CN102399554A - Nitride red luminescence material, and luminescent part and luminescent device containing the same - Google Patents
Nitride red luminescence material, and luminescent part and luminescent device containing the same Download PDFInfo
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- CN102399554A CN102399554A CN2011103151974A CN201110315197A CN102399554A CN 102399554 A CN102399554 A CN 102399554A CN 2011103151974 A CN2011103151974 A CN 2011103151974A CN 201110315197 A CN201110315197 A CN 201110315197A CN 102399554 A CN102399554 A CN 102399554A
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Abstract
The invention discloses a nitride red luminescent material, and a luminescent part and a luminescent device containing the same. The luminescent material has a general formula of Ma(Al,B)bSicNdOe:Eum, Rn, wherein M represents at least an alkali earth metal selected from Mg, Ca, Sr, Ba and Zn, and R represents at least a rare earth element selected from Y, La, Ce, Gd and Lu; and a, b, c, d, e, m and n satisfy the relations of: 0.9<=a<1.1, 0.9<=b<=1, 1<=c<=1.5, 2.5<d<5, 0<e<0.1, 0<m<0.05, 0<n<0.1, and 1<c/b<1.5. The luminescent material can be excitated by radiant light with a wavelength under 500 nm and irradiates wide spectrum visible red light of 500nm-780nm. The luminescent material of the invention has characteristics of high luminescence efficiency, excellent temperature characteristics and wide half width, and can be individually used for or combined with other luminescent materials for preparing luminescent devices with high performance.
Description
Technical field
The invention belongs to the luminescent material technical field, especially relate to a kind of nitride red luminescent material, the illuminating part that comprises it and luminescent device.
Background technology
Red illuminating material is indispensable as the important component part in the red, green, blue three primary colours.Present widely used red illuminating material has Y
2O
3: Eu
3+(Bi
3+), Y
2O
2S:Eu
3+(Bi
3+), Y (V, P) O
4: Eu
3+(Bi
3+), (Y, Gd) BO
3: Eu
3+, (Ca, Sr) S:Eu
2+(Tm
3+) etc.; But along with the change of conventional art modes such as demonstration and illumination, these traditional red illuminating materials that once yielded unusually brilliant results can not satisfy the needs of development of new techniques such as 3D demonstration, white light LEDs well owing to the change of Application Areas, mode of excitation.
Since the end of the nineties in last century, one type of novel nitrogen/oxynitride luminescent material is developed, and the anionic group of this type luminescent material contains the N of high negative charge
3-, the electronic cloud bulking effect makes its excitation spectrum move to long wave directions such as near ultraviolet, visible lights, and their matrix has network structure comparatively closely, physicochemical property are stable.
Calendar year 2001 patent documentation EP1104799A1 discloses one type of M
xSi
yN
z: Eu (M is at least a among the Ca/Sr/Ba, z=2/3x+4/3y) nitride red luminescent material, and its representational luminescent material mainly contains MSiN
2: Eu, M
2Si
5N
8: Eu and MSi
7N
10: three kinds of Eu etc.According to non-patent literature Chem.Mater.2006,18:5578 report, this Sr
2Si
5N
8: the nitride red luminescent material of Eu 86% when luminous intensity has only room temperature in the time of 150 ℃.
Chinese invention patent ZL 200480040967.7 has invented one type of M
aA
bD
cE
dX
eRed illuminating material; A+b=1 and M are one or both elements among the Mn/Ce/Pr/Nd/Sm/Eu/Tb/Dy/Ho/Er/Tm/Yb in the formula; A is one or both elements among the Mg/Ca/Sr/Ba; D is one or both elements among the Si/Ge/Sn/Ti/Zr/Hf, and E is one or both elements among the B/Al/Ga/In/Sc/Y/La/Ga/Lu, and X is selected from one or both elements among O, N and the F; This mineral compound has and CaAlSiN
3Identical crystalline structure, and 0.00001≤a≤0.1,0.5≤c≤4,0.5≤d≤8,0.8 * (2/3+4/3 * c+d)≤e and, e≤1.2 (2/3+4/3 * c+d). wherein classical group becomes CaAlSiN
3: Eu.According to non-patent literature Sci.Technol.Adv.Mat., 2007,8 (7-8): 588-600 report, this CaAlSiN
3: Eu luminescent material 89% when luminous intensity is room temperature in the time of 150 ℃ is better than Sr
2Si
5N
8: the Eu luminescent material.
Non-patent literature (Int.J.Appl.Ceram.Technol., 2010,7 (6): in 2009 787-802) at CaSiN
2: introduce a certain amount of AlN on the basis of Eu and obtained Cal-xAlzSiN
2+ z:Eux (0＜z＜0.3), but along with the introducing of AlN, the luminous efficiency of material significantly descends, it also has only 28.5% and 24.5% respectively in 405 external quantum efficiencys under exciting with 450nm; In addition, according to document report, Ca
0.999SiN
2: Eu
0.001The thermal quenching temperature lower, be approximately 110 ℃, temperature profile is not good.
The red fluorescence powder that relates in the above-mentioned document has than the sulfide red fluorescent material of tradition ((Ca, Sr) S:Eu
2+) more excellent temperature profile.Simultaneously, be not difficult to find out also that the red illuminating material that relates in the above-mentioned document 90% when luminous intensity all is lower than room temperature in the time of 150 ℃ still awaits further improvement; And concerning device application, as the red illuminating material that can effectively improve colour rendering index, its half-width requires wide, and the luminous half-width of above-mentioned luminescent material has the needs of further wideization generally about 90nm; In addition; Current employing adds the technical scheme that red illuminating material improves colour rendering index; Though can obtain high colour rendering index, the problem of having brought the device whole lighting efficiency to descend significantly simultaneously, this luminous efficiency that just need further improve red illuminating material is alleviated.
Summary of the invention
The object of the present invention is to provide the nitride red luminescent material that a kind of luminous efficiency is high, temperature profile is good, half-width is wide.
For this reason, the invention provides a kind of nitride red luminescent material, this nitride red luminescent material has structure in the general formula (1), and general formula (1) is M
a(Al, B)
bSi
cN
dO
e: Eu
m, R
n, wherein: M is at least a among Mg, Ca, Sr, Ba, the Zn; R is at least a among rare earth element y, La, Ce, Gd, the Lu; The mol ratio x of element B and Al satisfies 0≤x≤0.1; And 0.9≤a＜1.1,0.9≤b≤1,1≤c≤1.5,2.5＜d＜5,0＜e＜0.1,0＜m＜0.05,0＜n＜0.1,1＜c/b＜1.5.
Further, above-mentioned M comprises Ca and/or Sr at least.
Further, above-mentioned R comprises rare earth element y and/or Gd at least.
Further, above-mentioned R is a rare earth element y.
Further, the scope of said n is 0.001≤n≤0.05.
Further, the scope of above-mentioned m is 0.005≤m≤0.025.
Further, above-mentioned luminescent material is any in the following material:
Ca
0.99Al
0.9B
0.009Si
1.1N
3.8O
0.002:Eu
0.01，Y
0.001；
Ca
0.2Sr
0.89Al
0.99SiN
3O
0.001:Eu
0.008，Y
0.001，La
0.001；
Ca
0.75Sr
0.22Al
0.92B
0.07Si
1.2N
4O
0.015:Eu
0.025，Y
0.02，Gd
0.005，Lu
0.005；
Ca
0.45Sr
0.45Zn
0.02Al
0.9Si
14.8N
4O
0.05:Eu
0.04，Y
0.015，Lu
0.005；
Sr
1.05Al
0.9B
0.09Si
1.3N
3.5O
0.0005:Eu
0.005，Y
0.008；
Ca
0.675Sr
0.3Al
0.9SiN
2.6O
0.005:Eu
0.02，Gd
0.003，La
0.002；
Sr
1.05Al
0.9B
0.09Si
1.3N
3.5O
0.0005:Eu
0.005，Y
0.05；
Sr
1.05Al
0.9B
0.09Si
1.3N
3.5O
0.0005:Eu
0.005，Y
0.0008；
Sr
1.05Al
0.9B
0.09Si
1.3N
3.5O
0.0005: Eu
0.005, Y
0.095Perhaps
Ca
0.2Sr
0.89Al
0.99SiN
3O
0.001:Eu
0.005，Y
0.001，La
0.001。
Further, above-mentioned luminescent material is Powdered, film like or sheet.
Simultaneously; A kind of illuminating part also is provided in the present invention; This illuminating part is that above-mentioned nitride red luminescent material is dispersed in glass material, plastic material or the resin material formed; Perhaps, be formed at glass material, plastic material or resin material by above-mentioned nitride red luminescent material and other luminescent material co-dispersed.
Further, above-mentioned other luminescent materials be in the following fluorescent material one or more:
(Y，Gd，Lu，Tb)
3(Al，Ga)
5O
12:Ce、(Mg，Ca，Sr，Ba)
2SiO
4:Eu、(Ca，Sr)
3SiO
5:Eu、(La，Ca)
3Si
6N
11:Ce、α-SiAlON:Eu、β-SiAlON:Eu、Ba
3Si
6O
12N
2:Eu、Ca
3(Sc，Mg)
2Si
3O
12:Ce、CaSc
2O
4:Eu、BaAl
8O
13:Eu、(Ca，Sr，Ba)Al
2O
4:Eu、(Sr，Ca，Ba)(Al，Ga，In)
2S
4:Eu、(Ca，Sr)
8(Mg，Zn)(SiO
4)
4Cl
2:Eu/Mn、(Ca，Sr，Ba)
3MgSi
2O
8:Eu/Mn、(Ca，Sr，Ba)
2(Mg，Zn)Si
2O
7:Eu、Zn
2SiO
4:Mn、(Y，Gd)BO
3:Tb、ZnS:Cu，Cl/Al、ZnS:Ag，Cl/Al、(Sr，Ca)
2Si
5N
8:Eu、(Li，Na，K)
3ZrF
7:Mn、(Li，Na，K)
2(Ti，Zr)F
6:Mn、(Ca，Sr，Ba)(Ti，Zr)F
6:Mn、Ba
0.65Zr
0.35F
2.7:Mn、(Sr，Ca)S:Eu、(Y，Gd)BO
3:Eu、(Y，Gd)(V，P)O
4:Eu、Y
2O
3:Eu、(Sr，Ca，Ba，Mg)
5(PO
4)
3Cl:Eu、(Ca，Sr，Ba)MgAl
10O
17:Eu、(Ca，Sr，Ba)Si
2O
2N
2:Eu、3.5MgO·0.5MgF
2·GeO
2:Mn。
Simultaneously, a kind of luminescent device is provided also in the present invention, this luminescent device comprises source of radiation and above-mentioned nitride red luminescent material at least.
Further, above-mentioned source of radiation is VUV or ultraviolet or purple light or blue emission source.
Further, also contain in the above-mentioned luminescent device by other luminescent materials of said source of radiation stimulated luminescence.
Further, above-mentioned other luminescent materials be in the following fluorescent material one or more:
(Y，Gd，Lu，Tb)
3(Al，Ga)
5O
12:Ce、(Mg，Ca，Sr，Ba)
2SiO
4:Eu、(Ca，Sr)
3SiO
5:Eu、(La，Ca)
3Si
6N
11:Ce、α-SiAlON:Eu、β-SiAlON:Eu、Ba
3Si
6O
12N
2:Eu、Ca
3(Sc，Mg)
2Si
3O
12:Ce、CaSc
2O
4:Eu、BaAl
8O
13:Eu、(Ca，Sr，Ba)Al
2O
4:Eu、(Sr，Ca，Ba)(Al，Ga，In)
2S
4:Eu、(Ca，Sr)
8(Mg，Zn)(SiO
4)
4Cl
2:Eu/Mn、(Ca，Sr，Ba)
3MgSi
2O
8:Eu/Mn、(Ca，Sr，Ba)
2(Mg，Zn)Si
2O
7:Eu、Zn
2SiO
4:Mn、(Y，Gd)BO
3:Tb、ZnS:Cu，Cl/Al、ZnS:Ag，Cl/Al、(Sr，Ca)
2Si
5N
8:Eu、(Li，Na，K)
3ZrF
7:Mn、(Li，Na，K)
2(Ti，Zr)F
6:Mn、(Ca，Sr，Ba)(Ti，Zr)F
6:Mn、Ba
0.65Zr
0.35F
2.7:Mn、(Sr，Ca)S:Eu、(Y，Gd)BO
3:Eu、(Y，Gd)(V，P)O
4:Eu、Y
2O
3:Eu、(Sr，Ca，Ba，Mg)
5(PO
4)
3Cl:Eu、(Ca，Sr，Ba)MgAl
10O
17:Eu、(Ca，Sr，Ba)Si
2O
2N
2:Eu、3.5MgO·0.5MgF
2·GeO
2:Mn。
Beneficial effect of the present invention: nitride red luminescent material luminous efficiency provided by the present invention is high, temperature profile is good, half-width is wide, is improved significantly by its prepared luminescent device brightness simultaneously.
Except top described purpose, feature and advantage, the present invention also has other purpose, feature and advantage.To do further detailed explanation to the present invention with reference to figure below.
Description of drawings
Accompanying drawing constitute this specification sheets a part, be used for further understanding the present invention, accompanying drawing shows the preferred embodiments of the present invention, and is used for explaining principle of the present invention with specification sheets.Among the figure:
Fig. 1 shows the emmission spectrum comparison diagram of the prepared luminescent material of the embodiment of the invention 1 and Comparative Examples; And
Fig. 2 shows the excitation spectrum comparison diagram of the prepared luminescent material of the embodiment of the invention 1 and Comparative Examples.
Embodiment
Be noted that following detailed description all is an exemplary, being intended to provides further explanation to the present invention.Unless otherwise, all technology used of this paper and scientific terminology have with the present invention under the identical meanings of those of ordinary skill common sense of technical field.
In a kind of typical embodiment of the present invention, a kind of nitride red luminescent material wherein contains divalent metal M, REE Eu (europium) and R, Al (aluminium), Si (silicon), N (nitrogen) and O (oxygen) simultaneously, and has the structure of general formula (1), and general formula (1) is M
a(Al, B)
bSi
cN
dO
e: Eu
m, R
nWherein, M is at least a among Mg, Ca, Sr, Ba, the Zn, and R is at least a among rare earth element y, La, Ce, Gd, the Lu, and the mol ratio x of element B and Al satisfies 0≤x≤0.1; And, 0.9≤a＜1.1,0.9≤b≤1 wherein; 1≤c≤1.5,2.5＜d＜5,0＜e＜0.1; 0＜m＜0.05,0＜n＜0.1,1＜c/b＜1.5.
The structure of above-mentioned luminescent material is based on SiN
4Tetrahedron makes up, with Eu
2+Be luminescence center.Through in luminescent material, introduce being prone to (Al, the B) component, and adopt a small amount of rare-earth element R (comprising Y, La, Ce, Gd, Lu) to come cover or calking of trend network structure; Simultaneously in order to keep the tetrahedral structure of this luminescent material; And don't as for causing bigger lattice distortion; (Al, add-on b B) is similar to the add-on a of divalent metal element M, and wherein the scope of a is 0.9≤a＜1.1; The scope of b is 0.9≤b≤1, and the ratio of b and Si satisfies 1＜c/b＜1.5; Above-mentioned synergy can make the structure of luminescent material more firm and compact, and then has improved the temperature profile of luminescent material.
Simultaneously, the adding of Al and B has also obtained other significant effects.Lower melting point and activity like element B (boron); Make it help very much to strengthen roasting, and then help improving the particle percent crystallinity of luminescent material, make this luminescent material have high luminous efficiency, good temperature profile and little light decay; The introducing amount of B (boron) should suit; The mol ratio x that should guarantee B (boron) and Al (aluminium) is in 0≤x≤0.1 scope, if surpass this scope, because the radius difference of B (boron) and Al (aluminium) is too big; Can cause lattice distortion, unfavorable to the luminous efficiency and the life-span of this luminescent material on the contrary.
Codoped at above-mentioned luminescent material middle-weight rare earths element R (comprising Y, La, Ce, Gd, Lu) helps strengthening the absorption of luminescent material to the exciting light quantity of radiant energy; And can the transmission ofenergy that absorb be given luminescence center Eu and improved luminosity; And can not produce with the competition of luminescence center and absorb or heavily absorb, thereby guaranteed that material has superior luminous efficiency; The effect of strengthening the luminescent material roasting is also played in the introducing of rare-earth element R (comprising Y, La, Ce, Gd, Lu), improves luminescent material particle percent crystallinity jointly with the B (boron) that adds, and strengthens luminous efficiency, reduces light decay and thermal quenching simultaneously; Likewise, rare-earth element R (comprising Y, La, Ce, Gd, Lu) also has an amount of add-on n:0＜n＜0.1, excessive obvious non-luminous dephasign, the infringement luminosity of then can producing of add-on.
In order to satisfy the application demand of high colour developing; On the basis of said components; Also introduced the half-width that an amount of O (oxygen) comes wide formed material emmission spectrum; As the introducing amount e of oxygen during at 0＜e＜0.1 scope, the half-width of the luminescent spectrum of luminescent material can be adjusted between 95～130nm, be wider than existing M
xSi
yN
z: Eu and (Ca, Sr) AlSiN
3: the half-width about the 90nm of red illuminating materials such as Eu, and light efficiency keeps better.But when the add-on e of oxygen surpasses 0.1 and since its be easier to structure in (Al, B), Si and rare earth etc. are compound and change structure and crystal field, can make that on the contrary the luminosity of red illuminating material greatly weakens.
In luminescent material of the present invention, Eu
2+Be luminescence center, it can effectively be excited by the radiant light that wavelength is positioned at below the 500nm, launches the wide range visible red that spectrum is positioned at 500-780nm.
Simultaneously; In order to satisfy the application requiring of different luminescent devices to the photochromic performance of luminescent material etc., luminescent material of the present invention comprehensively adopts the approach such as concentration of kind and ratio and the activator Eu of the dyad Mg that regulates M representative in its general formula, Ca, Sr, Ba, Zn to realize the controllable adjustment of its emission main peak and spectrum area coverage.As along with the increase of Sr content and the minimizing of Ca content, the emission main peak red shift gradually of material, glow color trends towards redder; Improve the concentration of activator Eu, luminescence center increases, the also red shift of emission main peak; Luminous intensity strengthens simultaneously, but when the concentration of Eu surpasses 0.025, concentration quenching effect will appear in the luminous of this material; Can make the luminous intensity of luminescent material reduce on the contrary even if continue to increase Eu concentration this moment; And when the concentration of Eu increased to 0.05, concentration quenching effect was very serious, and the luminosity of material significantly descends.When divalent metal M components contents a is in 0.9≤a＜1.1, Eu concentration m and satisfies 0＜m＜0.05, can realize the controllable adjustment of such luminescent material emmission spectrum at 500～780nm visible light wave range.Those skilled in the art are through reading application documents of the present invention; Under the instruction of application documents of the present invention; Can reasonably use the routine techniques means, realize the controllable adjustment of such luminescent material emmission spectrum, repeat no more at this at 500～780nm visible light wave range.
Preferably, M comprises Ca and/or Sr at least in the above-mentioned nitride red luminescent material.When comprising among Ca, the Sr one or both among the M at least, under the condition that obtains identical colourity, this luminescent material has excellent luminosity and temperature profile.
Preferably, R comprises rare earth element y and/or Gd at least in the above-mentioned nitride red luminescent material.When comprising among rare earth element y, the Gd one or both among the R at least, under the condition that obtains identical colourity, this luminescent material has excellent luminosity and temperature profile.More preferably, R is a rare earth element y.
Preferably, the scope of the add-on n of R is 0.001≤n≤0.05 in the above-mentioned nitride red luminescent material.This luminescent material has excellent luminosity and temperature profile in this scope.
Preferably, the add-on m of Eu in the above-mentioned nitride red luminescent material, 0.005≤m≤0.025 this luminescent material in this scope have excellent luminosity and temperature profile.This be because when the add-on of Eu less than 0.005 the time, luminescence center Eu very little, luminosity is low; When Eu surpasses 0.025, again concentration quenching effect can take place, luminosity is along with the increase of Eu descends on the contrary, and also variation of the temperature profile of fluorescent material.
In addition, there is micro-C (carbon) in unavoidable meeting in the nitride red luminescent material of the present invention, and the quality percentage composition of C is no more than 0.1% of this luminescent material total mass in the nitride red in the present invention luminescent material.Having of C of trace is beneficial to stabilized illumination material luminescence center Eu
2+Valence state, prevent to change into Eu
3+And the infringement luminous efficiency; But when its content surpasses 0.1%, can pollute luminescent material, not only influence body colour, and light efficiency decline to a great extent also.
Preferably, above-mentioned nitride red luminescent material is any in the following material:
Ca
0.99Al
0.9B
0.009Si
1.1N
3.8O
0.002:Eu
0.01，Y
0.001；
Ca
0.2Sr
0.89Al
0.99SiN
3O
0.001:Eu
0.008，Y
0.001，La
0.001；
Ca
0.75Sr
0.22Al
0.92B
0.07Si
1.2N
4O
0.015:Eu
0.025，Y
0.02，Gd
0.005，Lu
0.005；
Ca
0.45Sr
0.45Zn
0.02Al
0.9Si
1.48N
4O
0.05:Eu
0.04，Y
0.015，Lu
0.005；
Sr
1.05Al
0.9B
0.09Si
1.3N
3.5O
0.0005:Eu
0.005，Y
0.008；
Ca
0.675Sr
0.3A
10.9SiN
2.6O
0.005:Eu
0.02，Gd
0.003，La
0.002；
Sr
1.05Al
0.9B
0.09Si
1.3N
3.5O
0.0005:Eu
0.005，Y
0.05；
Sr
1.05Al
0.9B
0.09Si
1.3N
3.5O
0.0005:Eu
0.005，Y
0.0008；
Sr
1.05Al
0.9B
0.09Si
1.3N
3.5O
0.0005: Eu
0.005, Y
0.095Perhaps
Ca
0.2Sr
0.89Al
0.99SiN
3O
0.001:Eu
0.005，Y
0.001，La
0.001。
Simultaneously, in order to be suitable for different application requirements, that the luminescent material that the present invention relates to can directly be formed to is Powdered, film like or sheet.
Below will provide the method for the nitride red luminescent material of a kind of the present invention of preparation, specific as follows:
According to the stoichiometric ratio shown in the general formula (1); Mix after the accurate weighing of raw materials such as compound with the compound of nitride, aluminium nitride AlN, SP 1, silicon nitride and the Eu of divalent metal M and rare earth R; And then roasting 4～20 hours in nitrogen or nitrogen and hydrogen mixture atmosphere, under 1400～1800 ℃ the high temperature, the product of roasting of gained again through broken, sieve, wash, step such as oven dry promptly can obtain red illuminating material of the present invention.
In a kind of typical embodiment of the present invention; A kind of illuminating part is provided; This can be that luminescent film also can be a light tiles; It is to be dispersed in glass material, plastic material or the resin material formedly by above-mentioned nitride red luminescent material, perhaps, is that to be evenly dispersed in glass material, plastic material or resin material by above-mentioned nitride red luminescent material with other luminescent materials formed.
This illuminating part provided by the present invention; As long as prepare in the process at glass material, plastic material or resin material; With the nitride red luminescent material of the present invention; Perhaps the nitride red luminescent material of the present invention and other luminescent materials add in the raw material of glass material, plastic material or resin material and mix; Be prepared into membranaceous according to the ordinary method of glass material, plastic material or resin material then or sheet gets final product; The nitride red luminescent material of the present invention, perhaps illuminating part prepares that the add-on of luminescent material equates to get final product in the process in the nitride red luminescent material of the present invention and the mixture of other luminescent materials amount that joins glass material, plastic material or resin material and the prior art.Those skilled in the art can prepare this luminescent film provided by the present invention or light tiles through rational technique means, so its making method is repeated no more on basis of the present invention.
Preferably, above-mentioned other luminescent materials be (Y, Gd, Lu, Tb)
3(Al, Ga)
5O
12: Ce, (Mg, Ca, Sr, Ba)
2SiO
4: Eu, (Ca, Sr)
3SiO
5: Eu, (La, Ca)
3Si
6N
11: Ce, α-SiAlON:Eu, β-SiAlON:Eu, Ba
3Si
6O
12N
2: Eu, Ca
3(Sc, Mg)
2Si
3O
12: Ce, CaSc
2O
4: Eu, BaAl
8O
13: Eu, (Ca, Sr, Ba) Al
2O
4: Eu, (Sr, Ca, Ba) (Al, Ga, In)
2S
4: Eu, (Ca, Sr)
8(Mg, Zn) (SiO
4)
4Cl
2: Eu/Mn, (Ca, Sr, Ba)
3MgSi
2O
8: Eu/Mn, (Ca, Sr, Ba)
2(Mg, Zn) Si
2O
7: Eu, Zn
2SiO
4: Mn, (Y, Gd) BO
3: Tb, ZnS:Cu, Cl/Al, ZnS:Ag, Cl/Al, (Sr, Ca)
2Si
5N
8: Eu, (Li, Na, K)
3ZrF
7: Mn, (Li, Na, K)
2(Ti, Zr) F
6: Mn, (Ca, Sr, Ba) (Ti, Zr) F
6: Mn, Ba
0.65Zr
0.35F
2.7: Mn, (Sr, Ca) S:Eu, (Y, Gd) BO
3: Eu, (Y, Gd) (V, P) O
4: Eu Y
2O
3: Eu, (Sr, Ca, Ba, Mg)
5(PO
4)
3Cl:Eu, (Ca, Sr, Ba) MgAl
10O
17: Eu, (Ca, Sr, Ba) Si
2O
2N
2: Eu, 3.5MgO0.5MgF
2GeO
2: one or more among the Mn.
The mixed proportion of nitride red luminescent material provided by the present invention and other luminescent materials can reasonably regulate based on the demand of application and photochromic adjusting in the process of making illuminating part; Those skilled in the art through reasonable analysis, have the ability to prepare required illuminating part on basis of the present invention.
In a kind of typical embodiment of the present invention, a kind of luminescent device also is provided, this luminescent device comprises source of radiation and above-mentioned nitride red luminescent material with general formula (1) at least, general formula (1) is M
a(Al, B)
bSi
cN
dO
e: Eu
m, R
n
Above-mentioned luminescent material can be Powdered, film like or sheet, also can be through being dispersed in the illuminating part that is prepared in glass material, plastic material or the resin material.
Source of radiation can be anyly can send the source of radiation that wavelength is positioned at the radiant light below the 500nm; Preferably; Source of radiation is VUV, ultraviolet, purple light or blue ray radiation source, and exciting respectively down of they, the luminescent material that the present invention relates to all can send ruddiness efficiently.
Preferably; In the above-mentioned luminescent device; Except that nitride red luminescent material with the middle structure of general formula (1); Can also add the luminescent material that other can effectively be excited by corresponding source of radiation, as in " blue-ray LED+the present invention relates to luminescent material " combination, adding can be formed white light emitting device by blue-light excited yellow or green luminescent material; Adding can also can be formed white light emitting device by VUV, ultraviolet or purple light excited blueness and green luminescent material in " VUV, ultraviolet or purple LED+the present invention relates to luminescent material "; Or the like, these white light emitting devices can be used in illumination or demonstration field.
Can be used for mixing other luminescent materials that use with the nitride red luminescent material of the present invention in the above-mentioned luminescent device mainly contains: (Y, Gd, Lu, Tb)
3(Al, Ga)
5O
12: Ce, (Mg, Ca, Sr, Ba)
2SiO
4: Eu, (Ca, Sr)
3SiO
5: Eu, (La, Ca)
3Si
6N
11: Ce, α-SiAlON:Eu, β-SiAlON:Eu, Ba
3Si
6O
12N
2: Eu, Ca
3(Sc, Mg)
2Si
3O
12: Ce, CaSc
2O
4: Eu, BaAl
8O
13: Eu, (Ca, Sr, Ba) Al
2O
4: Eu, (Sr, Ca, Ba) (Al, Ga, In)
2S
4: Eu, (Ca, Sr)
8(Mg, Zn) (SiO
4)
4Cl
2: Eu/Mn, (Ca, Sr, Ba)
3MgSi
2O
8: Eu/Mn, (Ca, Sr, Ba)
2(Mg, Zn) Si
2O
7: Eu, Zn
2SiO
4: Mn, (Y, Gd) BO
3: Tb, ZnS:Cu, Cl/Al, ZnS:Ag, Cl/Al, (Sr, Ca)
2Si
5N
8: Eu, (Li, Na, K)
3ZrF
7: Mn, (Li, Na, K)
2(Ti, Zr) F
6: Mn, (Ca, Sr, Ba) (Ti, Zr) F
6: Mn, Ba
0.65Zr
0.35F
2.7: Mn, (Sr, Ca) S:Eu, (Y, Gd) BO
3: Eu, (Y, Gd) (V, P) O
4: EuY
2O
3: Eu, (Sr, Ca, Ba, Mg)
5(PO
4)
3Cl:Eu, (Ca, Sr, Ba) MgAl
10O
17: Eu, (Ca, Sr, Ba) Si
2O
2N
2: Eu, 3.5MgO0.5MgF
2GeO
2: Mn etc.
Below will combine specific embodiment 1-22 and Comparative Examples to further specify chromaticity coordinate, relative brightness and the half-width situation of nitride red luminescent material provided by the present invention.Simultaneously, with combining embodiment 23-33 to further specify the beneficial effect of luminescent device provided by the present invention.
The chemical formula of nitride red luminescent material is as shown in table 1 among the embodiment 1-22, and Comparative Examples is selected pure Ca
0.99AlSiN
3: Eu
0.01Luminescent material.
Luminescent material preparation method in embodiment 1-22 and the Comparative Examples:
According to the stoichiometric ratio in the general formula shown in the general formula embodiment 1-22; Mix after the accurate weighing of raw materials such as compound with the compound of nitride, aluminium nitride AlN, SP 1, silicon nitride and the Eu of divalent metal M and rare earth R; Wherein the oxygen in the component is introduced by the compound of Eu or the compound of rare earth R; And then roasting 6～8 hours in nitrogen or nitrogen and hydrogen mixture atmosphere, under 1500～1600 ℃ the high temperature; The product of roasting of gained passes through fragmentation (being crushed to 5～20 microns) again, crosses 100～500 mesh sieves, through diluted acid pickling or deionized water washing, 80～120 ℃ of oven dry, promptly obtain having the sample of embodiment 1-22 and Comparative Examples chemical formula.
Testing method:
Adopt spectrophotometer that nitride red luminescent material among Comparative Examples and the embodiment 1-22 is carried out chromaticity coordinate, relative brightness and half-width test; Wherein setting excitation wavelength is 460nm; And the relative brightness of definition Comparative Examples luminescent material is 100, and test result is as shown in table 1.
The temperature profile data of table 2 Comparative Examples and the relative brightness of embodiment 1-22 luminescent material
1-22 result is not difficult to find out from table 1 listed examples, and the novel red luminescent material that the present invention relates to all has than Comparative Examples Ca
0.99AlSiN
3: Eu
0.01Luminosity that luminescent material is higher and wideer half-width, these all are very beneficial for the lifting of application device luminous efficiency and colour rendering index.And the temperature profile data of the embodiment 1-22 luminescent material that provides from table 2 when 150 ℃ of high temperature, in 91～94% scopes when luminosity of the luminescent material that embodiment 1-22 relates to is in room temperature, are higher than Comparative Examples Ca
0.99AlSiN
3: Eu
0.0189% of luminescent material.
Simultaneously, be not difficult to find following phenomenon by the corresponding data of embodiment 1-22 in the table 1:
(1) when M did not contain Ca or Sr in the luminescent material of the present invention, the luminosity of prepared luminescent material was obviously on the low side.
Like embodiment in the table 1 11,12, shown in 13; M does not contain Ca or Sr in the luminescent material in embodiment 11,12 and 13; Can know that by result in the table 1 embodiment 11,12 and the 13 prepared luminosity of luminescent material under three kinds of different chromaticity coordinatess all are starkly lower than the luminosity that M contains the prepared luminescent material of other embodiment of Ca or Sr.This shows that when containing Ca, Sr among the luminescent material M of the present invention, its luminous efficiency obviously increases.
(2) when R was rare earth element y and/or Gd in the luminescent material of the present invention, luminescent material had better luminosity.
Embodiment 10 and 14 in the contrast table 1; Luminescent material has increased component Gd with respect to luminescent material among the embodiment 14 among the embodiment 10; Their chromaticity coordinates is basic identical, but the brightness of luminescent material obviously is superior to the luminosity of luminescent material among the embodiment 14 among the embodiment 10.
Embodiment 3 and 15 in the contrast table 1, luminescent material is for luminescent material among the embodiment 15 among the embodiment 3, and R selects for use and is Y, Gd and Lu among the embodiment 3, and R selects for use and is Ce and Lu among the embodiment 15.Their chromaticity coordinates is basic identical, but the brightness of luminescent material obviously is superior to the luminosity of luminescent material among the embodiment 14 among the embodiment 10.
This shows that when R was rare earth element y and/or Gd in the luminescent material, luminescent material had better luminosity.
(3) when R was rare earth element y in the luminescent material of the present invention, luminescent material had better luminosity.
Embodiment 8 and 16-19 in the contrast table 1; Wherein, The luminescent material R of embodiment 16 selects for use and is Gd; R selects for use and is Y in embodiment 8,17,18 and 19 the luminescent material, and their chromaticity coordinates is basic identical, but the brightness of luminescent material obviously is superior to the luminosity of luminescent material among the embodiment 8 in embodiment 8,17,18 and 19.This shows, the invention luminescent material in R be rare earth element y, the time, luminescent material has better luminosity.
(4) when the consumption n of R in the luminescent material of the present invention was 0.001≤n≤0.05, luminescent material had better luminosity.
In order to increase comparative, the embodiment 8 when selecting Y for use with R in the luminescent material is an example with 17-19, and their chromaticity coordinates is basic identical, but the brightness of luminescent material obviously is superior to the luminosity of luminescent material in embodiment 18 and 19 in embodiment 8 and 17.This shows that the consumption n of R is 0.001≤n≤0.05 o'clock in the invention luminescent material, luminescent material has better luminosity.
(5) when the consumption m of Eu in the luminescent material of the present invention was 0.005≤m≤0.025, luminescent material had better luminosity.
In order to further specify the beneficial effect of the prepared luminescent material of the present invention with respect to luminescent material in the Comparative Examples; Test respectively by embodiment 1 prepared luminescent material with by the emmission spectrum and the excitation spectrum of the prepared luminescent material of Comparative Examples, referring to accompanying drawing 1 and accompanying drawing 2.X-coordinate is that wavelength, ordinate zou are relative emissive porwer in accompanying drawing 1 and accompanying drawing 2, and L1 represents the prepared luminescent material of the embodiment of the invention 1, and L2 represents the prepared luminescent material of Comparative Examples.
As shown in Figure 1, the embodiment of the invention 1 prepared nitride luminescent material has higher emissive porwer and wideer transmitting boundary with respect to Comparative Examples, and its half-width is 108nm, is wider than the 91nm of Comparative Examples, helps improving the colour rendering index of application device; Through their relative brightness of spectral radiance analytical system test, be 100 with the brightness of Comparative Examples, the relative brightness that test obtains embodiment 1 is 138.
As shown in Figure 2 by embodiment 1 prepared luminescent material with by the excitation spectrum of the prepared luminescent material of Comparative Examples; In 250-500nm excites scope; The embodiment of the invention 1 prepared nitride luminescent material has higher launching efficiency with respect to Comparative Examples; Under identical excitation wavelength, the luminosity of the luminescent material that embodiment 1 is prepared is better than Comparative Examples.The excitation spectrum of the luminescent material that relates to from embodiment 1 is simultaneously found out easily; Such nitride red luminescent material all has very high launching efficiency at 250-500nm, and this shows that such luminescent material can be applied to make with ultraviolet, purple light or the combination of blue ray radiation source and is used for making luminescent device.
Below will further specify the beneficial effect of luminescent material provided by the present invention when preparing luminescent device according to embodiment 23-33.
Embodiment 23:
It is in 1.41 the silicone resin that the red illuminating material that embodiment 1 is obtained is dispersed in specific refractory power; Through on 410nm purple LED chip, putting glue, curing behind the pulping that stirs; And welded circuit, use the resin sealed knot, the luminescent device that can obtain glowing; Its chromaticity coordinates is (0.6727,0.3214).
Embodiment 24
Red illuminating material and Y that embodiment 17 is obtained
3Al
5O
12: it is in 1.53 the silicone resin that the Yellow luminous material of Ce is dispersed in specific refractory power in 1: 6 ratio, through being coated in behind the pulping that stirs on the blue-light LED chip of 460nm, solidifies; And welded circuit, use the resin sealed knot, the luminescent device that can obtain emitting white light; Its chromaticity coordinates is (0.4417; 0.3905), colour rendering index 85, correlated(color)temperature 2809K.
Embodiment 25
The red illuminating material that embodiment 2 is obtained with (Mg, Ca, Sr, Ba)
2SiO
4: it is in 1.52 the silicone resin that the Yellow luminous material of Eu is dispersed in specific refractory power in 1: 10 ratio, through being coated in behind the pulping that stirs on the blue-light LED chip of 455nm, solidifies; And welded circuit, use the resin sealed knot, the luminescent device that can obtain emitting white light; Its chromaticity coordinates is (0.4228; 0.3943), colour rendering index 82, correlated(color)temperature 3173K.
Embodiment 26
It is in 1.51 the epoxy resin that red illuminating material that embodiment 9 is obtained and the Yellow luminous material of α-SiAlON:Eu are dispersed in specific refractory power in 1: 12 ratio, through being coated in behind the pulping that stirs on the blue-light LED chip of 450nm, solidifies; And welded circuit, use the resin sealed knot, the luminescent device that can obtain emitting white light; Its chromaticity coordinates is (0.3902; 0.3520), colour rendering index 76, correlated(color)temperature 3518K.
Embodiment 27
Red illuminating material and Ba that embodiment 6 is obtained
3Si
6O
12N
2: it is in 1.52 the epoxy resin that the Eu green luminescent material is dispersed in specific refractory power in 1: 8 ratio, through being coated in behind the pulping that stirs on the 452.5nm blue-light LED chip, solidifies; And welded circuit, use the resin sealed knot, the luminescent device that can obtain emitting white light; Its chromaticity coordinates is (0.3728; 0.3336), colour rendering index 90.6, correlated(color)temperature 3859K.
Embodiment 28
The red illuminating material that embodiment 3 is obtained with (Sr, Ba)
2SiO
4: it is in 1.52 the silicone resin that the Eu green luminescent material is dispersed in specific refractory power in 1: 5 ratio, through being coated in behind the pulping that stirs on the 460nm blue-light LED chip, solidifies; And welded circuit, use the resin sealed knot, the luminescent device that can obtain emitting white light; Its chromaticity coordinates is (0.4306; 0.3804), colour rendering index 86, correlated(color)temperature 2907K.
Embodiment 29
The red illuminating material that embodiment 8 is obtained with (Y, Lu)
3(Al, Ga)
5O
12: it is in 1.52 the epoxy resin that the Ce green luminescent material is dispersed in specific refractory power in 1: 4 ratio, through being coated in behind the pulping that stirs on the 445nm blue-light LED chip, solidifies; And welded circuit, use the resin sealed knot, the luminescent device that can obtain emitting white light; Its chromaticity coordinates is (0.4377; 0.3691), colour rendering index 89, correlated(color)temperature 2685K.
Embodiment 30
The red illuminating material that embodiment 7 is obtained and β-SiAlON:Eu green luminescent material, Sr
5(PO
4)
3It is in 1.52 the silicone resin that the Cl:Eu blue emitting material is dispersed in specific refractory power in 1: 5: 3 ratio, on the near ultraviolet LED chip that is coated in 380nm behind the pulping that stirs, solidifies; And welded circuit, use the resin sealed knot, the luminescent device that can obtain emitting white light; Its chromaticity coordinates is (0.3832; 0.3505), colour rendering index 89.7, correlated(color)temperature 3698K.
Embodiment 31
Red illuminating material and Ca that embodiment 14 is obtained
3(Sc, Mg)
2Si
3O
12: Ce green luminescent material, BaMgAl
10O
17: it is in 1.46 the silicone resin that the Eu blue emitting material is dispersed in specific refractory power in 1: 6: 2 ratio, on the ultraviolet LED chip that is coated in 360nm behind the pulping that stirs, solidifies; And welded circuit, use the resin sealed knot, the luminescent device that can obtain emitting white light; Its chromaticity coordinates is (0.3571; 0.3002), colour rendering index 82.7, correlated(color)temperature 4123K.
Embodiment 32
Red illuminating material and Zn that embodiment 20 is obtained
2SiO
4: Mn green luminescent material, BaMgA
110O
17: Eu blue emitting material three sizes mixing respectively, roller is pricked; And adopt silk screen printing evenly to be coated in the barrier groove of PDP metacoxa; Afterwards the substrate low temperature that prints roasting is shielded, encapsulates, charges into the Ne-Xe mixed inert gas, and welded circuit and processed the chromatic plasma luminescent device, the chromaticity coordinate of this device is (0.3211; 0.3308), brightness 864cd/m
2
Embodiment 33
The red illuminating material that embodiment 2 is obtained and (Y, Gd) BO
3: Eu rouge and powder mixes, (Zn
2SiO
4: Mn+ (Y, Lu)
3A
15O
12: Ce) blended green luminescent material and BaMgA
110O
17: Eu blue emitting material three sizes mixing respectively, roller is pricked; And adopt silk screen printing evenly to be coated in the barrier groove of PDP metacoxa; Afterwards the substrate low temperature that prints roasting is shielded, encapsulates, charges into the Ne-Xe mixed inert gas, and welded circuit and processed the chromatic plasma luminescent device, the chromaticity coordinate of this device is (0.3340; 0.3264), brightness 788cd/m
2
By the prepared luminescent device of embodiment 23-31; And can find out by embodiment 32 and 33 prepared chromatic plasma luminescent devices; Nitride red luminescent material provided by the present invention can satisfy different wave length ultraviolet, purple light or blue ray radiation source excite needs, be used for making luminescent device thereby can make with different optical color parameters with they combinations.Can find out that by data among the embodiment 23-31 nitride red luminescent material provided by the present invention can make up with the luminescent material of source of radiation and other glow colors to be made colour temperature and be lower than 4000K, colour rendering index greater than 80 low colour temperature, high colour developing white light LED part.
Embodiment 23-33 only is embodiments of the invention; It can not limit protection scope of the present invention; In the luminescent device that the present invention protected luminescent material can with glass, plastics and resin material mixing formation luminous element; And then realize luminous effect; Glass material, plastic material and resin material can be chosen wantonly in the present invention, as long as can reach luminescent material and chemical reaction does not take place for they, and still can effectively be excited and luminous getting final product by ultraviolet, purple light or blue ray radiation source after being dispersed in the illuminating part that forms among them.
More than be merely the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (14)
1. a nitride red luminescent material is characterized in that, said nitride red luminescent material has the structure of general formula (1),
Said general formula (1) is M
a(Al, B)
bSi
cN
dO
e: Eu
m, R
n, wherein:
Said M is at least a among Mg, Ca, Sr, Ba, the Zn;
Said R is at least a among rare earth element y, La, Ce, Gd, the Lu;
The mol ratio x of said element B and Al satisfies 0≤x≤0.1; And
0.9≤a＜1.1，0.9≤b≤1，1≤c≤1.5，2.5＜d＜5，0＜e＜0.1，0＜m＜0.05，0＜n＜0.1，1＜c/b＜1.5。
2. nitride red luminescent material according to claim 1 is characterized in that said M comprises Ca and/or Sr at least.
3. nitride red luminescent material according to claim 1 and 2 is characterized in that said R comprises rare earth element y and/or Gd at least.
4. according to each described nitride red luminescent material among the claim 1-3, it is characterized in that said R is a rare earth element y.
5. according to each described nitride red luminescent material among the claim 1-4, it is characterized in that the scope of said n is 0.001≤n≤0.05.
6. according to each described nitride red luminescent material among the claim 1-5, it is characterized in that the scope of said m is 0.005≤m≤0.025.
7. nitride red luminescent material according to claim 1 is characterized in that, said luminescent material is any in the following material:
Ca
0.99Al
0.9B
0.009Si
1.1N
3.8O
0.002:Eu
0.01，Y
0.001；
Ca
0.2Sr
0.89Al
0.99SiN
3O
0.001:Eu
0.008，Y
0.001，La
0.001；
Ca
0.75Sr
0.22Al
0.92B
0.07Si
1.2N4O
0.015:Eu
0.025，Y
0.02，Gd
0.005，Lu
0.005；
Ca
0.45Sr
0.45Zn
0.02Al
0.9Si
1.48N
4O
0.05:Eu
0.04，Y
0.015，Lu
0.005；
Sr
1.05Al
0.9B
0.09Si
1.3N
3.5O
0.0005:Eu
0.005，Y
0.008；
Ca
0.675Sr
0.3Al
0.9SiN
2.6O
0.005:Eu
0.02，Gd
0.003，La
0.002；
Sr
1.05Al
0.9B
0.09Si
1.3N
3.5O
0.0005:Eu
0.005，Y
0.05；
Sr
1.05Al
0.9B
0.09Si
1.3N
3.5O
0.0005:Eu
0.005，Y
0.0008；
Sr
10.5Al
0.9B
0.09Si
1.3N
3.5O
0.0005: Eu
0.005, Y
0.095Perhaps
Ca
0.2Sr
0.89Al
0.99SiN
3O
0.001:Eu
0.005，Y
0.001，La
0.001。
8. according to each described nitride red luminescent material among the claim 1-7, it is characterized in that said luminescent material is Powdered, film like or sheet.
9. illuminating part; It is characterized in that; Said illuminating part is to be dispersed in glass material, plastic material or the resin material formed by each described nitride red luminescent material among the claim 1-7; Perhaps, be formed at glass material, plastic material or resin material by each described nitride red luminescent material and other luminescent material co-dispersed among the claim 1-7.
10. illuminating part according to claim 9 is characterized in that, said other luminescent materials be in the following fluorescent material one or more:
(Y，Gd，Lu，Tb)
3(Al，Ga)
5O
12:Ce、(Mg，Ca，Sr，Ba)
2SiO
4:Eu、(Ca，Sr)
3SiO
5:Eu、(La，Ca)
3Si
6N
11:Ce、α-SiAlON:Eu、β-SiAlON:Eu、Ba
3Si
6O
12N
2:Eu、Ca
3(Sc，Mg)
2Si
3O
12:Ce、CaSc
2O
4:Eu、BaAl
8O
13:Eu、(Ca，Sr，Ba)Al
2O
4:Eu、(Sr，Ca，Ba)(Al，Ga，In)
2S
4:Eu、(Ca，Sr)
8(Mg，Zn)(SiO
4)
4Cl
2:Eu/Mn、(Ca，Sr，Ba)
3MgSi
2O
8:Eu/Mn、(Ca，Sr，Ba)
2(Mg，Zn)Si
2O
7:Eu、Zn
2SiO
4:Mn、(Y，Gd)BO
3:Tb、ZnS:Cu，Cl/Al、ZnS:Ag，Cl/Al、(Sr，Ca)
2Si
5N
8:Eu、(Li，Na，K)
3ZrF
7:Mn、(Li，Na，K)
2(Ti，Zr)F
6:Mn、(Ca，Sr，Ba)(Ti，Zr)F
6:Mn、Ba
0.65Zr
0.35F
2.7:Mn、(Sr，Ca)S:Eu、(Y，Gd)BO
3:Eu、(Y，Gd)(V，P)O
4:Eu、Y
2O
3:Eu、(Sr，Ca，Ba，Mg)
5(PO
4)
3Cl:Eu、(Ca，Sr，Ba)MgAl
10O
17:Eu、(Ca，Sr，Ba)Si
2O
2N
2:Eu、3.5MgO·0.5MgF
2·GeO
2:Mn。
11. a luminescent device is characterized in that, said luminescent device comprises the nitride red luminescent material described in each among source of radiation and the claim 1-8 at least.
12. luminescent device according to claim 11 is characterized in that, said source of radiation is VUV or ultraviolet or purple light or blue emission source.
13. according to claim 11 or 12 described luminescent devices, it is characterized in that, also contain in the said luminescent device by other luminescent materials of said source of radiation stimulated luminescence.
14. luminescent device according to claim 13 is characterized in that, said other luminescent materials be in the following fluorescent material one or more:
(Y，Gd，Lu，Tb)
3(Al，Ga)
5O
12:Ce、(Mg，Ca，Sr，Ba)
2SiO
4:Eu、(Ca，Sr)
3SiO
5:Eu、(La，Ca)
3Si
6N
11:Ce、α-SiAlON:Eu、β-SiAlON:Eu、Ba
3Si
6O
12N
2:Eu、Ca
3(Sc，Mg)
2Si
3O
12:Ce、CaSc
2O
4:Eu、BaAl
8O
13:Eu、(Ca，Sr，Ba)Al
2O
4:Eu、(Sr，Ca，Ba)(Al，Ga，In)
2S
4:Eu、(Ca，Sr)
8(Mg，Zn)(SiO
4)
4Cl
2:Eu/Mn、(Ca，Sr，Ba)
3MgSi
2O
8:Eu/Mn、(Ca，Sr，Ba)
2(Mg，Zn)Si
2O
7:Eu、Zn
2SiO
4:Mn、(Y，Gd)BO
3:Tb、ZnS:Cu，Cl/Al、ZnS:Ag，Cl/Al、(Sr，Ca)
2Si
5N
8:Eu、(Li，Na，K)
3ZrF
7:Mn、(Li，Na，K)
2(Ti，Zr)F
6:Mn、(Ca，Sr，Ba)(Ti，Zr)F
6:Mn、Ba
0.65Zr
0.35F
2.7:Mn、(Sr，Ca)S:Eu、(Y，Gd)BO
3:Eu、(Y，Gd)(V，P)O
4:Eu、Y
2O
3:Eu、(Sr，Ca，Ba，Mg)
5(PO
4)
3Cl:Eu、(Ca，Sr，Ba)MgAl
10O
17:Eu、(Ca，Sr，Ba)Si
2O
2N
2:Eu、3.5MgO·0.5MgF
2·GeO
2:Mn。
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| CN104031640A (en) * | 2014-06-11 | 2014-09-10 | 杭州电子科技大学 | Orange yellow fluorescent powder for white LED and preparation method of fluorescent powder |
| CN104031640B (en) * | 2014-06-11 | 2017-01-04 | 杭州电子科技大学 | A kind of orange yellow fluorescent powder for white light LED and preparation method thereof |
| CN107001933A (en) * | 2014-12-16 | 2017-08-01 | 电化株式会社 | Fluorophor and application thereof |
| US10519370B2 (en) | 2014-12-16 | 2019-12-31 | Denka Company Limited | Phosphor and application therefor |
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