CN102559179B - Single-matrix white light fluorescent powder for white light light-emitting diode (LED) and preparation method thereof - Google Patents
Single-matrix white light fluorescent powder for white light light-emitting diode (LED) and preparation method thereof Download PDFInfo
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- CN102559179B CN102559179B CN201110457807.4A CN201110457807A CN102559179B CN 102559179 B CN102559179 B CN 102559179B CN 201110457807 A CN201110457807 A CN 201110457807A CN 102559179 B CN102559179 B CN 102559179B
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- 239000000843 powder Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 239000011159 matrix material Substances 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 48
- 239000000126 substance Substances 0.000 claims abstract description 30
- 229910052788 barium Inorganic materials 0.000 claims abstract description 7
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 125
- 239000002994 raw material Substances 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 39
- 239000000395 magnesium oxide Substances 0.000 claims description 31
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 31
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 20
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical group [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 19
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 19
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 19
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 18
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical group O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 16
- 238000007873 sieving Methods 0.000 claims description 16
- 229910000018 strontium carbonate Chemical group 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052693 Europium Inorganic materials 0.000 claims description 9
- 239000012467 final product Substances 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 150000003016 phosphoric acids Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 3
- -1 organic acid salt Chemical class 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000001228 spectrum Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 229910016285 MxNy Inorganic materials 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- 239000000047 product Substances 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 230000005284 excitation Effects 0.000 description 19
- 239000004570 mortar (masonry) Substances 0.000 description 19
- 229910052593 corundum Inorganic materials 0.000 description 18
- 239000010431 corundum Substances 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 238000013467 fragmentation Methods 0.000 description 18
- 238000006062 fragmentation reaction Methods 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- 238000005245 sintering Methods 0.000 description 18
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 16
- 230000000694 effects Effects 0.000 description 11
- 239000003610 charcoal Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 230000004907 flux Effects 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 238000009877 rendering Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241001025261 Neoraja caerulea Species 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- UFQXGXDIJMBKTC-UHFFFAOYSA-N oxostrontium Chemical compound [Sr]=O UFQXGXDIJMBKTC-UHFFFAOYSA-N 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- KQAGKTURZUKUCH-UHFFFAOYSA-L strontium oxalate Chemical compound [Sr+2].[O-]C(=O)C([O-])=O KQAGKTURZUKUCH-UHFFFAOYSA-L 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention relates to single-matrix white light fluorescent powder for a white light light-emitting diode (LED). The chemical formula is MxNy(PO4)2-z-(BO3)z: aEu<2+>, bMn<2+>; M is one or two or three of Ba, Ca or Sr; N is one or two of Mg or Zn; a, b, x, y and z are respective molar fractions; x is larger than 1.5 and less than 3; y is larger than 0.5 and less than 2; z is larger than or equal to 0 and less than 1; a is larger than 0.001 and less than 0.2; b is larger than or equal to 0 and less than 0.4; and z and b cannot be zero at the same time. The invention discloses a preparation method of the single-matrix white light fluorescent powder for a white light LED. The invention has the beneficial effects that: the product has stable performance, wide laser and emitting light spectrum range and high color developing index; the process is simple and easy to operate; pollution is avoided; and cost is low.
Description
(1) technical field
The invention belongs to rare earth luminescent material and semiconductor solid lighting field, particularly a kind of can effectively being excited by near-ultraviolet light LED chip and single substrate fluorescent powder of emitting white light and preparation method thereof.
(2) background technology
Semiconductor light-emitting-diode (light emitting diode, be called for short LED) be a kind of New Solid lighting source, there is the advantages such as volume is little, light efficiency is high, energy-conservation, the life-span long, pollution-free, can be widely used in the fields such as landscape light in city, auto lamp, LCD backlight, indoor and outdoor general lighting, be described as the 4th generation lighting source, to energy-saving and environmental protection, improve people's quality of life etc. and be all significant.The implementation of white light LEDs mainly contains chip combination type and fluor light conversion hysteria at present.Chip combination type refers to by red, green, blue three-color LED chip portfolio realizes white light.Because the phototranstormation efficiency of red-light LED is apparently higher than green light LED and blue-ray LED, must could realize colour mixture balance by complicated pilot circuit, therefore the cost of the method is higher, manufacturability is poor.Fluor light conversion hysteria refers to that, by blue-ray LED excitation fluorescent material transmitting gold-tinted, remaining blue light transmits and gold-tinted complementation mixes generation white light; Or the transmitting that utilizes the fluorescent material being coated on ultraviolet or near ultraviolet LED chip to absorb LED completely produces red, green, blue, and then is mixed to form white light.The main flow scheme of current LED solid light source is fluor light conversion of white light LED, and its key problem is to develop high-efficiency fluorescence body.But because white light is to be formed by the yellow fluorescence of fluor and the blue light of LED, the glow color of device changes with the variation of driving voltage and fluorescent coating thickness, and color reducibility is poor, and colour rendering index is low.For addressing the above problem, adopting near-ultraviolet light InGaN tube core to excite three-color phosphor to realize white light LEDs has become at present one of focus of these field research and development in the world.But at present, the three color base fluor that match with near-ultraviolet light tube core lack, and between phosphor blends, exist color to absorb and proportioning regulation and control problem, luminous efficiency and colour rendering index are a greater impact again.Panchromatic single-substrate white fluorescent powder can overcome the deficiency of mixing phosphor to a certain extent, has improved luminous efficiency and colour rendering index; Also can simplify packaging process simultaneously.Therefore the efficient single-substrate white fluorescent powder that exploitation is applicable to burst of ultraviolel, by the study hotspot that is White-light LED illumination of new generation, has wide Economic Application and is worth.
(3) summary of the invention
The present invention is directed to the three color base fluor that current shortage and near-ultraviolet light tube core match, and between phosphor blends, exist color to absorb again and the problem of proportioning regulation and control, proposed a kind ofly there is high color rendering index (CRI), be suitable for white light LEDs single-substrate white fluorescent powder that ultraviolet leds chip excites and preparation method thereof.
The technical solution used in the present invention is:
A kind of white light LEDs single-substrate white fluorescent powder, the chemical expression of described fluorescent material is:
M
xN
y(PO
4)
2-z-(BO
3)
z:aEu
2+，bMn
2+
Wherein, described M is one or more the arbitrary combination of Ba, Ca or Sr; Described N is one or both the arbitrary combination of Mg or Zn; O represents oxygen; Eu
2+and Mn
2+it is dopant ion.Described a, b, x, y, z is molar fraction separately, wherein 1.5 < x < 3,0.5 < y < 2,0≤z < 1,0.001 < a < 0.2,0≤b < 0.4 is zero when wherein z is different with b.Preferably, in described chemical expression, x+y+a+b=3.
Z is 0 o'clock, represents in described fluorescent material not containing B element.B is 0 o'clock, and Mn represents to undope in described fluorescent material
2+.
Described M is preferably the mixing of Ba and Sr arbitrary proportion, more preferably Ba and Sr mixing with mol ratio 1: 0.6～1: 1.4.
Described N is preferably Mg.
Further, the preferred white light LEDs single-substrate white fluorescent powder of the present invention, described M is the combination of Ba and Sr; Described N is Mg; Described a, b, x, y, z is molar fraction separately, wherein 1.8 < x < 2.5,0.6 < y < 1.5,0.01 < z < 0.2,0.005 < a < 0.08,0.001 < b < 0.2.
The present invention also provides the preparation method of described white light LEDs single-substrate white fluorescent powder, and described method is one of following:
(A) 0 < z < 1, while containing B element in fluorescent material, described preparation method is:
(1) with the compound of each self-contained M, N, Eu or Mn, containing the compound of B, with be raw material containing the compound of P, molar ratio according to each element in described white fluorescent material chemical expression takes corresponding described raw material, directly with pressed powder add a small amount of ethanol or acetone wetting, be mixed evenly to obtain mixture; The described compound containing M, N, Eu or Mn is for containing M, N, Eu or the each self-corresponding oxide compound of Mn, oxyhydroxide, carbonate, nitrate, phosphoric acid salt, borate or organic acid salt; Oxide compound, boric acid or borate that the described compound containing B is boracic; The described compound containing P is phosphorous oxide compound, phosphoric acid or phosphoric acid salt.
(2) mixture step (1) being obtained in 600～1500 DEG C of roastings 1～5 time (preferably 1～2 time), obtains final product of roasting in air or reducing atmosphere, and each roasting time is 1～25h; Between every double roasting, cool to room temperature carries out milled processed, and last roasting is carried out under reducing atmosphere; Described reducing atmosphere is the nitrogen mixture containing 5-10v% hydrogen, containing the nitrogen mixture of 5-10v% carbon monoxide, or the carbon monoxide atmosphere that at high temperature produces with airborne oxygen reaction of gac.
(3) broken, levigate, the size grading of final product of roasting process step (2) being obtained, and make described white light LEDs single-matrix white fluorescent powder through washing impurity-removing, oven dry; (B) z=0, while not containing B element in fluorescent material, described preparation method is:
(1) with the compound of each self-contained M, N, Eu or Mn, with be raw material containing the compound of P, molar ratio according to each element in described white fluorescent material chemical expression takes corresponding described raw material, under the existence of reaction flux, directly with pressed powder add a small amount of ethanol or acetone wetting, be mixed evenly to obtain mixture; Described reaction flux is containing the halogenide of M or contains at least one in the halogenide of N; The consumption of described reaction flux is 0.001～5wt% of the gross weight of described phosphor raw material; The described compound containing M, N, Eu or Mn is for containing M, N, Eu or the each self-corresponding oxide compound of Mn, oxyhydroxide, carbonate, nitrate, phosphoric acid salt, borate or organic acid salt; The described compound containing P is phosphorous oxide compound, phosphoric acid or phosphoric acid salt.
(2) mixture step (1) being obtained in 600～1500 DEG C of roastings 1～5 time (preferably 1～2 time), obtains final product of roasting in air or reducing atmosphere, and each roasting time is 1～25h; Between every double roasting, cool to room temperature carries out milled processed, and last roasting is carried out under reducing atmosphere; Described reducing atmosphere is the nitrogen mixture containing 5-10v% hydrogen, containing the nitrogen mixture of 5-10v% carbon monoxide, or the carbon monoxide atmosphere that at high temperature produces with airborne oxygen reaction of gac.
(3) broken, levigate, the size grading of final product of roasting process step (2) being obtained, and make described white light LEDs single-matrix white fluorescent powder through washing impurity-removing, oven dry.
Grinding of the present invention can be carried out in agate mortar or ball mill.Described grinding can add a small amount of ethanol or acetone to soak, and plays the effect of uniform dielectric, and add-on makes solid material become pasty state conventionally, and this is well known to a person skilled in the art.
Wherein the described classification method used of step (3) is selected from one or more in settling process, method of sieving or air-flow method.This is to well known to a person skilled in the art particle size grading method.
In step (3), described final product of roasting is through broken, levigate, size grading, be to adopt after hand-crushed to make the particle size of sintered compact levigate with ball milling method again, through settling process, method of sieving or the classification of air-flow method, get granularity and be the pressed powder of 3～10 microns.
In the inventive method, described washing impurity-removing, dry and can use one or more in acid, alkali, alcohol or water to wash successively, then get solid phase in 100～115 DEG C of oven dry.
The preparation method of single-substrate white fluorescent powder for white light LEDs of the present invention, is preferably barium carbonate and Strontium carbonate powder, is preferably magnesium oxide (MgO), is preferably europiumsesquioxide, is preferably manganous carbonate containing the compound of Mn containing the compound of Eu containing the compound of N containing the compound of M in described raw material.Preferably the described compound containing B is boric acid.Preferably the described compound containing P is Secondary ammonium phosphate.
In described method (A), while having the compound containing B, do not add reaction flux when grinding in raw material, this is because can play the effect of fusing assistant containing the compound of B, and the existence of B and Mn can effectively improve the colour rendering index of fluorescent material.
In described method (B), owing to not containing the compound of B in raw material, when grinding, need to add a small amount of reaction flux.In described method (B), described reaction flux is containing the halogenide of M or contains at least one in the halogenide of N, the mole number of the M wherein containing or N element is also not counted in fluorescent material expression formula because reaction flux can after washing impurity-removing in remove through pickling or alkali cleaning.
The invention has the beneficial effects as follows: adopt the chemical constitution of fluorescent material prepared by method of the present invention to determine the non-constant width of its excitation spectrum, within the scope of 250～430nm, there is strong absorption, be suitable for ultraviolet leds chip and excite.The emmission spectrum of fluorescent material of the present invention has covered the whole visible region from 390nm to 750nm, is a kind of new phosphors that has high color rendering index (CRI), is very suitable for white light LEDs.This fluorescent material has stable performance simultaneously, luminous efficiency advantages of higher.And preparation method's technique is simple, easy handling, pollution-free, cost is low.
(4) brief description of the drawings
Fig. 1 is excitation spectrum and the emmission spectrum of the fluorescent material that makes of embodiment 1, and dotted portion is excitation spectrum, and solid line part is emmission spectrum; X-coordinate represents wavelength (nm), and ordinate zou represents relative intensity (A.U.).
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1: chemical formula is Ba
0.87sr
1.09mg
0.9(PO
4)
1.94-(BO
3)
0.06: 0.04Eu
2+, 0.10Mn
2+the preparation of fluorescent material.
Preparation method is as follows:
Take respectively 0.8584g barium carbonate (BaCO
3), 0.8046g Strontium carbonate powder (SrCO
3), 0.1814g magnesium oxide (MgO), 1.2810g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0185g boric acid (H
3bO
3), 0.0352g europiumsesquioxide (Eu
2o
3), 0.0575g manganous carbonate (MnCO
3), above raw material is analytical pure.Above-mentioned raw materials mixture, in agate mortar, is added to 2mL acetone and grinds, grind and evenly obtain mixture later, pack in corundum crucible, first with 800 DEG C of roastings 8 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then taking containing the nitrogen mixture of 5-10% hydrogen as, at 1100 DEG C of temperature, sintering 20 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate with ball milling, and method of sieving obtains granularity at the pressed powder of 3～10 microns.Then use successively sodium hydroxide solution (30ml), deionized water (30ml) and the each washed twice of methyl alcohol (20ml) of 1M, finally filter to isolate fluorescent material, in the baking oven of 110 DEG C, dry and within 20 hours, obtain fluorescent material product.The emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 2: chemical formula is Ba
0.67sr
1.29mg
0.95(PO
4)
1.8-(BO
3)
0.2: 0.04Eu
2+, 0.05Mn
2+the preparation of fluorescent material.
Preparation method is as follows:
Take respectively 0.6611g barium carbonate (BaCO
3), 0.9522g Strontium carbonate powder (SrCO
3), 0.1914g magnesium oxide (MgO), 1.1885g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0618g boric acid (H
3bO
3), 0.0352g europiumsesquioxide (Eu
2o
3), 0.0287g manganous carbonate (MnCO
3), above raw material is analytical pure.Above-mentioned raw materials mixture, in agate mortar, is added to 2mL ethanol and grinds, after grinding evenly, pack in corundum crucible, first with 800 DEG C of roastings 5 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then using activity charcoal powder as the condition that produces reducing atmosphere, at 1200 DEG C of temperature, sintering 5 hours, is cooled to room temperature.The sintered products obtaining is for the second time after fragmentation, levigate through ball milling, obtains granularity at the fluorescent material of 3～10 microns after method of sieving.Then use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 110 DEG C, dry and within 20 hours, obtain fluorescent material product.The emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 3: chemical formula is Ba
0.995srMg
0.99(PO
4)
1.94-(BO
3)
0.06: 0.005Euw, 0.01Mn
2+the preparation of fluorescent material.
Preparation method is as follows:
Take respectively 0.9818g barium carbonate (BaCO
3), 0.7382g Strontium carbonate powder (SrCO
3), 0.1995g magnesium oxide (MgO), 1.2810g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0185g boric acid (H
3bO
3), 0.0044g europiumsesquioxide (Eu
2o
3), 0.0057g manganous carbonate (MnCO
3), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 800 DEG C of roastings 4 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then taking the nitrogen mixture containing 5-10v% carbon monoxide as reducing atmosphere, at 1200 DEG C of temperature, sintering 10 hours, is cooled to room temperature.The sintered products obtaining is for the second time after fragmentation, levigate through ball milling, after method of sieving, obtain granularity at the fluorescent material of 3～10 microns, use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 110 DEG C, dry and within 20 hours, obtain fluorescent material product.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 4: chemical formula is Ba
0.87sr
1.09mg
0.9(PO
4)
2: 0.04Eu
2+, 0.10Mn
2+the preparation of fluorescent material.
Preparation method is as follows:
Take respectively 1.1893g barium acetate ((CH
3cOO)
2baH
2o), 0.8046g Strontium carbonate powder (SrCO
3), 0.1814g magnesium oxide (MgO), 1.3206g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0359g barium fluoride (BaF
2), 0.0352g europiumsesquioxide (Eu
2o
3), 0.0575g manganous carbonate (MnCO
3), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 800 DEG C of roastings 8 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then taking the nitrogen mixture containing 5-10% hydrogen as reducing atmosphere, at 1100 DEG C of temperature, sintering 20 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate through ball milling, and air-flow method obtains granularity at the fluorescent material of 3～10 microns.Then use successively 1M hydrochloric acid soln (30ml), deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, dries and within 24 hours, obtain fluorescent material product in the baking oven of 105 DEG C.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 5: chemical formula is Ba
0.77sr
1.19mg (PO
4)
1.9-(BO
3)
0.1: 0.04Eu
2+the preparation of fluorescent material
Preparation method is as follows:
Take respectively 0.7598g barium carbonate (BaCO
3), 0.8784g Strontium carbonate powder (SrCO
3), 0.2015g magnesium oxide (MgO), 1.2546g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0309g boric acid (H
3bO
3), 0.0352g europiumsesquioxide (Eu
2o
3), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 800 DEG C of roastings 5 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then using activity charcoal powder as the condition that produces reducing atmosphere, at 1400 DEG C of temperature, sintering 5 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate through ball milling, and settling process obtains granularity at the fluorescent material of 3～10 microns.Then use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 110 DEG C, dry and within 20 hours, obtain fluorescent material product.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 6: chemical formula is Ba
0.85sr
1.1mg
0.88(PO
4)
1.94-(BO
3)
0.06: 0.05Eu
2+, 0.12Mn
2+the preparation of fluorescent material
Preparation method is as follows:
Take respectively 0.8387g barium carbonate (BaCO
3), 0.8120g Strontium carbonate powder (SrCO
3), 0.1773g magnesium oxide (MgO), 1.2810g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0185g boric acid (H
3bO
3), 0.0440g europiumsesquioxide (Eu
2o
3), 0.0690g manganous carbonate (MnCO
3), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 900 DEG C of roastings 5 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then using activity charcoal powder as the condition that produces reducing atmosphere, at 1200 DEG C of temperature, sintering 8 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate through ball milling, and method of sieving obtains granularity at the fluorescent material of 3～10 microns.Then use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 110 DEG C, dry and within 20 hours, obtain fluorescent material product.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 7: chemical formula is Ba
0.86ca
1.05mg
0.9(PO
4)
1.8-(BO
3)
0.2: 0.04Eu
2+, 0.15Mn
2+the preparation preparation method of fluorescent material is as follows:
Take respectively 0.8486g barium carbonate (BaCO
3), 0.5255g calcium carbonate (CaCO
3), 0.1814g magnesium oxide (MgO), 1.1885g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0618g boric acid (H
3bO
3), 0.0352g europiumsesquioxide (Eu
2o
3), 0.0862g manganous carbonate (MnCO
3), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 700 DEG C of roastings 10 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then using activity charcoal powder as the condition that produces reducing atmosphere, at 1100 DEG C of temperature, sintering 25 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate through ball milling, and method of sieving obtains granularity at the fluorescent material of 3～10 microns.Then use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 110 DEG C, dry and within 20 hours, obtain fluorescent material product.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 8: chemical formula is Ca
0.7sr
1.2mg
0.82(PO
4)
1.8-(BO
3)
0.2: 0.08Eu
2+, 0.2Mn
2+the preparation preparation method of fluorescent material is as follows:
Take respectively 0.3503g calcium carbonate (CaCO
3), 0.8858g Strontium carbonate powder (SrCO
3), 0.1652g magnesium oxide (MgO), 1.1885g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0618g boric acid (H
3bO
3), 0.0704g europiumsesquioxide (Eu
2o
3), 0.1150g manganous carbonate (MnCO
3), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 800 DEG C of roastings 5 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then using activity charcoal powder as the condition that produces reducing atmosphere, at 1200 DEG C of temperature, sintering 5 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate through ball milling, and settling process obtains granularity at the fluorescent material of 3～10 microns.Then use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 110 DEG C, dry and within 20 hours, obtain fluorescent material product.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 9: chemical formula is Ba
0.85sr
1.1zn
0.88(PO
4)
1.9-(BO
3)
0.1: 0.05Eu
2+, 0.12Mn
2+the preparation of fluorescent material.
Take respectively 0.8387g barium carbonate (BaCO
3), 0.8120g Strontium carbonate powder (SrCO
3), 0.3581g zinc oxide (ZnO), 1.2546g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0309g boric acid (H
3bO
3), 0.0440g europiumsesquioxide (Eu
2o
3), 0.0690g manganous carbonate (MnCO
3), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 800 DEG C of roastings 5 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then using activity charcoal powder as the condition that produces reducing atmosphere, at 1200 DEG C of temperature, sintering 5 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate through ball milling, and air-flow method obtains granularity at the fluorescent material of 3～10 microns.Then use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 110 DEG C, dry and within 20 hours, obtain fluorescent material product.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 10: chemical formula is Ba
1.3ca
0.62zn
0.92(PO
4)
1.95-(BO
3)
0.05: 0.04Eu
2+, 0.12Mn
2+the preparation preparation method of fluorescent material is as follows:
Take respectively 1.2827g barium carbonate (BaCO
3), 0.3103g calcium carbonate (CaCO
3), 0.3743g zinc oxide (ZnO), 1.2876g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0155g boric acid (H
3bO
3), 0.0352g europiumsesquioxide (Eu
2o
3), 0.0690g manganous carbonate (MnCO
3), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 800 DEG C of roastings 5 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then using activity charcoal powder as the condition that produces reducing atmosphere, at 1200 DEG C of temperature, sintering 10 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate through ball milling, and method of sieving obtains granularity at the fluorescent material of 3～10 microns.Then use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 110 DEG C, dry and within 20 hours, obtain fluorescent material.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 11: chemical formula is Ba
0.88sr
0.62ca
0.45mg
0.91(PO
4)
1.85-(BO
3)
0.15: 0.04Eu
2+, 0.10Mn
2+the preparation preparation method of fluorescent material is as follows:
Take respectively 0.8683g barium carbonate (BaCO
3), 0.4577g Strontium carbonate powder (SrCO
3), 0.2882g caoxalate (CaC
2o
4), 0.1834g magnesium oxide (MgO), 1.2216g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0464g boric acid (H
3bO
3), 0.0352g europiumsesquioxide (Eu
2o
3), 0.0575g manganous carbonate (MnCO
3), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 800 DEG C of roastings 5 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then using activity charcoal powder as the condition that produces reducing atmosphere, at 1300 DEG C of temperature, sintering 5 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate through ball milling, and method of sieving obtains granularity at the fluorescent material of 3～10 microns.Then use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 110 DEG C, dry and within 20 hours, obtain fluorescent material.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 12: chemical formula is Ba
0.72sr
1.2mg
0.4zn
0.5(PO
4)
1.94-(BO
3)
0.06: 0.08Eu
2+, 0.10Mn
2+the preparation preparation method of fluorescent material is as follows:
Take respectively 0.7104g barium carbonate (BaCO
3), 0.8858g Strontium carbonate powder (SrCO
3), 0.0806g magnesium oxide (MgO), 0.2035g zinc oxide (ZnO), 1.2810g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0185g boric acid (H
3bO
3), 0.0704g europiumsesquioxide (Eu
2o
3), 0.0575g manganous carbonate (MnCO
3), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 800 DEG C of roastings 5 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then using activity charcoal powder as the condition that produces reducing atmosphere, at 1200 DEG C of temperature, sintering 5 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate through ball milling, and method of sieving obtains granularity at the fluorescent material of 3～10 microns.Then use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 110 DEG C, dry and within 20 hours, obtain fluorescent material.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 13: chemical formula is Ba
0.87sr
1.09mg
0.9(PO
4)
1.94-(BO
3)
0.06: 0.04Eu
2+, 0.10Mn
2+the preparation of fluorescent material.
Preparation method is as follows:
Take respectively 0.8584g barium carbonate (BaCO
3), 0.8046g strontium oxalate (SrC
2o
4), 0.1814g magnesium oxide (MgO), 1.2810g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0185g boric acid (H
3bO
3), 0.0352g europiumsesquioxide (Eu
2o
3), 0.0575g manganous carbonate (MnCO
3), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 800 DEG C of roastings 8 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then taking the nitrogen mixture containing 5-10% hydrogen as reducing atmosphere, at 1100 DEG C of temperature, sintering 20 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate through ball milling, and method of sieving obtains granularity at the fluorescent material of 3～10 microns.Then use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 110 DEG C, dry and within 20 hours, obtain fluorescent material.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 14: chemical formula is Ba
0.975r
0.99mg
0.9(PO
4)
1.94-(BO
3)
0.06: 0.04Eu
2+, 0.10Mn
2+the preparation of fluorescent material.
Preparation method is as follows:
Take respectively 0.9571g barium carbonate (BaCO
3), 0.7308g Strontium carbonate powder (SrCO
3), 1.1542g magnesium nitrate (MgN
2o
6.6H
2o), 1.2810g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0185g boric acid (H
3bO
3), 0.0352g europiumsesquioxide (Eu
2o
3), 0.0575g manganous carbonate (MnCO
3), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 800 DEG C of roastings 8 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then taking the nitrogen mixture containing 5-10v% hydrogen as reducing atmosphere, at 1050 DEG C of temperature, sintering 24 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate through ball milling, and settling process obtains granularity at the fluorescent material of 3～10 microns.Then use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 105 DEG C, dry and within 20 hours, obtain fluorescent material product.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 15: chemical formula is Ba
0.98sr
0.98mg
0.9(PO
4)
1.94-(BO
3)
0.06: 0.04Eu
2+, 0.10Mn
2+the preparation of fluorescent material.
Preparation method is as follows:
Take respectively 0.9669g barium carbonate (BaCO
3), 0.5078g strontium oxide (SrO), 0.1814g magnesium oxide (MgO), 1.2810g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0185g boric acid (H
3bO
3), 0.0352g europiumsesquioxide (Eu
2o
3), 0.0575g manganous carbonate (MnCO
3), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 800 DEG C of roastings 8 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then taking the nitrogen mixture containing 5-10% hydrogen as reducing atmosphere, at 1300 DEG C of temperature, sintering 20 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate through ball milling, and air-flow method obtains granularity at the fluorescent material of 3～10 microns.Then use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 115 DEG C, dry and within 20 hours, obtain fluorescent material product.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 16: chemical formula is Ba
0.87sr
1.09mg
0.9(PO
4)
1.9-(BO
3)
0.1: 0.04Eu
2+, 0.10Mn
2+the preparation of fluorescent material.
Preparation method is as follows:
Take respectively 0.8584g barium carbonate (BaCO
3), 0.8046g Strontium carbonate powder (SrCO
3), 0.2625g magnesium hydroxide (Mg (OH)
2), 1.2546g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0309g boric acid (H
3bO
3), 0.0352g europiumsesquioxide (Eu
2o
3), 0.0575g manganous carbonate (MnCO
3), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 800 DEG C of roastings 8 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then taking the nitrogen mixture containing 5-10% hydrogen as reducing atmosphere, at 1050 DEG C of temperature, sintering 20 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate through ball milling, and method of sieving obtains granularity at the fluorescent material of 3～10 microns.Then use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 115 DEG C, dry and within 20 hours, obtain fluorescent material product.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 17: chemical formula is Ba
0.87sr
1.09mg
0.4zn
0.5(PO
4)
1.9-(BO
3)
0.1: 0.04Eu
2+, 0.10Mn
2+the preparation of fluorescent material.
Preparation method is as follows:
Take respectively 0.6670g barium oxide (BaO), 0.8046g Strontium carbonate powder (SrCO
3), 0.0806g magnesium oxide (MgO), 0.2035g zinc oxide (ZnO), 1.2546g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0309g boric acid (H
3bO
3), 0.0575g manganous carbonate (MnCO
3), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 800 DEG C of roastings 8 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then taking the nitrogen mixture containing 5-10% hydrogen as reducing atmosphere, at 1100 DEG C of temperature, sintering 20 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate through ball milling, and method of sieving obtains granularity at the fluorescent material of 3～10 microns.Then use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 110 DEG C, dry and within 20 hours, obtain fluorescent material product.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Embodiment 18: chemical formula is Ba
0.87sr
1.09mg
0.9(PO
4)
1.94-(BO
3)
0.06: 0.04Eu
2+, 0.10Mn
2+the preparation of fluorescent material.
Preparation method is as follows:
Take respectively 0.8584g barium carbonate (BaCO
3), 0.8046g Strontium carbonate powder (SrCO
3), 0.1814g magnesium oxide (MgO), 1.2810g Secondary ammonium phosphate [(NH
4)
2hPO
4], 0.0185g boric acid (H
3bO
3), 0.0352g europiumsesquioxide (Eu
2o
3), 0.0435g Manganse Dioxide (MnO
2), above raw material is analytical pure.After above-mentioned raw materials mixture being ground in agate mortar evenly, pack in corundum crucible, first with 800 DEG C of roastings 8 hours, be cooled to room temperature with High Temperature Furnaces Heating Apparatus, taking-up grinds; Then taking the nitrogen mixture containing 5-10% hydrogen as reducing atmosphere, at 1100 DEG C of temperature, sintering 20 hours, is cooled to room temperature.The sintered products obtaining is for the second time through fragmentation, levigate through ball milling, and method of sieving obtains granularity at the fluorescent material of 3～10 microns.Then use successively deionized water (30ml) and the each washed twice of methyl alcohol (20ml), finally filter to isolate fluorescent material, in the baking oven of 110 DEG C, dry and within 20 hours, obtain fluorescent material product.The main emission peak of this fluorescent material between 750nm, is the white light that has covered whole visible-range at 390nm.This fluorescent material can be by the ultraviolet excitation from 250nm to 430nm, is suitable for the new phosphors of the white light LEDs application that ultraviolet leds chip excites.
Claims (8)
1. a white light LEDs single-substrate white fluorescent powder, is characterized in that the chemical expression of described fluorescent material is:
M
xN
y(PO
4)
2-z-(BO
3)
z:aEu
2+,bMn
2+
Wherein, described M be Ba and Sr with amount of substance than the mixing of 1:0.6～1:1.4; Described N is Mg; O represents oxygen; Described a, b, x, y, z is molar fraction separately, wherein 1.8 < x < 2.5,0.6 < y < 1.5,0.01 < z < 0.2,0.005 < a < 0.08,0.001 < b < 0.2.
2. white light LEDs single-substrate white fluorescent powder as claimed in claim 1, is characterized in that in described chemical expression x+y+a+b=3.
3. the preparation method of single-substrate white fluorescent powder for white light LEDs as claimed in claim 1, is characterized in that the chemical expression of described white light LEDs single-substrate white fluorescent powder is:
M
xN
y(PO
4)
2-z-(BO
3)
z:aEu
2+,bMn
2+
Wherein, described M be Ba and Sr with amount of substance than the mixing of 1:0.6～1:1.4; Described N is Mg; O represents oxygen; Described a, b, x, y, z is molar fraction separately, wherein 1.8 < x < 2.5,0.6 < y < 1.5,0.01 < z < 0.2,0.005 < a < 0.08,0.001 < b < 0.2
Described white light LEDs is prepared by the following method with single-substrate white fluorescent powder:
(1) with the compound of each self-contained M, N, Eu or Mn, containing the compound of B, with be raw material containing the compound of P, molar ratio according to each element in described white fluorescent material chemical expression takes corresponding described raw material, directly with pressed powder add a small amount of ethanol or acetone wetting, be mixed evenly to obtain mixture; The described compound containing M, N, Eu or Mn is for containing M, N, Eu or the each self-corresponding oxide compound of Mn, oxyhydroxide, carbonate, nitrate, phosphoric acid salt, borate or organic acid salt; Oxide compound, boric acid or borate that the described compound containing B is boracic; The described compound containing P is phosphorous oxide compound, phosphoric acid or phosphoric acid salt;
(2) mixture step (1) being obtained in 600～1500 DEG C of roastings 1～5 time, obtains final product of roasting in air or reducing atmosphere, and each roasting time is 1～25h; Between every double roasting, cool to room temperature carries out milled processed, and last roasting is carried out under reducing atmosphere; Described reducing atmosphere is the nitrogen mixture containing 5-10v% hydrogen, containing the nitrogen mixture of 5-10v% carbon monoxide, or the carbon monoxide atmosphere that at high temperature produces with airborne oxygen reaction of gac;
(3) broken, levigate, the size grading of final product of roasting process step (2) being obtained, and make described white light LEDs single-matrix white fluorescent powder through washing impurity-removing, oven dry.
4. the preparation method of single-substrate white fluorescent powder for white light LEDs as claimed in claim 3, is characterized in that in step (3), and the method for described size grading is one or more in settling process, method of sieving or air-flow method.
5. the preparation method of single-substrate white fluorescent powder for white light LEDs as claimed in claim 3, it is characterized in that in step (3), described final product of roasting is through broken, levigate, size grading, to make the particle size of sintered compact levigate with ball milling method again after adopting hand-crushed, through settling process, method of sieving or the classification of air-flow method, get granularity and be the pressed powder of 3～10 microns.
6. the preparation method of single-substrate white fluorescent powder for white light LEDs as claimed in claim 3, is characterized in that the described compound containing M is barium carbonate and Strontium carbonate powder, is magnesium oxide, is europiumsesquioxide, is manganous carbonate containing the compound of Mn containing the compound of Eu containing the compound of N.
7. the preparation method of single-substrate white fluorescent powder for white light LEDs as claimed in claim 3, is characterized in that the described compound containing B is boric acid, and the compound of P is Secondary ammonium phosphate.
8. the preparation method of single-substrate white fluorescent powder for white light LEDs as claimed in claim 3, it is characterized in that described washing impurity-removing, dry to be to use one or more in acid, alkali, alcohol or water to wash successively, then get solid phase in 100～115 DEG C of oven dry.
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| CN104804738B (en) * | 2015-05-18 | 2021-01-12 | 厦门砺德光电高科技股份有限公司 | Near ultraviolet excited white light LED fluorescent powder and preparation method thereof |
| CN105176529A (en) * | 2015-09-19 | 2015-12-23 | 青岛科技大学 | Europium-manganese coactivated phosphate white light fluorescent powder and preparation method thereof |
| CN105542769A (en) * | 2015-12-11 | 2016-05-04 | 青岛科技大学 | Green phosphor for white LED and preparation method thereof |
| CN106085429A (en) * | 2016-07-11 | 2016-11-09 | 河北大学 | Wide range LED fluorescent powder of a series of Color tunable and preparation method thereof |
| CN106753363B (en) * | 2016-11-29 | 2019-05-07 | 河北大学 | A kind of fluorescent powder and preparation method thereof for warm white LED |
| CN110510871B (en) * | 2019-08-30 | 2020-10-16 | 华南农业大学 | Red and blue light double-emission glass ceramic light conversion device, preparation method and gardening illuminating lamp |
| CN112852415B (en) * | 2021-01-11 | 2023-04-07 | 江苏师范大学 | High-color-purity and high-stability light-emitting green fluorescent powder and preparation method thereof |
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