CN102399554B - 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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- CN102399554B CN102399554B CN201110315197.4A CN201110315197A CN102399554B CN 102399554 B CN102399554 B CN 102399554B CN 201110315197 A CN201110315197 A CN 201110315197A CN 102399554 B CN102399554 B CN 102399554B
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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 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 red, green, blue three primary colours.Now 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 the conventional art modes such as display and lighting, these traditional red illuminating materials that once yielded unusually brilliant results can not meet the needs of the development of new techniques such as 3D demonstration, white light LEDs well due to the change of Application Areas, mode of excitation.
Since the end of the nineties in last century, the novel nitrogen/oxynitride luminescent material of a class is developed, and the anionic group of this class luminescent material contains the N of high negative charge
3-, electronic cloud bulking effect makes its excitation spectrum move to the long wave such as near ultraviolet, visible ray direction, and their matrix has network structure comparatively closely, and physicochemical property are stable.
Calendar year 2001 patent documentation EP1104799A1 discloses a class M
xsi
yn
z: the nitride red luminescent material of Eu (M is at least one in Ca/Sr/Ba, z=2/3x+4/3y), 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 only has room temperature in the time of 150 DEG C.
Chinese invention patent ZL 200480040967.7 has invented a class M
aa
bd
ce
dx
ered illuminating material, in formula, a+b=1 and M are one or both elements in Mn/Ce/Pr/Nd/Sm/Eu/Tb/Dy/Ho/Er/Tm/Yb, A is one or both elements in Mg/Ca/Sr/Ba, D is one or both elements in Si/Ge/Sn/Ti/Zr/Hf, E is one or both elements in B/Al/Ga/In/Sc/Y/La/Ga/Lu, and X is selected from one or both elements in O, N and 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 reports, this CaAlSiN
3: Eu luminescent material 89% when luminous intensity is room temperature in the time of 150 DEG C, is better than Sr
2si
5n
8: Eu luminescent material.
2009 non-patent literature (Int.J.Appl.Ceram.Technol., 2010,7 (6): 787-802) at CaSiN
2: on the basis of Eu, introduce a certain amount of AlN and obtained Cal-xAlzSiN
2+ z:Eux (0 < z < 0.3), but along with the introducing of AlN, the luminous efficiency of material significantly declines, it 405 and the external quantum efficiency of 450nm under exciting also only have respectively 28.5% and 24.5%; In addition, according to document report, Ca
0.999siN
2: Eu
0.001thermal quenching temperature lower, be approximately 110 DEG C, temperature profile is not good.
The red fluorescence powder relating in above-mentioned document has than the sulfide red fluorescent material of tradition ((Ca, Sr) S:Eu
2+) more excellent temperature profile., be also not difficult to find out, the red illuminating material relating in above-mentioned document 90% when luminous intensity is all lower than room temperature in the time of 150 DEG C, still awaits further improvement meanwhile; 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 is generally in 90nm left and right, has the needs of further broadening; In addition, current employing adds red illuminating material to improve the technical scheme of colour rendering index, although can obtain high colour rendering index, problem simultaneously that brought device whole lighting efficiency significantly to decline, this luminous efficiency that just need to 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 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 one in Mg, Ca, Sr, Ba, Zn; R is at least one in rare earth element y, La, Ce, Gd, Lu; The mol ratio x of element B and Al meets 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 at least comprises Ca and/or Sr.
Further, above-mentioned R at least comprises rare earth element y and/or Gd.
Further, above-mentioned R is 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 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
0.095; Or
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 is also provided in the present invention, this illuminating part is that above-mentioned nitride red luminescent material is dispersed in glass material, plastic material or resin material and forms, or, be to be jointly dispersed in glass material, plastic material or resin material by above-mentioned nitride red luminescent material and other luminescent materials to form.
Further, above-mentioned other luminescent materials are one or more in following fluorescent material:
(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。
Meanwhile, also provide in the present invention a kind of luminescent device, this luminescent device at least comprises source of radiation and above-mentioned nitride red luminescent material.
Further, above-mentioned source of radiation is vacuum ultraviolet (VUV) or ultraviolet or purple light or blue emission source.
Further, in above-mentioned luminescent device, also contain by other luminescent materials of described source of radiation stimulated luminescence.
Further, above-mentioned other luminescent materials be in 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 object described above, feature and advantage, the present invention also has other object, feature and advantage.Below with reference to figure, the present invention is further detailed explanation.
Brief description of the drawings
Accompanying drawing forms the part of this specification sheets, for further understanding the present invention, accompanying drawing shows the preferred embodiments of the present invention, and is used for illustrating principle of the present invention together with specification sheets.In figure:
Fig. 1 shows the emmission spectrum comparison diagram of the prepared luminescent material of the embodiment of the present invention 1 and comparative example; And
Fig. 2 shows the excitation spectrum comparison diagram of the prepared luminescent material of the embodiment of the present invention 1 and comparative example.
Embodiment
Be noted that following detailed description is all exemplary, is intended to the invention provides further instruction.Unless otherwise, all technology used herein and scientific terminology have the identical meanings of conventionally understanding with general technical staff of the technical field of the invention.
In the typical embodiment of one of the present invention, a kind of nitride red luminescent material, wherein contain divalent metal M, rare earth element Eu (europium) and R, Al (aluminium), Si (silicon), N (nitrogen) and O (oxygen) simultaneously, and thering is the structure of general formula (1), general formula (1) is M
a(Al, B)
bsi
cn
do
e: Eu
m, R
n.Wherein, M is Mg, Ca, Sr, Ba, at least one in Zn, R is rare earth element y, La, Ce, Gd, in Lu at least one, the mol ratio x of element B and Al meets 0≤x≤0.1, and, wherein 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.
The structure of above-mentioned luminescent material is based on SiN
4tetrahedron builds, with Eu
2+for luminescence center.By introduce easily (Al, B) component of trend network structure in luminescent material, and adopt a small amount of rare-earth element R (comprising Y, La, Ce, Gd, Lu) to come cover or calking; Simultaneously in order to maintain the tetrahedral structure of this luminescent material, and don't as for causing larger lattice distortion, (Al, B) add-on b is similar to the add-on a of divalent metal element M, 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 meets 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.
Meanwhile, other significant effects have also been obtained adding of Al and B.As low melting point and the activity of element B (boron), make it contribute to very much to strengthen roasting, and then be conducive to improve the particle degree of crystallinity of luminescent material, make this luminescent material there is high luminous efficiency, good temperature profile and little light decay, the introduction volume of B (boron) should be suitable, should ensure that the mol ratio x of B (boron) and Al (aluminium) is in the scope of 0≤x≤0.1, if exceed this scope, because the radius difference of B (boron) and Al (aluminium) is too large, can cause lattice distortion, the luminous efficiency to this luminescent material and life-span are unfavorable on the contrary.
Codoped at above-mentioned luminescent material rare earth elements R (comprising Y, La, Ce, Gd, Lu) is conducive to strengthen the absorption of luminescent material to exciting light quantity of radiant energy, and the transmission ofenergy of absorption can be improved to luminosity to luminescence center Eu, and can not produce with the competition of luminescence center and absorb or heavily absorb, thereby ensure that material has superior luminous efficiency; The effect of strengthening luminescent material roasting is also played in the introducing of rare-earth element R (comprising Y, La, Ce, Gd, Lu), jointly improve luminescent material particle degree of crystallinity with the B adding (boron), strengthen luminous efficiency, reduce light decay and thermal quenching simultaneously; Similarly, rare-earth element R (comprising Y, La, Ce, Gd, Lu) also has an appropriate add-on n:0 < n < 0.1, excessive obvious non-luminous dephasign, the infringement luminosity of can producing of add-on.
In order to meet the application demand of high colour developing, on the basis of said components, also introduce the half-width that appropriate O (oxygen) carrys out broadening material emmission spectrum, when the introduction volume e of oxygen is during in 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 of the 90nm left and right of the red illuminating materials such as Eu, and light efficiency keeps better.But in the time that the add-on e of oxygen exceedes 0.1, due to its be easier to structure in (Al, B), Si and rare earth etc. compound and change structure and crystal field can make the luminosity of red illuminating material greatly weaken on the contrary.
In luminescent material of the present invention, Eu
2+for luminescence center, its radiant light that can be positioned at below 500nm by wavelength effectively excites, and launches spectrum and be positioned at the wide range visible red of 500-780nm.
Simultaneously, in order to meet the application requiring of different luminescent devices to luminescent material Photochromic Properties etc., luminescent material of the present invention comprehensively adopts the controllable adjustment that regulates the approach such as dyad Mg, Ca, Sr, Ba, the kind of Zn and the concentration of ratio and activator Eu of M representative in its general formula to realize its transmitting main peak and spectrum area coverage.As the minimizing of the increase along with Sr content and Ca content, the transmitting 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 transmitting main peak, luminous intensity strengthens simultaneously, but in the time that the concentration of Eu exceedes 0.025, concentration quenching effect will appear in the luminous of this material, can make on the contrary the luminous intensity of luminescent material reduce even if now continue to increase Eu concentration, and in the time that the concentration of Eu increases to 0.05, concentration quenching effect is very serious, and the luminosity of material significantly declines.When the content a of divalent metal M component is in the time that 0.9≤a < 1.1, Eu concentration m meet 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 by reading the present patent application file, under the instruction of the present patent application file, can reasonably use routine techniques means, realize the controllable adjustment of such luminescent material emmission spectrum at 500～780nm visible light wave range, not repeat them here.
Preferably, in above-mentioned nitride red luminescent material, M at least comprises Ca and/or Sr.In the time at least comprising one or both in Ca, Sr in M, obtaining under the condition of identical colourity, this luminescent material has excellent luminosity and temperature profile.
Preferably, in above-mentioned nitride red luminescent material, R at least comprises rare earth element y and/or Gd.In the time at least comprising one or both in rare earth element y, Gd in R, obtaining under the condition of identical colourity, this luminescent material has excellent luminosity and temperature profile.More preferably, R is rare earth element y.
Preferably, in above-mentioned nitride red luminescent material, the scope of the add-on n of R is 0.001≤n≤0.05.Within the scope of this, this luminescent material has excellent luminosity and temperature profile.
Preferably, the add-on m of Eu in above-mentioned nitride red luminescent material, 0.005≤m≤0.025 this luminescent material within the scope of this has excellent luminosity and temperature profile.This is that very little, luminosity is low for luminescence center Eu because in the time that the add-on of Eu is less than 0.005; Concentration quenching effect can occur again in the time that Eu exceedes 0.025, and luminosity is along with the increase of Eu declines 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 in nitride red luminescent material, the quality percentage composition of C is no more than 0.1% of this luminescent material total mass in the present invention.Having of C of trace is beneficial to stabilized illumination material luminescence center Eu
2+valence state, prevent from changing into Eu
3+and infringement luminous efficiency; But in the time that its content exceedes 0.1%, can pollute luminescent material, not only affect body colour, and light efficiency also decline to a great extent.
Preferably, above-mentioned nitride red luminescent material is any in 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
0.095; Or
Ca
0.2Sr
0.89Al
0.99SiN
3O
0.001:Eu
0.005，Y
0.001，La
0.001。
Meanwhile, in order to be suitable for different application demands, that the luminescent material the present invention relates to can directly be formed to is Powdered, film like or sheet.
To provide the method for the nitride red luminescent material of a kind of the present invention of preparation below, specific as follows:
According to the stoichiometric ratio shown in general formula (1), after accurately being weighed, the raw materials such as the compound of the compound of the nitride of divalent metal M, aluminium nitride, boron nitride, silicon nitride and Eu and rare earth R mix, and then roasting 4～20 hours in nitrogen or nitrogen and hydrogen mixture atmosphere, under the high temperature of 1400～1800 DEG C, the product of roasting of gained again through broken, sieve, wash, the step such as oven dry can obtain red illuminating material of the present invention.
In the typical embodiment of one of the present invention, a kind of illuminating part is provided, this can be that luminescent film can be also light tiles, it is to be dispersed in glass material, plastic material or resin material and to be formed by above-mentioned nitride red luminescent material, or, be to be evenly dispersed in glass material, plastic material or resin material by above-mentioned nitride red luminescent material together with other luminescent materials to form.
This illuminating part provided by the present invention, as long as at glass material, in plastic material or resin material preparation process, by nitride red the present invention luminescent material, or the nitride red luminescent material of the present invention and other luminescent materials add glass material to, in the raw material of plastic material or resin material, mix, then according to glass material, the ordinary method of plastic material or resin material is prepared into membranaceous or sheet, the nitride red luminescent material of the present invention, or the mixture of the nitride red luminescent material of the present invention and other luminescent materials joins glass material, the amount of plastic material or resin material equates with the add-on of luminescent material in illuminating part preparation process in prior art.Those skilled in the art, on basis of the present invention, can prepare this luminescent film provided by the present invention or light tiles by rational technique means, therefore its making method is repeated no more.
Preferably, above-mentioned other luminescent materials are (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 in Mn.
In the process of making illuminating part, the blending ratio of nitride red luminescent material provided by the present invention and other luminescent materials can reasonably regulate according to the demand of application and photochromic adjusting, those skilled in the art through reasonably analyzing, have the ability to prepare required illuminating part on basis of the present invention.
In the typical embodiment of one of the present invention, a kind of luminescent device is also provided, this luminescent device at least comprises source of radiation and the above-mentioned nitride red luminescent material with general formula (1), 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 by being dispersed in the illuminating part being prepared in glass material, plastic material or resin material.
Source of radiation can be any source of radiation that can send wavelength and be positioned at the radiant light below 500nm, preferably, source of radiation is vacuum ultraviolet (VUV), ultraviolet, purple light or blue ray radiation source, and under they excite respectively, the luminescent material the present invention relates to all can send efficient ruddiness.
Preferably, in above-mentioned luminescent device, except having the nitride red luminescent material of the middle structure of general formula (1), the luminescent material that can also add other effectively to be excited by corresponding source of radiation, as in " blue-ray LED+the present invention relates to luminescent material " combination, add and can be formed white light emitting device by blue-light excited yellow or green luminescent material; In " vacuum ultraviolet (VUV), ultraviolet or purple LED+the present invention relates to luminescent material ", add and can also can be formed white light emitting device by vacuum ultraviolet (VUV), ultraviolet or purple light excited blueness and green luminescent material, etc., these white light emitting devices can be used in illumination or demonstration field.
In above-mentioned luminescent device, can be used for mixing with the nitride red luminescent material of the present invention other luminescent materials that use 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.
Further illustrate chromaticity coordinate, relative brightness and the half-width situation of nitride red luminescent material provided by the present invention below with reference to specific embodiment 1-22 and comparative example.Meanwhile, further illustrate the beneficial effect of luminescent device provided by the present invention in connection with embodiment 23-33.
In embodiment 1-22, the chemical formula of nitride red luminescent material is as shown in table 1, and comparative example is selected pure Ca
0.99alSiN
3: Eu
0.01luminescent material.
Luminescent material preparation method in embodiment 1-22 and comparative example:
According to the stoichiometric ratio in the general formula shown in general formula embodiment 1-22, by the nitride of divalent metal M, aluminium nitride, boron nitride, the raw materials such as the compound of the compound of silicon nitride and Eu and rare earth R mix after accurately weighing, wherein the oxygen in component is introduced by the compound of Eu or the compound of rare earth R, and then in nitrogen or nitrogen and hydrogen mixture atmosphere, roasting 6～8 hours under the high temperature of 1500～1600 DEG C, the product of roasting of gained passes through fragmentation (being crushed to 5～20 microns) again, cross 100～500 mesh sieves, through diluted acid pickling or deionized water washing, 80～120 DEG C of oven dry, obtain having the sample of embodiment 1-22 and comparative example chemical formula.
Testing method:
Adopt spectrophotometer to carry out chromaticity coordinate, relative brightness and half-width test to nitride red luminescent material in comparative example and embodiment 1-22, wherein setting excitation wavelength is 460nm, and the relative brightness that defines comparative example luminescent material is 100, test result is as shown in table 1.
The temperature profile data of table 2 comparative example and the relative brightness of embodiment 1-22 luminescent material
The embodiment 1-22 result of enumerating from table 1 is not difficult to find out, the novel red luminescent material the present invention relates to all has than comparative example Ca
0.99alSiN
3: Eu
0.01the luminosity that luminescent material is higher and wider half-width, these are all 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 providing from table 2, in the time of 150 DEG C of high temperature, in 91～94% scopes of the luminosity of the luminescent material that embodiment 1-22 relates in the time of room temperature, higher than comparative example Ca
0.99alSiN
3: Eu
0.0189% of luminescent material.
Meanwhile, be not difficult to find following phenomenon by the corresponding data of embodiment 1-22 in table 1:
(1) in the time that in luminescent material of the present invention, M does not contain Ca or Sr, the luminosity of prepared luminescent material is obviously on the low side.
As shown in embodiment in table 1 11,12,13, in embodiment 11,12 and 13, in luminescent material, M does not contain Ca or Sr, from result in table 1, the luminosity of the prepared luminescent material of embodiment 11,12 and 13 under three kinds of different chromaticity coordinatess is all starkly lower than the luminosity of the prepared luminescent material of other embodiment that M contains Ca or Sr.As can be seen here, while containing Ca, Sr in luminescent material M of the present invention, its luminous efficiency obviously increases.
(2) in the time that in luminescent material of the present invention, R is rare earth element y and/or Gd, luminescent material has better luminosity.
Embodiment 10 and 14 in contrast table 1, in embodiment 10, luminescent material has increased component Gd with respect to luminescent material in embodiment 14, their chromaticity coordinates is basic identical, but in embodiment 10, the brightness of luminescent material is obviously better than the luminosity of luminescent material in embodiment 14.
In contrast table 1, in embodiment 3 and 15, embodiment 3, luminescent material is for luminescent material in embodiment 15, and in embodiment 3, R selects as Y, Gd and Lu, and in embodiment 15, R selects as Ce and Lu.Their chromaticity coordinates is basic identical, but in embodiment 10, the brightness of luminescent material is obviously better than the luminosity of luminescent material in embodiment 14.
As can be seen here, when in luminescent material, R is rare earth element y and/or Gd, luminescent material has better luminosity.
(3) in the time that in luminescent material of the present invention, R is rare earth element y, luminescent material has better luminosity.
Embodiment 8 and 16-19 in contrast table 1, wherein, the luminescent material R of embodiment 16 selects as Gd, in the luminescent material of embodiment 8,17,18 and 19, R selects as Y, their chromaticity coordinates is basic identical, but in embodiment 8,17,18 and 19, the brightness of luminescent material is obviously better than the luminosity of luminescent material in embodiment 8.As can be seen here, in invention luminescent material R be rare earth element y, time, luminescent material has better luminosity.
(4) in the time that the consumption n of R in luminescent material of the present invention is 0.001≤n≤0.05, luminescent material has better luminosity.
In order to increase comparative, the embodiment 8 while selecting Y taking R in luminescent material and 17-19 are as example, and their chromaticity coordinates is basic identical, but in embodiment 8 and 17, the brightness of luminescent material is obviously better than the luminosity of luminescent material in embodiment 18 and 19.As can be seen here, in invention luminescent material, the consumption n of R is 0.001≤n≤0.05 o'clock, and luminescent material has better luminosity.
(5) in the time that the consumption m of Eu in luminescent material of the present invention is 0.005≤m≤0.025, luminescent material has better luminosity.
In order to further illustrate the beneficial effect of the prepared luminescent material of the present invention with respect to luminescent material in comparative example, test respectively by the prepared luminescent material of embodiment 1 with by emmission spectrum and the excitation spectrum of the prepared luminescent material of comparative example, referring to accompanying drawing 1 and accompanying drawing 2.Be that wavelength, ordinate zou are relative emissive porwer at accompanying drawing 1 and X-coordinate in accompanying drawing 2, L1 represents the luminescent material that the embodiment of the present invention 1 is prepared, and L2 represents the luminescent material that comparative example is prepared.
As shown in Figure 1, the prepared nitride luminescent material of the embodiment of the present invention 1 has higher emissive porwer and wider transmitting boundary with respect to comparative example, and its half-width is 108nm, is wider than the 91nm of comparative example, is conducive to improve the colour rendering index of application device; Through their relative brightness of spectral radiance analytical system test, taking the brightness of comparative example as 100, the relative brightness that test obtains embodiment 1 is 138.
As shown in Figure 2 by the prepared luminescent material of embodiment 1 with by the excitation spectrum of the prepared luminescent material of comparative example, in 250-500nm excites scope, the prepared nitride luminescent material of the embodiment of the present invention 1 has higher launching efficiency with respect to comparative example, under identical excitation wavelength, the luminosity of the prepared luminescent material of embodiment 1 is better than comparative example.The excitation spectrum of the luminescent material relating to from embodiment 1 is easily found out simultaneously, 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 ultraviolet, purple light or blue ray radiation source and is used in combination to manufacture luminescent device.
The beneficial effect of luminescent material provided by the present invention in the time preparing luminescent device will be further illustrated according to embodiment 23-33 below.
Embodiment 23:
It is in 1.41 silicone resin that the red illuminating material that embodiment 1 is obtained is dispersed in specific refractory power, after the pulping that stirs, on 410nm purple LED chip, put glue, solidify, and weldering is turned on the electricity, use resin sealed knot, the luminescent device that can obtain glowing, its chromaticity coordinates is (0.6727,0.3214).
Embodiment 24
The red illuminating material that embodiment 17 is obtained and Y
3al
5o
12: it is in 1.53 silicone resin that the Yellow luminous material of Ce is dispersed in specific refractory power in 1: 6 ratio, after the pulping that stirs, be coated on the blue-light LED chip of 460nm, solidify, and weld and turn on the electricity, use 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 and (Mg, Ca, Sr, Ba)
2siO
4: it is in 1.52 silicone resin that the Yellow luminous material of Eu is dispersed in specific refractory power in 1: 10 ratio, after the pulping that stirs, be coated on the blue-light LED chip of 455nm, solidify, and weld and turn on the electricity, use 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 epoxy resin that the Yellow luminous material of the red illuminating material that embodiment 9 is obtained and α-SiAlON:Eu is dispersed in specific refractory power in 1: 12 ratio, after the pulping that stirs, be coated on the blue-light LED chip of 450nm, solidify, and weld and turn on the electricity, use 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
The red illuminating material that embodiment 6 is obtained and Ba
3si
6o
12n
2: it is in 1.52 epoxy resin that Eu green luminescent material is dispersed in specific refractory power in 1: 8 ratio, after the pulping that stirs, be coated on 452.5nm blue-light LED chip, solidify, and weld and turn on the electricity, use 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 and (Sr, Ba)
2siO
4: it is in 1.52 silicone resin that Eu green luminescent material is dispersed in specific refractory power in 1: 5 ratio, after the pulping that stirs, be coated on 460nm blue-light LED chip, solidify, and weld and turn on the electricity, use 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 and (Y, Lu)
3(Al, Ga)
5o
12: it is in 1.52 epoxy resin that Ce green luminescent material is dispersed in specific refractory power in 1: 4 ratio, after the pulping that stirs, be coated on 445nm blue-light LED chip, solidify, and weld and turn on the electricity, use 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 silicone resin that Cl:Eu blue emitting material is dispersed in specific refractory power in 1: 5: 3 ratio, after the pulping that stirs, be coated on the near ultraviolet LED chip of 380nm, solidify, and weld and turn on the electricity, use 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
The red illuminating material that embodiment 14 is obtained and Ca
3(Sc, Mg)
2si
3o
12: Ce green luminescent material, BaMgAl
10o
17: it is in 1.46 silicone resin that Eu blue emitting material is dispersed in specific refractory power in 1: 6: 2 ratio, after the pulping that stirs, be coated on the ultraviolet LED chip of 360nm, solidify, and weld and turn on the electricity, use 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
The red illuminating material that embodiment 20 is obtained and Zn
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 to be evenly coated in the barrier groove of PDP metacoxa, afterwards the substrate low temperature printing is baked and shielded, encapsulates, is filled with Ne-Xe mixed inert gas, and weld to turn on the electricity and make 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) mix green luminescent material and BaMgA
110o
17: Eu blue emitting material three sizes mixing respectively, roller is pricked, and adopt silk screen printing to be evenly coated in the barrier groove of PDP metacoxa, afterwards the substrate low temperature printing is baked and shielded, encapsulates, is filled with Ne-Xe mixed inert gas, and weld to turn on the electricity and make 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 be found out by embodiment 32 and 33 prepared chromatic plasma luminescent devices, nitride red luminescent material provided by the present invention can meet different wave length ultraviolet, purple light or blue ray radiation source excite needs, thereby can be used in combination to manufacture the luminescent device with different optical color parameters from them.Can be found out by data in embodiment 23-31, nitride red luminescent material provided by the present invention can combine to manufacture colour temperature with the luminescent material of source of radiation and other glow colors and be greater than 80 low colour temperature, high colour developing white light LED part lower than 4000K, colour rendering index.
Embodiment 23-33 is only embodiments of the invention; it can not limit protection scope of the present invention; in the luminescent device that the present invention protects, luminescent material can be mixed to form luminous element with glass, plastics and resin material; and then realize luminous effect; glass material, plastic material and resin material can be optional in the present invention; as long as can reach luminescent material and chemical reaction does not occur for they, and be dispersed in and still can be effectively excited by ultraviolet, purple light or blue ray radiation source after the illuminating part forming among them and luminous.
These are only 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 modifications and variations.Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (14)
1. a nitride red luminescent material, is characterized in that, described nitride red luminescent material has the structure of general formula (1), and described general formula (1) is M
a(Al, B)
bsi
cn
do
e: Eu
m, R
n, wherein:
Described M is at least one in Mg, Ca, Sr, Ba, Zn;
Described R is at least one in rare earth element y, La, Ce, Gd, Lu;
The mol ratio x of described element B and Al meets 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, described M at least comprises Ca and/or Sr.
3. nitride red luminescent material according to claim 1, is characterized in that, described R at least comprises rare earth element y and/or Gd.
4. according to the nitride red luminescent material described in any one in claim 1-3, it is characterized in that, described R is rare earth element y.
5. according to the nitride red luminescent material described in any one in claim 1-3, it is characterized in that, the scope of described n is 0.001≤n≤0.05.
6. according to the nitride red luminescent material described in any one in claim 1-3, it is characterized in that, the scope of described m is 0.005≤m≤0.025.
7. nitride red luminescent material according to claim 1, is characterized in that, described luminescent material is any in following material:
Ca
0.99Al
0.9B
0.009Si
1.1N
3.8O
0.002:Eu
0.01,Y
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；
Sr
1.05Al
0.9B
0.09Si
1.3N
3.5O
0.0005:Eu
0.005,Y
0.008；
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; Or
Sr
1.05Al
0.9B
0.09Si
1.3N
3.5O
0.0005:Eu
0.005,Y
0.095。
8. according to the nitride red luminescent material described in any one in claim 1-3,7, it is characterized in that, described luminescent material is Powdered, film like or sheet.
9. an illuminating part, it is characterized in that, described illuminating part is to be dispersed in glass material, plastic material or resin material and to be formed by the nitride red luminescent material described in any one in claim 1-7, or, be to be jointly dispersed in glass material, plastic material or resin material by the nitride red luminescent material described in any one in claim 1-7 and other luminescent materials to form.
10. illuminating part according to claim 9, is characterized in that, described other luminescent materials are one or more in following fluorescent material:
(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. 1 kinds of luminescent devices, is characterized in that, described luminescent device at least comprises the nitride red luminescent material described in any one in source of radiation and claim 1-8.
12. luminescent devices according to claim 11, is characterized in that, described source of radiation is vacuum ultraviolet (VUV) or ultraviolet or purple light or blue emission source.
13. according to the luminescent device described in claim 11 or 12, it is characterized in that, also contains by other luminescent materials of described source of radiation stimulated luminescence in described luminescent device.
14. luminescent devices according to claim 13, is characterized in that, described other luminescent materials be in 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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