CN106010528A - Bismuth-manganese-doped blue fluorescent powder and preparation method and application thereof - Google Patents
Bismuth-manganese-doped blue fluorescent powder and preparation method and application thereof Download PDFInfo
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- CN106010528A CN106010528A CN201610437880.8A CN201610437880A CN106010528A CN 106010528 A CN106010528 A CN 106010528A CN 201610437880 A CN201610437880 A CN 201610437880A CN 106010528 A CN106010528 A CN 106010528A
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- 239000000843 powder Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 75
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 29
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 28
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000011572 manganese Substances 0.000 claims description 75
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 68
- 239000000654 additive Substances 0.000 claims description 44
- 230000000996 additive effect Effects 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 36
- 239000012153 distilled water Substances 0.000 claims description 33
- 229910052748 manganese Inorganic materials 0.000 claims description 33
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000000084 colloidal system Substances 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 17
- 229910002651 NO3 Inorganic materials 0.000 claims description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- 239000012141 concentrate Substances 0.000 claims description 2
- 230000005284 excitation Effects 0.000 abstract description 13
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005286 illumination Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 22
- 229910001437 manganese ion Inorganic materials 0.000 description 21
- 239000007788 liquid Substances 0.000 description 18
- 229910001451 bismuth ion Inorganic materials 0.000 description 16
- 229910052593 corundum Inorganic materials 0.000 description 10
- 150000001621 bismuth Chemical class 0.000 description 9
- 239000010431 corundum Substances 0.000 description 9
- 125000005587 carbonate group Chemical group 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 7
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- -1 inorganic acid salt Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical group Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical group [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7708—Vanadates; Chromates; Molybdates; Tungstates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- 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
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- Manufacturing & Machinery (AREA)
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- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses bismuth-manganese-doped blue fluorescent powder and a preparation method and application thereof. The general formula of the bismuth-manganese-doped blue fluorescent powder is BixMnyY(6-x-y)WO12, wherein 0.005<=x<=0.05, and 0.001<=y<=0.01. According to the bismuth-manganese-doped blue fluorescent powder, yttrium tungstate is taken as a base body, the manganese element and the bismuth element are doped, and the obtained blue fluorescent powder is high in purity and good in color purity, particle consistency and thermal stability; the excitation wave length is increased and can be increased to 369 nm, and meanwhile the illumination intensity is effectively improved, so that the energy utilization rate is greatly increased; the preparation process is simple and easy to operate, the calcination temperature is low, the conditions are mild and easy to control, the prepared sample is high in purity and yield, no precipitant needs to be added, the cost is low, and the blue fluorescent powder is suitable for scale production. The bismuth-manganese-doped blue fluorescent powder can be applied to a light-emitting material for white LED lights.
Description
Technical field
The present invention relates to blue colour fluorescent powder of a kind of bismuth, additive Mn and its preparation method and application, particularly belong to luminescent material technology
Field.
Background technology
White light LEDs is as a kind of novel all solid state lighting source, and owing to it has numerous advantages, wide application prospect is with latent
Market, be considered the green illumination light source of 21 century.White light is to be mixed by polychromatic light, in order to obtain efficient, Gao Xian
Colour index and the white light of different-colour, according to luminescence and photoptometry principle, available three primary colours or the combination of multiple bases light.But
In the technology of glow color, in resting on, long wavelength's (green, HONGGUANG), owing to lacking the blue light of short wavelength the most always so that
LED still seems that in overall application some is not enough.Therefore, the white light research and development of LED blue-fluorescence powder body, for photic
Illumination field has huge market prospect and using value.
At present, research worker both domestic and external mainly based on metal or the inorganic acid salt of alkaline-earth metal, as phosphate, borate,
Silicate, aluminate, vanadate, molybdate, tungstates etc., expand a series of research.The most business-like can be by near purple
The blue colour fluorescent powder that outer LED effectively excites mainly has two classes:
①Eu2+Activate, Eu2++Mn2+Coactivated BaMgAl10O17And BaMg2Al16O27Aluminate；Wherein BaMg2Al16O27Matrix
It is hexagonal aluminate BaMgAl10O17、Al2O3And spinel structure MgAl2O4Mixture, actual luminous host is still that six
Aluminate BaMgAl10O17；
2. there is (Sr, Ba, Ca, the Mg) of apatite structure5(PO4)3Cl:Eu2+The halogen-phosphate of system.They are conventional fluorescent
With blue colour fluorescent powder, can effectively be excited by the UV light of 200～400nm scopes, therefore have people that they have been extended near ultraviolet and send out
Optical diode (NUV-LED) field.Although the commercialization of these fluorescent material, but yet suffer from poor heat stability, near ultraviolet
, the most easily there is luminosity decline, the degradation phenomena of color coordinate drift in the shortcomings such as launching efficiency is the highest.Also deposit
Relatively low at capacity usage ratio, luminous intensity is relatively low, and material is difficult to the problems such as preparation.Therefore, research one has capacity usage ratio
Height, luminous intensity is high, the blue colour fluorescent powder of the characteristics such as material easily preparation, it appears particularly necessary.
Summary of the invention
For solving the deficiencies in the prior art, it is an object of the invention to provide a kind of bismuth, the blue colour fluorescent powder of additive Mn and preparation thereof
Methods and applications, this blue colour fluorescent powder capacity usage ratio is high, and preparation method is simple, can be applicable in white light LEDs luminescent material.
In order to realize above-mentioned target, the present invention adopts the following technical scheme that:
A kind of bismuth, the blue colour fluorescent powder of additive Mn, its formula is: BixMnyY6-x-yWO12, wherein, 0.005≤x≤0.05,
0.001≤y≤0.01.Preferably, the chemical formula of aforementioned blue fluorescent material is: Bi0.01Mn0.005Y5.985WO12。
A kind of bismuth, the preparation method of blue colour fluorescent powder of additive Mn, comprise the following steps:
(1) weighing ammonium tungstate according to mol ratio in formula, be dissolved in distilled water, be subsequently added hydrogen peroxide, stirring obtains solution
A；
(2) weigh the soluble-salt of yttrium, the soluble-salt of manganese and the soluble-salt of bismuth according to mol ratio in formula, be dissolved in solution
In A, stirring obtains solution B；
(3) solution B heated and stirred is concentrated, be subsequently dried and obtain class colloid C；
(4) class colloid C is calcined, obtain blue colour fluorescent powder.
Aforementioned bismuth, the preparation method of blue colour fluorescent powder of additive Mn, specifically include following steps:
(1) weighing ammonium tungstate according to mol ratio in formula, be dissolved in distilled water, be subsequently added hydrogen peroxide, stirring obtains solution
A；Add hydrogen peroxide and contribute to material dissolution；
(2) weigh the soluble-salt of yttrium, the soluble-salt of manganese and the soluble-salt of bismuth according to mol ratio in formula, be dissolved in solution
In A, stirring obtains solution B；
(3) by solution B heated and stirred 3～concentrate for 6 hours under the conditions of 50 DEG C～90 DEG C, it is subsequently dried and obtains class colloid
C；
(4) class colloid C is placed in corundum crucible, puts in Muffle furnace and carry out calcining 3～6 under the conditions of 900 DEG C～1200 DEG C
Hour, obtain blue colour fluorescent powder.
Aforementioned bismuth, the preparation method of blue colour fluorescent powder of additive Mn, in step (1), the consumption of distilled water is: according to mol ratio,
Ammonium tungstate distilled water=1 20～40；The consumption of hydrogen peroxide is: according to mol ratio, ammonium tungstate hydrogen peroxide=1 1.
Aforementioned bismuth, the preparation method of blue colour fluorescent powder of additive Mn, in step (2), the soluble-salt of yttrium is nitrate, carbonic acid
One or more in salt, acetate.
Aforementioned bismuth, the preparation method of blue colour fluorescent powder of additive Mn, in step (2), the soluble-salt of manganese and the soluble-salt of bismuth
For one or more in nitrate, carbonate, acetate.
Aforementioned bismuth, the preparation method of blue colour fluorescent powder of additive Mn, in step (3), being dried is under the conditions of 50 DEG C～90 DEG C
It is dried 8～12 hours.
Aforementioned bismuth, the preparation method of blue colour fluorescent powder of additive Mn, in step (3), stirring uses magnetic agitation or mechanical agitation.
A kind of bismuth, the blue colour fluorescent powder application in white light LEDs luminescent material of additive Mn.
Pure Yttrium Tungstate is adulterated with identical manganese element doping ratio, different bismuth element by the present invention by DX2500 type X-ray diffractometer
The sample of ratio is tested.Scanning speed is 0.08 °/min, and 2 θ scopes are 15～85 °, test result such as Fig. 1 institute
Show.Pure Yttrium Tungstate powder body is rhombic system, and space group is R-3 [148], and pure Yttrium Tungstate sample cell parameter is: As shown in Figure 1, after doping with rare-earth ions, powder body still keeps original configuration, does not substantially have
There is impurity phase.
Fig. 2 is described manganese ion doping amount when being 0.5%, and bismuth ion doping is the scanning electron microscope (SEM) photograph of fluorescent powder when 1%.Its
In, manganese ion doping amount is 0.5%, bismuth ion doping is manganese ion, bismuth ion in 1% general formula compound referring to finally give
Molar content be respectively 0.5%, 1%.It can be seen that the granule of fluorescent powder of the present invention is uniform, particle identity is good.
During independent doped with manganese ion (manganese ion doping amount is 0.5%), gained powder body is tested under the conditions of monitoring wavelength 420nm and is excited
Spectrum is as it is shown on figure 3, its main excitation peak is 247nm.During independent doped with manganese ion (manganese ion doping amount is 0.5%)
As shown in Figure 4, its main emission peak, at 420nm, belongs to one to powder body test emission spectrum under 247nm shooting condition
Plant blue light.Powder body during bismuth ion (bismuth ion doping is 1%) of individually adulterating is tested under the conditions of monitoring wavelength 492nm and is excited
Spectrum is as it is shown in figure 5, its main excitation peak is 332nm.
The blue colour fluorescent powder of the present invention uses tetravalent manganese ion, independent doped with manganese ion, exist two excitation peaks (247nm and
At 369nm), wherein, at 247nm, excitation peak energy loss should not use the most greatly, and at 369nm, excitation peak peak value is the lowest, causes
Blue light is more weak.Individually adulterate bismuth ion, then the light sent is the green glow that energy is the strongest.Therefore, simultaneously doped with manganese ion and bismuth from
Son, can be greatly increased the Mn emission peak intensity in blue light region, and energy loss declines to a great extent, and the blue light sent is extremely strong, hence it is evident that carry
Excitation peak at high usage, and sensitization 369nm.
With 420nm for monitoring wavelength, manganese ion doping amount is 0.5%, the exciting light of a series of powder body of different bismuth ion dopings
Spectrum display is in figure 6.When manganese ion doping amount is 0.5%, the doping of different bismuth ions has certain shadow to fluorescence intensity level
Ring, when the doping of bismuth ion is 1%, there is optimal fluorescence intensity level.Demonstrate and between dopant ion, there occurs that energy passes
Pass, make the excitation wave wavelength of manganese ion brought up to 369nm by 247nm, make capacity usage ratio higher.
As shown in Fig. 7～Fig. 9.The bismuth of the present invention, additive Mn blue colour fluorescent powder photoluminescence spectra in, luminescent material
Excitation wavelength is 247nm, 332nm and 369nm；Two obvious emission peaks are had, respectively correspondence at 420nm and 492nm
In 420nm (Mn), 492nm (Bi), electron transition forms emission peak, can be as blue light emitting material.
The invention have benefit that: a kind of bismuth of present invention offer, the blue colour fluorescent powder of additive Mn, with Yttrium Tungstate as matrix
Mixing manganese element and bismuth element, the blue-fluorescence powder body purity height of gained, high color purity, particle identity are good and hot steady simultaneously
Qualitative good.The excitation wave wavelength of the blue colour fluorescent powder of the present invention gets a promotion, and can be promoted to 369nm, be effectively increased indigo plant simultaneously
Light luminous intensity so that capacity usage ratio is greatly improved.Present invention also offers the blue colour fluorescent powder of a kind of bismuth, additive Mn
Preparation method, preparation technology is simple to operation, and calcining heat is low, and mild condition is easy to control, and the sample purity for preparing is high,
Yield is high, it is not necessary to adds precipitant, low cost, is suitable for large-scale production.The bismuth of the present invention, additive Mn blue colour fluorescent powder can
In white light LEDs luminescent material.
Accompanying drawing explanation
Fig. 1 is the manganese ion doping amount of present invention when being 0.5%, the XRD figure spectrum of fluorescent powder during bismuth ion doping difference；
Fig. 2 is manganese ion doping amount when being 0.5%, and bismuth ion doping is the scanning electron microscope (SEM) photograph of fluorescent powder when 1%；
Exciting light spectrogram when Fig. 3 is independent doped with manganese ion (doping is 0.5%), under monitoring wavelength 420nm；
When Fig. 4 is independent doped with manganese ion (doping is 0.5%), the emission spectrum figure under excitation wavelength is 247nm；
When Fig. 5 is individually to adulterate bismuth ion (doping is 1%), it is the exciting light spectrogram under 492nm at monitoring wavelength；
Fig. 6 is manganese ion doping amount when being 0.5%, and different bismuth ion dopings are the exciting light spectrogram under 420nm at monitoring wavelength；
Fig. 7 be manganese ion doping amount be 0.5%, when bismuth ion doping is 1%, monitoring wavelength 420nm under exciting light spectrogram；
Fig. 8 is manganese ion doping amount when being 0.5%, different bismuth ion doping emission spectrum figures under in excitation wavelength 332nm；
Fig. 9 is manganese ion doping amount when being 0.5%, different bismuth ion doping emission spectrum figures under in excitation wavelength 369nm；
The implication of reference in figure: in Fig. 1, Fig. 6, Fig. 8 and Fig. 9: a-0.5%Mn+0.5%Bi, b-0.5%Mn+1%Bi,
The standard card of c-0.5%Mn+3%Bi, d-0.5%Mn+5%Bi, e-0.5%Mn+7Bi, f-Yttrium Tungstate.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further introduced.
In the present invention, agents useful for same is commercially available prod, analytical pure.
Embodiment 1
A kind of bismuth, the blue colour fluorescent powder of additive Mn, its formula is: BixMnyY6-x-yWO12, wherein, 0.005≤x≤0.05,
0.001≤y≤0.01。
This bismuth, the preparation method of blue colour fluorescent powder of additive Mn, comprise the following steps:
(1) weighing ammonium tungstate according to mol ratio in formula, be dissolved in distilled water, be subsequently added hydrogen peroxide, stirring obtains molten
Liquid A；
(2) weigh the soluble-salt of yttrium, the soluble-salt of manganese and the soluble-salt of bismuth according to mol ratio in formula, be dissolved in molten
In liquid A, stirring obtains solution B；
(3) solution B heated and stirred is concentrated, be subsequently dried and obtain class colloid C；
(4) class colloid C is calcined, obtain blue colour fluorescent powder.
Embodiment 2
A kind of bismuth, the blue colour fluorescent powder of additive Mn, its formula is: BixMnyY6-x-yWO12, wherein, x=0.005, y=0.001.
This bismuth, the preparation method of blue colour fluorescent powder of additive Mn, comprise the following steps:
(1) weighing ammonium tungstate according to mol ratio in formula, be dissolved in distilled water, be subsequently added hydrogen peroxide, stirring obtains molten
Liquid A；Wherein, the consumption of distilled water is: according to mol ratio, ammonium tungstate distilled water=1 20；The consumption of hydrogen peroxide is: press
According to mol ratio, ammonium tungstate hydrogen peroxide=1 1；
(2) weigh the soluble-salt of yttrium, the soluble-salt of manganese and the soluble-salt of bismuth according to mol ratio in formula, be dissolved in molten
In liquid A, stirring obtains solution B；The soluble-salt of yttrium is carbonate；The soluble-salt of manganese is nitrate and carbonate；Bismuth
Soluble-salt is nitrate, carbonate and acetate；
(3) solution B heated and stirred under the conditions of 50 DEG C is concentrated for 3 hours, be dried 8 hours under the conditions of 90 DEG C subsequently
Obtain class colloid C；Wherein, stirring uses magnetic agitation；
(4) class colloid C is placed in corundum crucible, puts in Muffle furnace and carry out calcining under the conditions of 900 DEG C 6 hours, obtain
Blue colour fluorescent powder.
Embodiment 3
A kind of bismuth, the blue colour fluorescent powder of additive Mn, its formula is: BixMnyY6-x-yWO12, wherein, x=0.05, y=0.01.
This bismuth, the preparation method of blue colour fluorescent powder of additive Mn, comprise the following steps:
(1) weighing ammonium tungstate according to mol ratio in formula, be dissolved in distilled water, be subsequently added hydrogen peroxide, stirring obtains molten
Liquid A；Wherein, the consumption of distilled water is: according to mol ratio, ammonium tungstate distilled water=1 40；The consumption of hydrogen peroxide is: press
According to mol ratio, ammonium tungstate hydrogen peroxide=1 1；
(2) weigh the soluble-salt of yttrium, the soluble-salt of manganese and the soluble-salt of bismuth according to mol ratio in formula, be dissolved in molten
In liquid A, stirring obtains solution B；The soluble-salt of yttrium is nitrate；The soluble-salt of manganese is nitrate and acetate；Bismuth
Soluble-salt is carbonate and acetate；
(3) solution B heated and stirred under the conditions of 90 DEG C is concentrated for 6 hours, under the conditions of 50 DEG C, be dried 12 subsequently little
Time obtain class colloid C；Wherein, stirring uses mechanical agitation；
(4) class colloid C is placed in corundum crucible, puts in Muffle furnace and carry out calcining under the conditions of 1200 DEG C 3 hours,
To blue colour fluorescent powder.
Embodiment 4
A kind of bismuth, the blue colour fluorescent powder of additive Mn, its formula is: BixMnyY6-x-yWO12, wherein, x=0.025, y=0.005.
This bismuth, the preparation method of blue colour fluorescent powder of additive Mn, comprise the following steps:
(1) weighing ammonium tungstate according to mol ratio in formula, be dissolved in distilled water, be subsequently added hydrogen peroxide, stirring obtains molten
Liquid A；Wherein, the consumption of distilled water is: according to mol ratio, ammonium tungstate distilled water=1 30；The consumption of hydrogen peroxide is: press
According to mol ratio, ammonium tungstate hydrogen peroxide=1 1；
(2) weigh the soluble-salt of yttrium, the soluble-salt of manganese and the soluble-salt of bismuth according to mol ratio in formula, be dissolved in molten
In liquid A, stirring obtains solution B；The soluble-salt of yttrium is acetate；The soluble-salt of manganese is carbonate and acetate；Bismuth
Soluble-salt is nitrate and acetate；
(3) solution B heated and stirred under the conditions of 60 DEG C is concentrated for 5 hours, under the conditions of 80 DEG C, be dried 11 subsequently little
Time obtain class colloid C；Wherein, stirring uses magnetic agitation；
(4) class colloid C is placed in corundum crucible, puts in Muffle furnace and carry out calcining under the conditions of 1000 DEG C 5 hours,
To blue colour fluorescent powder.
Embodiment 5
A kind of bismuth, the blue colour fluorescent powder of additive Mn, its formula is: BixMnyY6-x-yWO12, wherein, x=0.01, y=0.005.
This bismuth, the preparation method of blue colour fluorescent powder of additive Mn, comprise the following steps:
(1) weighing ammonium tungstate according to mol ratio in formula, be dissolved in distilled water, be subsequently added hydrogen peroxide, stirring obtains molten
Liquid A；Wherein, the consumption of distilled water is: according to mol ratio, ammonium tungstate distilled water=1 35；The consumption of hydrogen peroxide is: press
According to mol ratio, ammonium tungstate hydrogen peroxide=1 1；
(2) weigh the soluble-salt of yttrium, the soluble-salt of manganese and the soluble-salt of bismuth according to mol ratio in formula, be dissolved in molten
In liquid A, stirring obtains solution B；The soluble-salt of yttrium is carbonate and acetate；The soluble-salt of manganese is nitrate；Bismuth
Soluble-salt is nitrate and carbonate；
(3) solution B heated and stirred under the conditions of 70 DEG C is concentrated for 4 hours, be dried 9 hours under the conditions of 70 DEG C subsequently
Obtain class colloid C；Wherein, stirring uses mechanical agitation；
(4) class colloid C is placed in corundum crucible, puts in Muffle furnace and carry out calcining under the conditions of 1100 DEG C 4 hours,
To blue colour fluorescent powder.
Embodiment 6
A kind of bismuth, the blue colour fluorescent powder of additive Mn, its formula is: BixMnyY6-x-yWO12, wherein, x=0.04, y=0.003.
This bismuth, the preparation method of blue colour fluorescent powder of additive Mn, comprise the following steps:
(1) weighing ammonium tungstate according to mol ratio in formula, be dissolved in distilled water, be subsequently added hydrogen peroxide, stirring obtains molten
Liquid A；Wherein, the consumption of distilled water is: according to mol ratio, ammonium tungstate distilled water=1 25；The consumption of hydrogen peroxide is: press
According to mol ratio, ammonium tungstate hydrogen peroxide=1 1；
(2) weigh the soluble-salt of yttrium, the soluble-salt of manganese and the soluble-salt of bismuth according to mol ratio in formula, be dissolved in molten
In liquid A, stirring obtains solution B；The soluble-salt of yttrium is nitrate and acetate；The soluble-salt of manganese is carbonate；Bismuth
Soluble-salt is acetate；
(3) solution B heated and stirred under the conditions of 80 DEG C is concentrated for 5.5 hours, under the conditions of 65 DEG C, be dried 10 subsequently
Hour obtain class colloid C；Wherein, stirring uses magnetic agitation；
(4) class colloid C is placed in corundum crucible, puts in Muffle furnace and carry out calcining under the conditions of 950 DEG C 5.5 hours,
To blue colour fluorescent powder.
Embodiment 7
A kind of bismuth, the blue colour fluorescent powder of additive Mn, its formula is: BixMnyY6-x-yWO12, wherein, x=0.007, y=0.006.
This bismuth, the preparation method of blue colour fluorescent powder of additive Mn, comprise the following steps:
(1) weighing ammonium tungstate according to mol ratio in formula, be dissolved in distilled water, be subsequently added hydrogen peroxide, stirring obtains molten
Liquid A；Wherein, the consumption of distilled water is: according to mol ratio, ammonium tungstate distilled water=1 32；The consumption of hydrogen peroxide is: press
According to mol ratio, ammonium tungstate hydrogen peroxide=1 1；
(2) weigh the soluble-salt of yttrium, the soluble-salt of manganese and the soluble-salt of bismuth according to mol ratio in formula, be dissolved in molten
In liquid A, stirring obtains solution B；The soluble-salt of yttrium is nitrate and carbonate；The soluble-salt of manganese is acetate；Bismuth
Soluble-salt is carbonate；
(3) solution B heated and stirred under the conditions of 75 DEG C is concentrated for 3.5 hours, under the conditions of 85 DEG C, be dried 9.5 subsequently
Hour obtain class colloid C；Wherein, stirring uses mechanical agitation；
(4) class colloid C is placed in corundum crucible, puts in Muffle furnace and carry out calcining under the conditions of 1050 DEG C 4.5 hours,
Obtain blue colour fluorescent powder.
Embodiment 8
A kind of bismuth, the blue colour fluorescent powder of additive Mn, its formula is: BixMnyY6-x-yWO12, wherein, x=0.02, y=0.009.
This bismuth, the preparation method of blue colour fluorescent powder of additive Mn, comprise the following steps:
(1) weighing ammonium tungstate according to mol ratio in formula, be dissolved in distilled water, be subsequently added hydrogen peroxide, stirring obtains molten
Liquid A；Wherein, the consumption of distilled water is: according to mol ratio, ammonium tungstate distilled water=1 27；The consumption of hydrogen peroxide is: press
According to mol ratio, ammonium tungstate hydrogen peroxide=1 1；
(2) weigh the soluble-salt of yttrium, the soluble-salt of manganese and the soluble-salt of bismuth according to mol ratio in formula, be dissolved in molten
In liquid A, stirring obtains solution B；The soluble-salt of yttrium is nitrate, carbonate and acetate；The soluble-salt of manganese is nitric acid
Salt, carbonate and acetate；The soluble-salt of bismuth is nitrate；
(3) solution B heated and stirred under the conditions of 55 DEG C is concentrated for 4.5 hours, under the conditions of 60 DEG C, be dried 12 subsequently
Hour obtain class colloid C；Wherein, stirring uses magnetic agitation；
(4) class colloid C is placed in corundum crucible, puts in Muffle furnace and carry out calcining under the conditions of 1150 DEG C 3.5 hours,
Obtain blue colour fluorescent powder.
Embodiment 9
A kind of bismuth, the blue colour fluorescent powder of additive Mn, its formula is: BixMnyY6-x-yWO12, wherein, x=0.01, y=0.005.
This bismuth, the preparation method of blue colour fluorescent powder of additive Mn, comprise the following steps:
(1) weighing ammonium tungstate according to mol ratio in formula, be dissolved in distilled water, be subsequently added hydrogen peroxide, stirring obtains molten
Liquid A；Wherein, the consumption of distilled water is: according to mol ratio, ammonium tungstate distilled water=1 30；The consumption of hydrogen peroxide is: press
According to mol ratio, ammonium tungstate hydrogen peroxide=1 1；
(2) weigh the soluble-salt of yttrium, the soluble-salt of manganese and the soluble-salt of bismuth according to mol ratio in formula, be dissolved in molten
In liquid A, stirring obtains solution B；The soluble-salt of yttrium is nitrate；The soluble-salt of manganese is carbonate；The soluble-salt of bismuth
For acetate；
(3) solution B heated and stirred under the conditions of 60 DEG C is concentrated for 4 hours, be dried 8 hours under the conditions of 90 DEG C subsequently
Obtain class colloid C；Wherein, stirring uses magnetic agitation；
(4) class colloid C is placed in corundum crucible, puts in Muffle furnace and carry out calcining under the conditions of 1200 DEG C 3 hours,
To blue colour fluorescent powder.
In above example 1～9, gained bismuth, the blue colour fluorescent powder of additive Mn all can be used in white light LEDs luminescent material.
Claims (9)
1. a bismuth, the blue colour fluorescent powder of additive Mn, it is characterised in that: the formula of described blue colour fluorescent powder is: BixMnyY6-x-yWO12,
Wherein, 0.005≤x≤0.05,0.001≤y≤0.01.
2. the preparation method of the blue colour fluorescent powder of bismuth as claimed in claim 1, additive Mn, it is characterised in that: comprise the following steps:
(1) weighing ammonium tungstate according to mol ratio in formula, be dissolved in distilled water, be subsequently added hydrogen peroxide, stirring obtains solution A；
(2) weigh the soluble-salt of yttrium, the soluble-salt of manganese and the soluble-salt of bismuth according to mol ratio in formula, be dissolved in solution A,
Stirring obtains solution B；
(3) solution B heated and stirred is concentrated, be subsequently dried and obtain class colloid C；
(4) class colloid C is calcined, obtain blue colour fluorescent powder.
Bismuth the most according to claim 2, the preparation method of blue colour fluorescent powder of additive Mn, it is characterised in that: comprise the following steps:
(1) weighing ammonium tungstate according to mol ratio in formula, be dissolved in distilled water, be subsequently added hydrogen peroxide, stirring obtains solution A；
(2) weigh the soluble-salt of yttrium, the soluble-salt of manganese and the soluble-salt of bismuth according to mol ratio in formula, be dissolved in solution A,
Stirring obtains solution B；
(3) by solution B heated and stirred 3～concentrate for 6 hours under the conditions of 50 DEG C～90 DEG C, it is subsequently dried and obtains class colloid C；
(4) carry out calcining 3～6 hours by class colloid C under the conditions of 900 DEG C～1200 DEG C, obtain blue colour fluorescent powder.
4. according to the bismuth described in Claims 2 or 3, the preparation method of the blue colour fluorescent powder of additive Mn, it is characterised in that: described step
(1) in, the consumption of distilled water is: according to mol ratio, ammonium tungstate distilled water=1mol 20～40mol；The consumption of hydrogen peroxide
For: according to mol ratio, ammonium tungstate hydrogen peroxide=1:1.
5. according to the bismuth described in Claims 2 or 3, the preparation method of the blue colour fluorescent powder of additive Mn, it is characterised in that: described step
(2), in, the soluble-salt of yttrium is one or more in nitrate, carbonate, acetate.
6. according to the bismuth described in Claims 2 or 3, the preparation method of the blue colour fluorescent powder of additive Mn, it is characterised in that: described step
(2), in, the soluble-salt of manganese and the soluble-salt of bismuth are one or more in nitrate, carbonate, acetate.
7. according to the bismuth described in Claims 2 or 3, the preparation method of the blue colour fluorescent powder of additive Mn, it is characterised in that: described step
(3), in, being dried is to be dried 8～12 hours under the conditions of 50 DEG C～90 DEG C.
8. according to the bismuth described in Claims 2 or 3, the preparation method of the blue colour fluorescent powder of additive Mn, it is characterised in that: described step
(3), in, stirring uses magnetic agitation or mechanical agitation.
9. the blue colour fluorescent powder application in white light LEDs luminescent material of bismuth as claimed in claim 1, additive Mn.
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| CN107573935A (en) * | 2017-08-23 | 2018-01-12 | 济南大学 | A kind of Eu3+Adulterate Gd6WO12The preparation method of red fluorescence powder |
| CN113563078A (en) * | 2021-07-29 | 2021-10-29 | 南京理工大学 | Trivalent bismuth ion enhanced manganese doped SrZn2S2O-oxysulfide scintillator and method for producing same |
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