CN101649199B - Ultraviolet light stimulated phosphor - Google Patents
Ultraviolet light stimulated phosphor Download PDFInfo
- Publication number
- CN101649199B CN101649199B CN200910087495.5A CN200910087495A CN101649199B CN 101649199 B CN101649199 B CN 101649199B CN 200910087495 A CN200910087495 A CN 200910087495A CN 101649199 B CN101649199 B CN 101649199B
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- ion
- caco
- sintering
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- 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
Abstract
The invention relates to an ultraviolet light stimulated phosphor made from the following materials: (1) one or the combination of CaCO 3 and Ca (HCO3)2; (2) MoO3 or WO3; and (3) Pr6O11. The invention has the following component proportion: the sum of the mole concentration of Pr ion and Ca ion is equal to the mole concentration of W ion or Mo ion, the mole ratio of the Pr ion and the W ion or the Mo ion is less than 0.03 and more than 0.01, including 0.01 and 0.03. The preparation method of the phosphor has three steps: firstly, weighing high-purity CaCO 3, Ca (HCO 3) 2, MoO 3, WO 3 and Pr6O 11 according to the chemical measurement and uniformly mixing the materials; secondly, milling the materials in an agate mortar or a ball mill for 1 to 3 hours, and then sintering the materials in a corundum crucible for 2 to 5 hours at the high sintering temperature of 700 to 1,200 DEG C; thirdly, cooling the sintered materials to reach the room temperature, and then milling the sintered materials in the agate mortar or the ball mill for 1 to 2 hours. The phosphor with stable chemical properties and single component is prepared by a high-temperature solid-phase integration analysis method, warm white light with low color temperature (3,000 to 4,000K) can be emitted under the stimulation of ultraviolet light, and the invention has the advantages of high practical value and wide application prospect.
Description
(1) technical field
The present invention relates to a kind of white emitting fluorescent powder of ultraviolet excitation, this white emitting fluorescent powder is ultraviolet (UV) ray can be converted to the phosphor material powder of white light, belongs to photoelectricity chemical technology field.
(2) background technology
The energy in fluorescent material electromagnetic wave absorption frequency spectrum Yi Ge district, launches the radiating capacity in another district of frequency spectrum, and the fluorescent material of powdery is called fluorescent material conventionally, and the fluorescent material of transparent solid shape is called scintillator conventionally.
Known fluorescent material has two large classes: self-excited type fluorescent material and impurity activation formula fluorescent material.
Self-excited type fluorescent material is a kind of pure crystal main material, and it rises to state of activation by electronics while absorbing high-energy photon, by transmitting photon, from this state of activation, returns to low-energy state.Self-excited type fluorescent material is because electronics its energy region when state of activation or the low-energy state is wider, thereby its spectral emissions figure is wide.Therefore, the electronics of being excited is the quite wide photon of emitted energy scope the process that proceeds to low-energy state from excited state, and the photon energy of launching is relevant with the concrete energy before and after electron emission state-transition.
Normally a kind of non-fluorescence main material of matrix of impurity activation formula fluorescent material, has added the activator that concentration is lower to make its modification in main material.For impurity activation formula fluorescent material activator ion, can absorb directly into and penetrate photon or by being delivered to active ions after lattice absorption, make the electronics of active ions rise to excited state.These electronics send fluorescent photon while returning to low-energy state.
White light emitting diode (LED) because its efficiency is high, power consumption is little, the life-span is long, the remarkable advantage such as solid-state energy-conservation and environmental protection is widely used in lighting field.At present, the method for utilizing LED technology to realize white light mainly contains 3 kinds: the direct mixed-color method of three-primary color LED, ultraviolet transformation approach and blue chip add the method for yellow fluorescent powder.
(1) Tricolor LED mixed color method
Directly the three primary colours chip portfolio of transmitting red, green, blue wavelength is packaged together, forms multi-chip type white light LEDs, by spacing color mixed principle, mate in accordance with the appropriate ratio, make the light of three kinds of colors be mixed into white light.The weakness of this method is its mounting structure more complicated, and the driving voltage of LED of all kinds, luminous efficiency, light distribution characteristic difference, need by the intensity of current setting red, green, blue three primary colours, and circuit is more complicated on realizing.Meanwhile, because its aging property of the LED of different colours passing are in time different, cause the difference of light decay.Therefore, the white luminous light decay difference due to different colours of adjusting in advance causes the variable color in use procedure, makes the white light less stable of mixing, has the difference of temperature profile.Luminous all from photodiode, relative cost is also higher.
(2) method of ultraviolet conversion
Take LED as basic light source, and the ultraviolet excitation fluorescent material sending with LED, realizes wavelength Conversion by fluorescent material and sends visible ray.Finally for the light that throws light on all from fluorescent material, and require the excitation spectrum of fluorescent material and the emmission spectrum of LED to match, can obtain higher light conversion efficiency like this.Fluorescent material can be the combination of multiple fluorescent material, and the light by different colours mixes white light, can be also single a kind of fluorescent material that can transmitting white.
(3) blue chip adds the method for yellow fluorescent powder
Utilizing wavelength is the basic light source of luminous conduct of the GaN base blue-ray LED of 460～470nm.The blue light part that it sends is used for excitated fluorescent powder, makes fluorescent material send yellow-green light; Another part blue light sees through fluorescent material and emits, and the luminous transmissive portion of the yellow-green light that fluorescent material sends and GaN base blue-ray LED is mixed to form white light, i.e. the mechanism of white light=indigo plant+Huang.Its weak point is that color developing is poorer, and this is mainly because red composition in luminous spectrum is few.For making up this deficiency, normally in fluorescent material, add in addition red fluorescence powder, thereby obtain the lower warm white of colour temperature.Because this kind of method will produce warm white, need to mix red fluorescence powder, technology difficulty is increased, and the red fluorescent material of application mostly at present is deliquescent sulfide, fluorochemical, make stability of photoluminescence poor.
So we provide a kind of single component fluorescent material of stable chemical nature, without multiple fluorescent material, mix, just can under the exciting of single excitaton source, send the warm white of low colour temperature.
(3) summary of the invention
1, object: the object of the invention is for a kind of white emitting fluorescent powder of ultraviolet excitation is provided, it mixes the white emitting fluorescent powder that obtains single component without multiple fluorescent material, that is the white lumination system that provides of the fluorescent material that obtains the enough single components of a kind of energy, and under the exciting of single excitaton source, lighting system can be sent the warm white of low colour temperature.
2, technical scheme:
The white emitting fluorescent powder of a kind of ultraviolet excitation of the present invention, it is comprised of following several starting material:
(1) CaCO
3(analytical pure), Ca (HCO
3)
2one or both combinations in (analytical pure)
(2) MoO
3(analytical pure), WO
3a kind of in (analytical pure)
(3) Pr
6o
11(purity 99.99%)
Its stoichiometric composition proportioning is: Pr ion and Ca ion volumetric molar concentration and equal W or Mo ion volumetric molar concentration, Pr ion and W or Mo ion mol ratio are less than 0.03, are greater than 0.01, comprise 0.01 and 0.03.
N (Pr)+n (Ca)=n (W) wherein, 0.01≤n (Pr)/n (W)≤0.03
Or n (Pr)+n (Ca)=n (Mo) is wherein, 0.01≤n (Pr)/n (Mo)≤0.03
The molecular formula of white emitting fluorescent powder consists of Ca
1-xpr
xmO
4, M is a kind of in molybdenum or tungsten, X value scope is preferably between 0.01 to 0.03, comprises 0.01 and 0.03.White emitting fluorescent powder has scheelite-type structure through synthetic, there is no rear-earth-doped main structure.Tungstate and molybdate are a kind of self-excitation materials, and it has unique wide range transmitting figure.Main absorption generally occurs at the wavelength place that is less than 350nm.It is by wolframic acid alkali [WO that host lattice absorbs
4]
2-or molybdic acid alkali [MoO
4]
2-cause.The in the situation that of sheelite main structure and UV rays excite, main structure emission spectrum is the broadband that concentrates on 540nm left and right.The fluorescent material that is mixed with praseodymium ion is to provide the self-excited type material of luminous main structure, is also impurity activation formula luminescent material simultaneously.The emmission spectrum that fluorescent material sends had both comprised the broadband emission of sending from host lattice structure, also comprised the narrowband emission that rare earth impurities activator sends.Produce Ca
1-xpr
xmoO
4, can be by calcium carbonate (CaCO
3), Calcium hydrogen carbonate (Ca (HCO
3)
2), Praseodymium trioxide (Pr
6o
11), molybdenum oxide (MoO
3) and Tungsten oxide 99.999 (WO
3) etc. by above-mentioned desired proportions, evenly mix.
Main structure plays a part activator, and it absorbs intensity of activation from UV source, and by this transmission ofenergy to praseodymium ion, and launch corresponding energy with the form of optical radiation.Fig. 3 illustrates Ca
1-xpr
xmoO
4emmission spectrum under the UV of 325nm rays excite, wherein x value equals 0.02.The wire transmitting of 489nm, 604nm and 651nm, is derived from Pr
3+stimulated radiation, the broad-band illumination of about 540nm is CaMO
4main structure luminous.The chromaticity coordinates (x=0.41, y=0.39) of this utilizing emitted light on C.I.E. colour chart is corresponding to 3450K colour temperature.In fluorescent material, during the deviation of concentration x=0.02 of Pr, the chromaticity coordinates of the light that fluorescent material sends can change, but as long as in 0.01 to 0.03 scope, even if the photochromic temperature variation of sending but still can obtain white light.Like this, from the material of single component, can draw the white light of a series of different-colours.
The white fluorescence powder, preparation method thereof of a kind of ultraviolet excitation of the present invention, its concrete steps are as follows:
Step 1: take high purity reagent CaCO
3, Ca (HCO
3)
2, MoO
3, WO
3, Pr
6o
11, by stoichiometric, evenly mixing, this stoichiometric is: Pr ion and Ca ion volumetric molar concentration and equal W or Mo ion volumetric molar concentration, Pr ion and W or Mo ion mol ratio are less than 0.03, are greater than 0.01, comprise 0.01 and 0.03;
Step 2: at agate mortar or grinding in ball grinder 1-3 hour, it is mixed them, pack said mixture into corundum crucible, and be placed in High Temperature Furnaces Heating Apparatus sintering, atmosphere is air or nitrogen, and sintering temperature is 700-1200 ℃, and sintering time is 2-5 hour; This step gained is that molecular formula is Ca
1-xpr
xmO
4sinter;
Step 3: sinter is dropped in air to room temperature, again at agate mortar or obtain required product---white emitting fluorescent powder for grinding in ball grinder 1-2 hour.
3, advantage of the present invention and effect: the white emitting fluorescent powder of a kind of ultraviolet excitation of the present invention, it compared with prior art, its advantage is to obtain a kind of white emitting fluorescent powder by the way of solid state reaction, thereby, can be under the exciting in single burst of ultraviolel source, single component fluorescent material absorption ultraviolet rays by stable chemical nature sends white light, and it mixes without multiple fluorescent material, obtains the warm white of low colour temperature (3000-4000K).
(4) accompanying drawing explanation
Fig. 1 lighting system schematic diagram of the present invention
Fig. 2 fluorescent material excitation spectrum of the present invention schematic diagram
The emmission spectrum schematic diagram of Fig. 3 fluorescent material of the present invention under 325nm excites
The chromaticity coordinates schematic diagram of Fig. 4 fluorescent material of the present invention
Fig. 5 white fluorescence powder, preparation method thereof of the present invention schematic flow sheet
In Fig. 1, nomenclature is as follows:
1 source of radiation; 2 ultraviolet rays; 3 fluorescent materials; 4 fluorescence.
(5) embodiment
The white emitting fluorescent powder of a kind of ultraviolet excitation of the present invention, it is comprised of following several starting material:
(1) CaCO
3(analytical pure), Ca (HCO
3)
2one or both combinations in (analytical pure)
(2) MoO
3(analytical pure), WO
3a kind of in (analytical pure)
(3) Pr
6o
11(purity 99.99%)
Its stoichiometric composition proportioning is: Pr ion and Ca ion volumetric molar concentration and equal W or Mo ion volumetric molar concentration, Pr ion and W or Mo ion mol ratio are less than 0.03, are greater than 0.01, comprise 0.01 and 0.03.
N (Pr)+n (Ca)=n (W) wherein, 0.01≤n (Pr)/n (W)≤0.03
Or n (Pr)+n (Ca)=n (Mo) is wherein, 00.01≤n (Pr)/n (Mo)≤0.03
The white fluorescence powder, preparation method thereof of a kind of ultraviolet excitation of the present invention, it is as follows that the concrete implementation step of the method is enumerated embodiment:
embodiment 1:
Step 1: take high purity reagent CaCO
3(analytical pure), MoO
3(analytical pure), Pr
6o
11(purity 99.99%), its mol ratio is as follows:
n(CaCO
3)∶n(Pr
6O
11)∶n(MoO
3)＝594∶1∶600；
Step 2: they are ground in agate mortar 1 hour, it is mixed, pack said mixture into corundum crucible, and be placed in High Temperature Furnaces Heating Apparatus sintering, atmosphere is air, and sintering temperature is 800 ℃, and sintering time is 2 hours;
Step 3: sinter is dropped in air to room temperature, again grind in agate mortar and obtain required product for 1 hour.A kind of ultraviolet ray excited white emitting fluorescent powder obtaining, sample is pale yellow powder.Excitation band is less than 350nm.When sample is under 325nm excites, at 498nm, 600nm and 650nm left and right, there is emission peak, and near 540nm, have broad-band illumination.
embodiment 2:
Step 1: take high purity reagent CaCO
3(analytical pure), WO
3(analytical pure), Pr
6o
11(purity 99.99%), its mol ratio is as follows:
n(CaCO
3)∶n(Pr
6O
11)∶n(WO
3)＝294∶1∶300；
Step 2: they are ground in agate mortar 1 hour, it is mixed, pack said mixture into corundum crucible, and be placed in High Temperature Furnaces Heating Apparatus sintering, atmosphere is air, and sintering temperature is 800 ℃, and sintering time is 2 hours;
Step 3: sinter is dropped in air to room temperature, again grind in agate mortar and obtain required product for 1 hour.A kind of ultraviolet ray excited white emitting fluorescent powder obtaining, sample is pale yellow powder.Excitation band is less than 350nm.When sample is under 325nm excites, at 498nm, 600nm and 650nm left and right, there is emission peak, and near 530nm, have broad-band illumination.
Above two routine gained fluorescent material are Powdered crystallization, are dissolved in mineral acid, are insoluble to ethanol, ether or water.Gained fluorescent material is coated on suitable substrate, for example, can launches on the LED or fluorescent tube of UV ray, just obtain lighting system provided by the invention.
See Fig. 1, a white emitting fluorescent powder white lumination system, it is comprised of source of radiation 1 and fluorescent material 3, source of radiation 1 sends ray 2 to fluorescent material 3, fluorescent material 3 absorb to its rise excitation UV ray, send the fluorescence 4 of visual range in spectrum.
Wherein, source of radiation 1 is the ultraviolet rays that the ray that photodiode (LED), source of radiation 1 send is 325nm.Wherein, fluorescent material 3 is white emitting fluorescent powder Ca
1-xpr
xmoO
4, x value equals 0.02.
Fig. 2 is white emitting fluorescent powder excitation spectrum schematic diagram of the present invention; Fig. 3 illustrates Ca
1-xpr
xmoO
4emmission spectrum under the UV of 325nm rays excite, wherein x value equals 0.02; The chromaticity coordinates schematic diagram of Fig. 4 white emitting fluorescent powder of the present invention, Fig. 5 white fluorescence powder, preparation method thereof of the present invention process blocks schematic diagram.
Claims (2)
1. a white fluorescence powder, preparation method thereof for ultraviolet excitation, is characterized in that: the method concrete steps are as follows:
Step 1: take high purity reagent CaCO
3, MoO
3, Pr
6o
11, its mol ratio is as follows:
n(CaCO
3):n(Pr
6O
11):n(MoO
3)=594:1:600；
CaCO
3and MoO
3for analytical pure; Pr
6o
11purity is 99.99%;
Step 2: they are ground in agate mortar 1 hour, it is mixed, pack said mixture into corundum crucible, and be placed in High Temperature Furnaces Heating Apparatus sintering, atmosphere is air, and sintering temperature is 800 ℃, and sintering time is 2 hours;
Step 3: sinter is dropped in air to room temperature, again grind in agate mortar and obtain required product for 1 hour; A kind of ultraviolet ray excited white emitting fluorescent powder obtaining, sample is pale yellow powder; Excitation band is less than 350nm; When sample is under 325nm excites, at 498nm, 600nm and 650nm left and right, there is emission peak, and near 540nm, have broad-band illumination; Gained fluorescent material is Powdered crystallization, is dissolved in mineral acid, is insoluble to ethanol, ether or water.
2. a white fluorescence powder, preparation method thereof for ultraviolet excitation, is characterized in that: the method concrete steps are as follows:
Step 1: take high purity reagent CaCO
3, WO
3, Pr
6o
11, its mol ratio is as follows:
n(CaCO
3):n(Pr
6O
11):n(WO
3)=294:1:300；
CaCO
3and WO
3for analytical pure; Pr
6o
11purity is 99.99%;
Step 2: they are ground in agate mortar 1 hour, it is mixed, pack said mixture into corundum crucible, and be placed in High Temperature Furnaces Heating Apparatus sintering, atmosphere is air, and sintering temperature is 800 ℃, and sintering time is 2 hours;
Step 3: sinter is dropped in air to room temperature, again grind in agate mortar and obtain required product for 1 hour; A kind of ultraviolet ray excited white emitting fluorescent powder obtaining, sample is pale yellow powder; Excitation band is less than 350nm; When sample is under 325nm excites, at 498nm, 600nm and 650nm left and right, there is emission peak, and near 530nm, have broad-band illumination; Gained fluorescent material is Powdered crystallization, is dissolved in mineral acid, is insoluble to ethanol, ether or water.
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|---|---|---|---|
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|---|---|---|---|
| CN200910087495.5A CN101649199B (en) | 2009-06-23 | 2009-06-23 | Ultraviolet light stimulated phosphor |
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|---|---|---|---|---|
| CN104312585A (en) * | 2014-09-18 | 2015-01-28 | 陕西科技大学 | Near ultraviolet light excited tungstate red fluorescence material and its preparation method |
| CN110513605B (en) * | 2019-08-20 | 2020-12-29 | 西安鸿钧睿泽新材料科技有限公司 | Garden landscape lamp with self-luminous function and manufacturing method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760326A (en) * | 2004-10-11 | 2006-04-19 | 北京有色金属研究总院 | Phosphor powder of composite oxide in use for white light LED and fabricated electric light source |
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2009
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760326A (en) * | 2004-10-11 | 2006-04-19 | 北京有色金属研究总院 | Phosphor powder of composite oxide in use for white light LED and fabricated electric light source |
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