this heatproof nitride fluorescent material emit required coloured light; Part or all of 0 by replacing with N, make heatproof nitride fluorescent material of the present invention have covalent bond structure, the bond strength enhancing is easy fracture not, and sintering temperature is at 1800 ℃, and tolerable temperature improves, and good thermal stability.When heatproof nitride fluorescent material of the present invention was applied to light-emitting device, luminous intensity and luminous efficacy were good, and tolerable temperature is high, and had good color rendering, and that emits is photochromic naturally not dazzling.
The above, it is only preferred embodiment of the present invention, when not limiting scope of the invention process with this, the simple equivalence of namely generally doing according to the present patent application the scope of the claims and invention description content changes and modifies, and all still remains within the scope of the patent.
the above, it is only preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, although the present invention discloses as above with preferred embodiment, yet be not to limit the present invention, any those skilled in the art, within not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be not break away from the technical solution of the present invention content, any simple modification that foundation technical spirit of the present invention is done above embodiment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (7)
1. heatproof nitride fluorescent material is characterized in that it has the chemical formula of following formula (I):
M
1 yM
2 5O
zN
x:M
3 w (I)
M
1To be selected from Sc
3+, Y
3+, La
3+, Sm
3+, Gd
3+, Pm
3+, Er
3+, Lu
3+, or an aforesaid combination;
M
2Be selected from Al
3+, In
3+, Ga
3+, or an aforesaid combination;
M
3To be selected from Tm
3+, Bi
3+, Tb
3+, Ce
3+, Eu
3+, Mn
3+, Er
3+, Yb
3+, Ho
3+, Gd
3+, Pr
3+, Dy
3+, Nd
3+, or an aforesaid combination; And
X is the integer of 3-8,2.7≤y≤3,0＜w≤0.3, and 0≤z≤7.5.
2. heatproof nitride fluorescent material as claimed in claim 1, is characterized in that 0.01≤w≤0.06.
3. heatproof nitride fluorescent material as claimed in claim 1, is characterized in that this heatproof nitride fluorescent material is to be selected from Y
2.98Al
5O
7.5N
3: Tm
0.02,
Y
2.95Al
5O
6N
4:Bi
0.05、
Y
2.94Al
5O
6N
4:Tb
0.06、
Y
2.95Al
5O
7.5N
3:Ce
0.05、
Y
2.95Al
5O
6N
4:Ce
0.05、
Y
2.95Al
5O
4.5N
5:Ce
0.05、
Y
2.95Al
5O
6N
4:Mn
0.05、
Y
2.75GaAl
4O
6N
4:Mn
0.25、
Y
2.94Al
5N
8:Bi
0.06、
Y
2.94Al
5N
8:Tm
0.06、
Y
2.95Al
5N
8:Ce
0.05、
Y
2.95Al
5N
8:Mn
0.05、
Y
2.95Ga
5N
8:Mn
0.05、
Y
2.94Al
5O
6N
4:Bi
0.06、
Y
2.94Al
5O
6N
4:Mn
0.06、
Y
2.94Al
5O
6N
4:Ce
0.06、
Lu
1.72Gd
1.2Al
5O
6N
4:Ce
0.05Pr
0.03、
Lu
1.72Er
1Ga
5O
4.5N
5:Mn
0.25Dy
0.03、
Lu
1.92Sc
1Al
5O
6N
4:Ce
0.05Yb
0.03、
Sm
1.92La
1Al
5O
6N
4:Ce
0.05Ho
0.03、
Y
2.32Gd
0.6In
1Al
4O
6N
4:Ce
0.05Nd
0.03，
Or Lu
1.95Pm
1Al
5O
6N
4: Ce
0.05
4. heatproof nitride fluorescent material as claimed in claim 1, the radiation wavelength region that it is characterized in that this heatproof nitride fluorescent material is 380-700nm.
5. heatproof nitride fluorescent material as claimed in claim 1, the excitation wavelength range that it is characterized in that this heatproof nitride fluorescent material is 250-500nm.
6. light-emitting device is characterized in that it comprises:
One light-emitting diodes material elements can send a light source; And
One by the described heatproof nitride fluorescent material of any one in claim the 1-5 item, is to be arranged on this light-emitting diodes material elements;
This heatproof nitride fluorescent material is luminous by absorbing this light source of at least a portion.
7. heatproof nitride fluorescent material as claimed in claim 6, the radiation wavelength region that it is characterized in that this heatproof nitride fluorescent material is 380-700nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110437449.0A CN103173217B (en) | 2011-12-23 | 2011-12-23 | Heatproof nitride fluorescent material and the light-emitting device containing it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110437449.0A CN103173217B (en) | 2011-12-23 | 2011-12-23 | Heatproof nitride fluorescent material and the light-emitting device containing it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103173217A true CN103173217A (en) | 2013-06-26 |
| CN103173217B CN103173217B (en) | 2017-03-01 |
Family
ID=48633423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110437449.0A Expired - Fee Related CN103173217B (en) | 2011-12-23 | 2011-12-23 | Heatproof nitride fluorescent material and the light-emitting device containing it |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103173217B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5998925A (en) * | 1996-07-29 | 1999-12-07 | Nichia Kagaku Kogyo Kabushiki Kaisha | Light emitting device having a nitride compound semiconductor and a phosphor containing a garnet fluorescent material |
| CN101137738A (en) * | 2005-03-08 | 2008-03-05 | 皇家飞利浦电子股份有限公司 | Illumination system comprising a radiation source and a luminescent material |
| JP2008285606A (en) * | 2007-05-18 | 2008-11-27 | Nec Lighting Ltd | Phosphor, method for producing the same and light-emitting device |
| CN101536193A (en) * | 2006-10-20 | 2009-09-16 | 英特曼帝克司公司 | Nano-YAG:Ce phosphor compositions and their methods of preparation |
| US20100142182A1 (en) * | 2007-04-17 | 2010-06-10 | Koninklijke Philips Electronics N.V. | Illumination system |
-
2011
- 2011-12-23 CN CN201110437449.0A patent/CN103173217B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5998925A (en) * | 1996-07-29 | 1999-12-07 | Nichia Kagaku Kogyo Kabushiki Kaisha | Light emitting device having a nitride compound semiconductor and a phosphor containing a garnet fluorescent material |
| CN101137738A (en) * | 2005-03-08 | 2008-03-05 | 皇家飞利浦电子股份有限公司 | Illumination system comprising a radiation source and a luminescent material |
| CN101536193A (en) * | 2006-10-20 | 2009-09-16 | 英特曼帝克司公司 | Nano-YAG:Ce phosphor compositions and their methods of preparation |
| US20100142182A1 (en) * | 2007-04-17 | 2010-06-10 | Koninklijke Philips Electronics N.V. | Illumination system |
| JP2008285606A (en) * | 2007-05-18 | 2008-11-27 | Nec Lighting Ltd | Phosphor, method for producing the same and light-emitting device |
Non-Patent Citations (1)
| Title |
|---|
| YOUNG-HYUN SONG ET AL.: "Enhancement of photoluminescence properties of green to yellow emitting Y3Al5O12:Ce3+ phosphor by AlN addition for white LED applications", 《MATERIALS LETTERS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103173217B (en) | 2017-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9711686B2 (en) | Lighting device with plural fluorescent materials | |
| US6765237B1 (en) | White light emitting device based on UV LED and phosphor blend | |
| US20020195587A1 (en) | Broad-spectrum terbium-containing garnet phosphors and white-light sources incorporating the same | |
| JP6496725B2 (en) | LED package with red light emitting phosphor | |
| CN103881706B (en) | A kind of nitric oxide fluorescent powder, its preparation method and the light-emitting device containing this fluorescent material | |
| CN1922286A (en) | Garnet phosphor materials having enhanced spectral characteristics | |
| CN102206488B (en) | Blue fluorescent powder used for white light LEDs and its preparation method | |
| JP2010270196A (en) | Phosphor, method for manufacturing phosphor, phosphor-containing composition, light-emitting device, lighting apparatus, image display, and fluorescent paint | |
| CN101250407A (en) | Borosilicate fluorescent powder and method for making same | |
| TWI582215B (en) | A phosphor composition and light emitting device using the same | |
| CN105670613A (en) | Non-rare-earth-ion-doped silicate yellow fluorescent powder, and preparation method and application thereof | |
| CN104962286A (en) | Garnet-structure multiphase fluorescent material and preparation method thereof | |
| CN100383988C (en) | White light LED and light converting luminophore | |
| CN102286281B (en) | Aluminate-based red fluorescent material and preparation method thereof | |
| EP3164464B1 (en) | Oxyfluoride phosphor compositions and lighting apparatus thereof | |
| CN104194788B (en) | A kind of white light LEDs phosphate green emitting phosphor and its preparation method | |
| CN103937500B (en) | Light-emitting device and heatproof carbide fluorescent material thereof | |
| CN102977885A (en) | Photoluminescence fluorescent material and white light emitting device | |
| CN106635016A (en) | Phosphor, preparation method thereof and light-emitting device | |
| CN103173217B (en) | Heatproof nitride fluorescent material and the light-emitting device containing it | |
| CN103855287B (en) | A kind of light-emitting device and the luminescent device with the light-emitting device | |
| JP7114750B2 (en) | optical device | |
| CN102746847B (en) | Fluorescent powder capable of exciting continuous spectrum with blue light and preparation method of fluorescent powder | |
| CN103361057A (en) | Fluorescent material, fluorescent material composition containing same, and light-emitting device prepared from same | |
| KR102113044B1 (en) | Lithium-based garnet phosphor, preparing method of the same, and luminescent property of the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170301 Termination date: 20191223 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |