CN102504812B - Single-component multi-wavelength panchromatic white-light material for LEDs and method of preparing single-component multi-wavelength panchromatic white-light material - Google Patents
Single-component multi-wavelength panchromatic white-light material for LEDs and method of preparing single-component multi-wavelength panchromatic white-light material Download PDFInfo
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Abstract
The invention discloses a single-component multi-wavelength panchromatic white-light material for LEDs and a method of preparing the single-component multi-wavelength panchromatic white-light material. Chemical composition of the single-component multi-wavelength panchromatic white-light material is E1-iAl12-jO19:iDy3+, jMn, wherein E refers to one or a plurality of Ca, Sr and Ba, i is smaller than or equal and larger than or equal to 0.2, j is smaller than or equal to 0 and larger than or equal to 0.12, and Mn is mixture of Mn4+ and Mn2+. The method for preparation includes: using Dy2O3 to prepare Dy(NO3)3 solution, mixing the solution with alkaline-earth metal nitrate, aluminum nitrate and manganese acetate, adding ethylene glycol, citric acid and urea, and sintering precursor to obtain the material. The single-component multi-wavelength panchromatic white-light material can be excited by an LED of near-ultraviolet with a wavelength 385-390nm to emit white light with a color coordinate controllable, regulation of cold and warm white light is easy to implement in a single component, and accordingly, shortages of complex processes such as powder matching, mixing and the like, self-attraction of different components and the like in application of multi-component luminescent materials are overcome.
Description
Technical field
The present invention relates to luminescent material, particularly relate to the luminescent material of a kind of single-component that can be used near ultraviolet LED, multi-wavelength, panchromatic white light.Be specifically related to a kind of can be effectively by near ultraviolet excitation, and launch the single-component white light material of four wavelength or dual wavelength.
Background technology
Leading product on white light LEDs market are the dual base color white LEDs that formed by yellow fluorescent powder YAG:Ce and blue-ray LED s encapsulation now.But this type of white LEDs Di colour temperature district colour rendering index is lower, cannot meet large-scale lighting demand, reason is in its white light, to only have gold-tinted and blue light ingredient, and red composition is less.Along with the wavelength of purple LED chip further moves toward shortwave direction, and the efficiency of near ultraviolet LED chip further improves, the indigo plant being excited by near-ultraviolet light LED chip (460nm), green (525nm), orange (590nm), four wavelength white lights of compositions such as red (640nm), when keeping luminous efficiency to be 306lm/W, its colour rendering index is still up to 95(L.Zhang, X.Guo, T.Liang, X.L.Gu, Q.M.Lin, G.D.Shen, Color rendering and luminous efficacy of trichromatic and tetrachromatic LED ?based white LEDs, Microelectronics is (1) J.38, 2007, 1 ?6).
Simultaneously; investigators have developed many blue light material (Y.Y.Jung that can be applied to near-ultraviolet light LED; J.H.Kim; Y.C.Kang; Luminescence enhancement of Eu ?doped calcium magnesium silicate blue phosphor for UV ?LED application; J.Lumin.129 (6), 2009,615 ?619; X.G.Zhang, X.P.Tang, J.L.Zhang, H.H.Wang, J.X.Shi, M.L.Gong,
luminescent properties of Sr 2 mgSi 2 o 7 : Eu 2+ asblue phosphor for
nUV?
light ?emitting diodes, Powder Technol.204 (2 ?3), 2010,263 ?267.), green light material (Y.Chen, J.Wang, X.G.Zhang, G.G.Zhang, M.L.Gong, Q.Su, An intense green emitting LiSrPO
4: Eu
2+, Tb
3+for phosphor ?converted LED, Sensor.Actuat.B:Chem.148 (1), 2010,259 ?263; W.J.Park, Y.H.Song, D.H.Yoon, Synthesis and luminescent characteristics of Ca
2-xsr
xsiO
4: Eu
2+as a potential green ?emitting phosphor near UV ?white LED applications, Mater.Sci.Engin.173 (1 ?3), 2010,76 ?79.) with red light material (F.B.Cao, Y.W.Tian, Y.J.Chen, L.J.Xiao, Q.Wu, Luminescence investigation of red phosphors Ca
0.54sr
0.34-1.5xeu
0.08sm
x(MoO
4)
y(WO
4)
1-yfor UV ?white LED device, J.Lumin.129 (6), 2009,585 ?588; T.Y.Kim, S.H.Kang, Potential red phosphor for UV ?white LED device, J.Lumin.122 ?123,2007,964 ?966.), these three primary colors fluorescent powders are mixed according to a certain ratio to the white light material that can obtain near ultraviolet LED, but in practical application work, the luminescent material of not sharing the same light join powder with batch mixing be together with the technique of complexity, also may produce self-absorption, reduce luminous efficiency.Therefore, if can realize multi-wavelength white light in same component, just can greatly simplify production process, reduce production costs.Although people make great efforts to develop single-component white light material, as by codoped mode, and in fact often because produce cross relaxation or concentration quenching between different active ions, overall luminous efficiency is weakened or material not luminous.
Summary of the invention
The object of the invention is to overcome the shortcoming of prior art, provide a kind of can be effectively by near ultraviolet excitation, and launch the single-component white light material of four wavelength or dual wavelength.Its chemical constitution is: E
1 ?ial
12 ?jo
19: iDy, jMn (E=Ca wherein, Sr, one or more in Ba; 0.01≤i≤0.2,0.01≤j≤0.12; Mn=Mn
4+with Mn
2+mixing).
Object of the present invention is achieved through the following technical solutions:
The panchromatic white light material of used near ultraviolet LED single-component multi-wavelength, this material is with alkaline earth aluminate EAl
12o
19for matrix, with Dy
3+as activator, with Mn
4+and Mn
2+for coactivator, chemical constitution is E
1 ?ial
12 ?jo
19: iDy
3+, jMn, wherein E is one or more in Ca, Sr and Ba; 0.01≤i≤0.2,0.01≤j≤0.12; Mn is Mn
4+with Mn
2+mixing; The near-ultraviolet light LED that this material is 385～390nm with wavelength excites, and obtains the controlled white light of chromaticity coordinates.
For further realizing the object of the invention, described chromaticity coordinates is positioned at: x=0.31, y=0.38.
Consisting of of described white light: 472nm blue light, 514nm green glow, 569nm orange light and 650nm ruddiness.
The preparation method of the panchromatic white light material of single-component multi-wavelength for described LED: by alkine earth metal nitrate E (NO
3)
2, aluminum nitrate, manganese acetate solution and Dy (NO
3)
3solution is mixed to get mixing solutions, wherein, counts in molar ratio E
2+: Al
3+: Dy
3+: Mn is (1 ?i): (12 ?j): i:j, wherein, 0.01≤i≤0.2,0.01≤j≤0.12; E is one or more in Ca, Sr and Ba; In mixing solutions, add citric acid, urea and ethylene glycol, mix, utilize combustion method in unlimited system calcination, obtain precursor, then at 800～1000 ℃, respectively process 3～5 hours respectively the panchromatic white light material of single-component multi-wavelength for the LED making with 1350～1500 ℃.
The volume ratio of described ethylene glycol and mixing solutions is preferably 1:(1～2).
Described citric acid and amount of urea are respectively the LED that makes with 1 to 5 times of the panchromatic white light material of single-component multi-wavelength total mass.
The invention provides a kind of with EAl
12o
19(wherein E=Ca, Sr, one or more in Ba) is matrix, with Dy
3+as activator, the panchromatic white light material of single-component four wavelength that the Mn ion of take is coactivator, can be 385～390nm near ultraviolet excitation by wavelength, and launch by 472nm blue light (Dy
3+transition
4f
9/2?
6h
15/2), 514nm green glow (Mn
2+'s
4t
1g(
4g) ?
6a
1(
6s) transition), 569nm orange light (Dy
3+'s
4f
9/2?
6h
13/2transition), 650nm ruddiness (Mn
4+'s
2e ?
4a
2transition) the four wavelength white lights that form.According to bibliographical information, under air conditions, at matrix EAl
12o
19in (wherein E=Ca, Sr, Ba), there is (T.Murata, T.Tanoue, M.Iwasaki, K.Morinaga, T.Hase, Fluorescence properties of Mn with tetravalence form in most mn ions
4+in CaAl
12o
19compounds as red ?emitting phosphor for white LED, J.Lumin.114 (3 ?4) 2005,207 ?212; Y.X.Pan, G.K.Liu, Influence of Mg
2+on luminescence efficiency and charge compensating mechanism in phosphor CaAl
12o
19: Mn
4+, Opt.Lett.33,2008,1 ?3; C.H.Kim, S.C.Choi, H.G.Kang, J.K.Park, Luminescence properties of MAl
12o
19: Mn
4+(M=Ca, Sr, Ba) for UV LEDs, J.Ceram.Soc.Jpn117,2009,647 ?649.), in emmission spectrum, do not observe Mn
2+peak.In the present invention, due to Dy
3+the Ca that replaces similar radius
2+, due to charge compensation effect, cause a part to replace Al
3+mn
4+change Mn into
2+, therefore in emmission spectrum, except observing Dy
3+characteristic peak outside, also observed Mn
4+with Mn
2+peak.Dy is singly mixed in contrast
3+sample and Dy
3+with Mn
4+the sample of mixing altogether sees, codoped makes Dy
3+transmitting increase to some extent, be mainly Dy
3+with Mn
4+between radiationless transmission ofenergy.
The white light effect (chromaticity coordinates) of the panchromatic white light material of single-component multi-wavelength in the present invention can be by adjusting kind, the Dy of alkaline-earth metal ions in matrix
3+regulate and control with the relative doping content of Mn ion, the near-ultraviolet light LED that is 385～390nm with wavelength excites, and can obtain the controlled white light of chromaticity coordinates.
With respect to prior art, tool of the present invention has the following advantages and effect:
(1) the present invention is applied to near-ultraviolet light LED, single-component, multi-wave length illuminating, between activator and coactivator, there is not cross relaxation quencher, by radiationless relaxation mode, make luminous enhancing on the contrary, when being applied to LED device, tricolor powder proportioning and compounding process have been avoided.
(2) in preparation method of the present invention, the raw materials such as urea of using produce the gases such as ammonia in combustion processes, make the dispersed enhancing of product, and ethylene glycol and citric acid form organic network, make product pattern subglobular.
(3) white light effect of the present invention can controlled fine setting in building-up process.
(4) the ultraviolet LED luminescent material that product of the present invention is synthetic in air, plant and instrument requires simply, cost of material has been developed lower than major part.
Accompanying drawing explanation
Fig. 1: (a) CaAl
12o
19the standard card data of thing phase and (b) the panchromatic white light material of single-component four wavelength (Ca for the embodiment of the present invention 1 gained LED
0.95dy
0.05) (Al
11.94mn
0.06) O
19xRD figure.
Fig. 2: the panchromatic white light material of single-component four wavelength (Ca for the embodiment of the present invention 1 gained LED
0.95dy
0.05) (Al
11.94mn
0.06) O
19exciting light spectrogram, monitoring wavelength be respectively (a) 472nm, (b) 514nm, (c) 569nm, (d) 650nm.
Fig. 3 (a) is the panchromatic white light material of the embodiment of the present invention 1 gained LED single-component four wavelength (Ca
0.95dy
0.05) (Al
11.94mn
0.06) O
19emmission spectrum under 380nm excites;
Fig. 3 (b) is the panchromatic white light material of the embodiment of the present invention 2 gained LED single-component dual wavelength (Ca
0.95dy
0.05) Al
12o
19emmission spectrum under 380nm excites.
Fig. 4 (a) is the panchromatic white light material of the embodiment of the present invention 2 gained LED single-component dual wavelength (Ca
0.95dy
0.05) Al
12o
19chromaticity coordinates figure;
Fig. 4 (b) is the panchromatic white light material of the embodiment of the present invention 1 gained LED single-component four wavelength (Ca
0.95dy
0.05) (Al
11.94mn
0.06) O
19chromaticity coordinates figure.
Fig. 5 (a) is the panchromatic white light material of the embodiment of the present invention 1 gained LED single-component four wavelength (Ca
0.95dy
0.05) (Al
11.94mn
0.06) O
19scanning electron microscope (SEM) photograph;
Fig. 5 (b) is the panchromatic white light material of the embodiment of the present invention 2 gained LED single-component dual wavelength (Ca
0.95dy
0.05) Al
12o
19scanning electron microscope (SEM) photograph.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
By nitrocalcite Ca (NO
3)
2, aluminum nitrate [Al (NO
3)
39H
2o] water-soluble, be made into the nitrate solution that concentration is 0.5mol/L, the Mn (Ac) that is 0.05mol/L by the water-soluble formation concentration of manganese acetate solid
2solution, by solid Dy
2o
3be dissolved in concentrated nitric acid and form 0.05mol/LDy (NO
3)
3solution, accurately pipettes each solution with valinche, mixes: Ca in following ratio
2+: Al
3+: Dy
3+: Mn
2+mol ratio is 0.95:11.94:0.05:0.06, makes mixing solutions.In mixing solutions, add and the isopyknic ethylene glycol of mixed solution and 2g citric acid and 2g urea, mix, form gluey settled solution, utilize combustion method calcination in the system of opening wide to brown solid, to obtain precursor.Precursor is successively respectively processed 5 hours with 1500 ℃ at 1000 ℃, and fully grind centre, obtains powder product, and after gained sintering, the total quality of powder product is 2g.As shown in Figure 1, XRD shows that product is pure CaAl
12o
19phase.Utilize Fluoromax ?4 fluorescence spectrophotometer (HORIBA Jobin Yvon Inc.), the luminescent properties of testing product at ambient temperature, this product is under the monitoring of blue light 472nm, green glow 514nm, orange light 569nm, ruddiness 650nm, and four excitation spectrums that obtain show that this product has stronger absorption (concrete visible Fig. 2) in UV-light region; In same fluorescence spectrophotometer, with the optical excitation of 380nm xenon lamp, obtain the white light (concrete visible Fig. 3 b) being formed by blue light 472nm, green glow 514nm, orange light 569nm, ruddiness 650nm tetra-wavelength; According to chromaticity diagram Formula of the blackbody radiation, calculating its corresponding chromaticity coordinates is: (x=0.31, y=0.38) (concrete visible Fig. 4 b), approaches ideal white light (x=0.32, y=0.32) (the concrete visible solid star of Fig. 4) (generally needing red, green, blue tricolor powder to mix just can obtain); Scanning electron microscope records on Nova NanoSEM200, under the effect of electron beam, amplifies 20,000 times, observes product microscopic appearance and is irregular sheet, and distribution of sizes is narrower, and diameter is about 3～5 microns, and thickness is about 500 nanometers, and (concrete visible Fig. 5 a).This product absorbs the near-ultraviolet light of 380nm left and right, produces the visible ray being comprised of four wavelength in single group of chemical composition, and its advantage is: in this system, and Mn
4+/ Mn
2+, Dy
3+simultaneously luminous, improve exciting light utilization ratio and luminous efficiency, and avoided product to join the complicated technologies such as powder and batch mixing in be coated with pipe application process.The particle of product is more even, and its particle size size and scope distribution be suitable painting pipe application also.
Embodiment 2
By nitrocalcite Ca (NO
3)
2, aluminum nitrate [Al (NO
3)
39H
2o] water-soluble, be made into the nitrate solution that concentration is 0.5mol/L, by solid Dy
2o
3be dissolved in concentrated nitric acid and form 0.05mol/LDy (NO
3)
3solution, accurately pipettes each solution with valinche, mixes: Ca in following ratio
2+: Al
3+: Dy
3+mol ratio is 0.95:12:0.05, makes mixed solution.In mixing solutions, add 10g citric acid and 5g urea, and the ethylene glycol of mixed solution two volumes, mix, form gluey settled solution, utilize combustion method in unlimited system calcination to brown solid, obtain precursor.Precursor is successively respectively processed 5 hours with 1500 ℃ at 800 ℃, and fully grind centre, obtains product.After sintering, the total quality of powder product is 2g.Utilize Fluoromax ?4 fluorescence spectrophotometer (HORIBA Jobin Yvon Inc.), the luminescent properties of testing product at ambient temperature, with the optical excitation of 380nm xenon lamp, this product is launched the dual wavelength white light being comprised of 472nm blue light and 569nm orange light, and (concrete visible Fig. 3 a); According to chromaticity diagram Formula of the blackbody radiation, calculate its corresponding chromaticity coordinates and be: (x=0.29, y=0.32) (concrete visible Fig. 4 a); Scanning electron microscope is surveyed on Nova NanoSEM200, under the effect of electron beam, amplifies 50,000 times, observes product microscopic appearance and is irregular particle shape, and size distribution is about 1～2 micron (concrete visible Fig. 5 b).
By with embodiment 1 ?2 method detect, embodiment 3 ?in 9 product luminescent properties method and embodiment 1 ?2 identical, result and embodiment 1 ?2 approach, explanation no longer one by one.
Embodiment 3
By nitrocalcite Ca (NO
3)
2, aluminum nitrate [Al (NO
3)
39H
2o] water-soluble, be made into the nitrate solution that concentration is 0.5mol/L, the Mn (Ac) that is 0.05mol/L by the water-soluble formation concentration of manganese acetate solid
2solution, by solid Dy
2o
3be dissolved in concentrated nitric acid and form 0.05mol/LDy (NO
3)
3solution, accurately pipettes each solution with valinche, mixes: Ca in following ratio
2+: Al
3+: Dy
3+: Mn
2+mol ratio is 0.99:10.88:0.01:0.12, makes mixed solution.In mixing solutions, add 5g citric acid and 10g urea, and the ethylene glycol of 1.5 times of volumes of mixed solution, mix, form gluey settled solution, utilize combustion method calcination in the system of opening wide to brown solid, to obtain precursor.Precursor is successively respectively processed 3 hours with 1400 ℃ at 900 ℃, and fully grind centre, obtains product.After sintering, the total quality of powder product is 2g.With 380nm, excite, this product is launched four wavelength white lights, and its corresponding chromaticity coordinates approaches ideal white light, and product microscopic appearance is irregular sheet.
Embodiment 4
By nitrocalcite Ca (NO
3)
2, aluminum nitrate [Al (NO
3)
39H
2o] water-soluble, be made into the nitrate solution that concentration is 0.5mol/L, the Mn (Ac) that is 0.05mol/L by the water-soluble formation concentration of manganese acetate solid
2solution, by solid Dy
2o
3be dissolved in concentrated nitric acid and form 0.05mol/LDy (NO
3)
3solution, accurately pipettes each solution with valinche, mixes: Ca in following ratio
2+: Al
3+: Dy
3+: Mn
2+mol ratio is 0.99:11.94:0.01:0.06, makes mixed solution.In mixing solutions, add 2g citric acid and 10g urea, and with the isopyknic ethylene glycol of mixed solution, mix, form gluey settled solution, utilize combustion method calcination in opening wide system to brown solid, to obtain precursor.Precursor is successively respectively processed 4 hours with 1400 ℃ at 900 ℃, and fully grind centre, obtains product.After sintering, the total quality of powder product is 2g.With 380nm, excite, this product is launched four wavelength white lights, and its corresponding chromaticity coordinates approaches ideal white light, and product microscopic appearance is irregular sheet.
Embodiment 5
By nitrocalcite Ca (NO
3)
2, nitrate of baryta Ba (NO
3)
2, aluminum nitrate [Al (NO
3)
39H
2o] water-soluble, be made into the nitrate solution that concentration is 0.5mol/L, the Mn (Ac) that is 0.05mol/L by the water-soluble formation concentration of manganese acetate solid
2solution, by solid Dy
2o
3be dissolved in concentrated nitric acid and form 0.05mol/LDy (NO
3)
3solution, accurately pipettes each solution with valinche, mixes: Ca in following ratio
2+: Ba
2+: Al
3+: Dy
3+: Mn
2+mol ratio is 0.48:0.48:11.99:0.04:0.01, makes mixed solution.In mixing solutions, add 8g citric acid and 4g urea, and with the isopyknic ethylene glycol of mixed solution, mix, form gluey settled solution, utilize combustion method calcination in opening wide system to brown solid, to obtain precursor.Precursor is successively respectively processed 5 hours with 1500 ℃ at 800 ℃, and fully grind centre, obtains product.After sintering, the total quality of powder product is 2g.With 380nm, excite, this product is launched four wavelength white lights, and its corresponding chromaticity coordinates approaches ideal white light, and product microscopic appearance is irregular particle shape, and size distribution is about 1～2 micron.
Embodiment 6
By nitrocalcite Ca (NO
3)
2, strontium nitrate Sr (NO
3)
2, aluminum nitrate [Al (NO
3)
39H
2o] water-soluble, be made into the nitrate solution that concentration is 0.5mol/L, the Mn (Ac) that is 0.05mol/L by the water-soluble formation concentration of manganese acetate solid
2solution, by solid Dy
2o
3be dissolved in concentrated nitric acid and form 0.05mol/LDy (NO
3)
3solution, accurately pipettes each solution with valinche, mixes: Ca in following ratio
2+: Sr
2+: Al
3+: Dy
3+: Mn
2+mol ratio is 0.49:0.49:11.90:0.02:0.10, makes mixed solution.In mixing solutions, add 2g citric acid and 8g urea, and the ethylene glycol of 2 times of volumes of mixed solution, mix, form gluey settled solution, utilize combustion method calcination in the system of opening wide to brown solid, to obtain precursor.Precursor is successively respectively processed 4 hours with 1350 ℃ at 1000 ℃, and fully grind centre, obtains product.After sintering, the total quality of powder product is 2g.With 380nm, excite, this product is launched four wavelength white lights, and its corresponding chromaticity coordinates approaches ideal white light, and product microscopic appearance is irregular sheet.
Embodiment 7
By strontium nitrate Sr (NO
3)
2, nitrate of baryta Ba (NO
3)
2, aluminum nitrate [Al (NO
3)
39H
2o] water-soluble, be made into the nitrate solution that concentration is 0.5mol/L, the Mn (Ac) that is 0.05mol/L by the water-soluble formation concentration of manganese acetate solid
2solution, by solid Dy
2o
3be dissolved in concentrated nitric acid and form 0.05mol/LDy (NO
3)
3solution, accurately pipettes each solution with valinche, mixes: Sr in following ratio
2+: Ba
2+: Al
3+: Dy
3+: Mn
2+mol ratio is 0.47:0.47:11.92:0.06:0.08, makes mixed solution.In mixing solutions, add 10g citric acid and 8g urea, and the ethylene glycol of 1.5 times of volumes of mixed solution, mix, form gluey settled solution, utilize combustion method calcination in the system of opening wide to brown solid, to obtain precursor.Precursor is successively respectively processed 4 hours with 1500 ℃ at 1000 ℃, and fully grind centre, obtains powder product.After sintering, the total quality of powder product is 2g.With 380nm, excite, this product is launched four wavelength white lights, and its corresponding chromaticity coordinates approaches ideal white light, and product microscopic appearance is irregular particle shape, and size distribution is about 1～2 micron, and disperses better.
Embodiment 8
By nitrocalcite Ca (NO
3)
2, strontium nitrate Sr (NO
3)
2, nitrate of baryta Ba (NO
3)
2, aluminum nitrate [Al (NO
3)
39H
2o] water-soluble, be made into the nitrate solution that concentration is 0.5mol/L, by solid Dy
2o
3be dissolved in concentrated nitric acid and form 0.05mol/LDy (NO
3)
3solution, accurately pipettes each solution with valinche, mixes: Ca in following ratio
2+: Sr
2+: Ba
2+: Al
3+: Dy
3+mol ratio is 0.36:0.30:0.30:12:0.04, makes mixed solution.In mixing solutions, add 10g citric acid and 6g urea, and the ethylene glycol of 2 times of volumes of mixed solution, mix, form gluey settled solution, utilize combustion method calcination in the system of opening wide to brown solid, to obtain precursor.Precursor is successively respectively processed 5 hours with 1500 ℃ at 900 ℃, and fully grind centre, obtains powder product.After sintering, the total quality of powder product is 2g.With 380nm, excite, this product is launched dual wavelength white light, and its corresponding chromaticity coordinates approaches ideal white light, and product microscopic appearance is irregular particle shape, and size distribution is about 1～2 micron.
Embodiment 9
By nitrocalcite Ca (NO
3)
2, aluminum nitrate [Al (NO
3)
39H
2o] water-soluble, be made into the nitrate solution that concentration is 0.5mol/L, by solid Dy
2o
3be dissolved in concentrated nitric acid and form 0.05mol/LDy (NO
3)
3solution, accurately pipettes each solution with valinche, mixes: Ca in following ratio
2+: Al
3+: Dy
3+mol ratio is 0.80:12:0.20, makes mixed solution.In mixing solutions, add 10g citric acid and 6g urea, and the ethylene glycol of 2 times of volumes of mixed solution, mix, form gluey settled solution, utilize combustion method calcination in the system of opening wide to brown solid, to obtain precursor.Precursor is successively processed 5 hours with 1500 ℃ at 900 ℃, and fully grind centre, obtains powder product.After sintering, the total quality of powder product is 2g.With 380nm, excite, this product is launched dual wavelength white light; Its corresponding chromaticity coordinates approaches ideal white light; Product microscopic appearance is irregular particle shape, and size distribution is about 1～2 micron.
Product of the present invention is in single-component fluorescent material, to launch multi-wavelength white light simultaneously, and its excitation wavelength is mated with near-ultraviolet light LED.And product of the present invention is synthetic in air, plant and instrument requires simple, and the ultraviolet LED luminescent material that cost of material has been developed lower than major part, when being applied to LED device, has avoided tricolor powder proportioning and compounding process, greatly reduces production costs.In addition, centralized particle diameter, is conducive to be coated with pipe application.
Claims (4)
1. the panchromatic white light material of used near ultraviolet LED single-component multi-wavelength, is characterized in that: this material is with alkaline earth aluminate EAl
12o
19for matrix, with Dy
3+as activator, with Mn
4+and Mn
2+for coactivator, chemical constitution is E
1 ?ial
12 ?jo
19: iDy
3+, jMn, wherein E is one or more in Ca, Sr and Ba; 0.01≤i≤0.2,0.01≤j≤0.12; Mn is Mn
4+with Mn
2+mixing; The near-ultraviolet light LED that this material is 385～390nm with wavelength excites, and obtains the controlled white light of chromaticity coordinates.
2. the preparation method of the panchromatic white light material of LED use single-component multi-wavelength described in claim 1, is characterized in that: by alkine earth metal nitrate E (NO
3)
2, aluminum nitrate, manganese acetate solution and Dy (NO
3)
3solution is mixed to get mixing solutions, wherein, counts in molar ratio E
2+: Al
3+: Dy
3+: Mn is (1 ?i): (12 ?j): i:j, wherein, 0.01≤i≤0.2,0.01≤j≤0.12; E is one or more in Ca, Sr and Ba; In mixing solutions, add citric acid, urea and ethylene glycol, mix, utilize combustion method calcination in the system of opening wide, obtain precursor, then at 800～1000 ℃, respectively process 3～5 hours respectively the panchromatic white light material of single-component multi-wavelength for the LED making with 1350～1500 ℃.
3. the preparation method of the panchromatic white light material of single-component multi-wavelength for LED according to claim 2, the volume ratio that it is characterized in that described ethylene glycol and mixing solutions is 1:(1～2).
4. the preparation method of the panchromatic white light material of single-component multi-wavelength for LED according to claim 2, is characterized in that: described citric acid and amount of urea are respectively 1 to 5 times of the panchromatic white light material of the LED use single-component multi-wavelength total mass that makes.
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