CN107629791A - A kind of Mn4+The red fluorescence powder of ion doping, preparation method and application - Google Patents
A kind of Mn4+The red fluorescence powder of ion doping, preparation method and application Download PDFInfo
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- CN107629791A CN107629791A CN201710814037.1A CN201710814037A CN107629791A CN 107629791 A CN107629791 A CN 107629791A CN 201710814037 A CN201710814037 A CN 201710814037A CN 107629791 A CN107629791 A CN 107629791A
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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
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Abstract
The invention discloses a kind of Mn4+The red fluorescence powder of ion doping, preparation method and application.The chemical general formula of the fluorescent material is Cs3Ge2Sb3O13:xMn4+, whereinxFor Mn4+The mol ratio of doping, 0.0005≤x≤0.015.The material that the present invention is prepared can respond in the range of blue light, near ultraviolet or ultraviolet equiwavelength, launch the red fluorescence in 620~750 nanometer wavelength ranges, available for the red light source for substituting Traditional dopant rare earth；Its excitation spectrum wider range, there is strong absorption in 355 nanometers, matched with the ultraviolet blue chip luminescence band of business.The features such as fluorescent material preparation method provided by the invention is simple, also selectively wide with raw material compared with fluorescent RE powder, and cost is low, is a kind of red fluorescence material of good luminous performance, can be applied to manufacture black light or blue light activated white light LED fluorescent powder.
Description
Technical field
The invention belongs to solid fluorescent material field, red illuminating material especially with respect to a kind of manganese (IV) doping and its
Specific access approaches.Prepared luminescent material can and YAG：Ce, InGaN blue chip combine, and can make up traditional commerce
White light LEDs high color temperature, the shortcomings that colour rendering index difference, the required warm white of people can be obtained.
Background technology
Social development at full speed also exacerbates the demand to the energy, not had in novel energy while human civilization is promoted
Before having ripe develop and utilize, traditional fossil fuel such as oil, coal, the primary energy such as natural gas is still us from big
Naturally the main of energy is obtained to rely on.But the discharge, haze etc. that the abuse of fossil fuel exacerbates carbon dioxide again is a series of
Problem of environmental pollution, in the case where human habitat is on the hazard, the strategy of high praise is fallen over each other in energy-saving and emission-reduction into various countries.
Incandescent lamp brought light at night in nearly more than 100 years for the mankind, but also due to its high energy consumption, fragile, no
The shortcomings of environmentally friendly, has been gradually backed out the arena of history.White LEDs are opened as a kind of new green light source by its plurality of advantages
Beginning is widely used in illuminator, display, is a milestone of energy-saving and emission-reduction in lighting field.At present, business should
It is most common or pass through the InGaN blue lights sent and YAG in:Ce3+The gold-tinted that fluorescent material is sent mixes and obtains white light,
But this design it is most basic the defects of be exactly that colour rendering is bad, and colour temperature is higher, causes the basic reason of this phenomenon
It is exactly the missing of red light source.Therefore, we need to be charged with a kind of fluorescent material that can send feux rouges in theory, except this it
Outside, it be able to also will effectively be excited by blue light.Doping with rare-earth ions Eu3+It is a kind of method for most easily obtaining red light source, but its
Can only be under near ultraviolet（<365 nanometers）It is excited, with blue chip InGaN（Excitation area is typically at 380 ~ 470 nanometers）Not
With so can not meet the application demand in WLEDs, and rare earth is a kind of strategic resource, price also costly, therefore, urgently
Wait to find a kind of low cost, can be by the light activated non-rear-earth-doped red fluorescence powder of short wavelength.
In several transition metals, Mn4+It is a kind of suitable red fluorescence powder activator, due to its uniqueness2E
- 4A2Spin-forbidden transition, this causes the light that it sends in the scope of red spectral band；Mn4+Also there is 3d3Electron configuration, certain
Coordination environment in, can present and effective launch and easily excited by near ultraviolet and blue light.In addition, Mn4+The original of ion
Expect that source is wide, price is cheaply many compared with rare earth, and this advantageously reduces WLEDs manufacturing cost.Due to Mn4+The wide application of ion
Prospect, increasing attention is obtained.
The content of the invention
The present invention is in view of the deficienciess of the prior art, provide a kind of ultraviolet, near purple for responding excitation source and inspiring
The wave bands such as outer or blue light, non-rare earth doped material --- the Mn of red fluorescence can be launched4+The red fluorescence powder of ion doping, system
Preparation Method and application.
To achieve the above object, the technical solution adopted by the present invention is to provide a kind of Mn4+The red fluorescence powder of ion doping,
Its chemical formula is：Cs3Ge2Sb3O13:xMn4+, wherein,xFor Mn4+The mol ratio of doping, 0.0005≤x≤0.015.
Fluorescent material of the present invention launches dominant wavelength in the case where the near ultraviolet that wavelength is 270~480 nanometers excites to blue light
For 620~750 nanometers of red fluorescence.
Technical solution of the present invention also includes Mn as described above4+The preparation method of the red fluorescence powder of ion doping, use
Chemical gel method, step are as follows：
1. with Cs containing cesium ion+Compound, Ge containing germanium ion4+Compound, Sb containing antimony ion5+Compound and containing manganese from
Sub- Mn4+Compound be raw material, by chemical formula Cs3Ge2-2xMn2xSb3O13Corresponding stoichiometric proportion, wherein, x Mn4+Rub
That percent coefficient, 0.0005≤x≤0.015, weighs each raw material, the raw material weighed is dissolved separately in into corresponding solvent
In, stir more than 3 hours；
2. using citric acid as complexing agent, complexing agent is added respectively by 0.5~2.0wt% of reactant quality in each raw material, in temperature
To stir 0.5~5h under conditions of 60~90 DEG C；
3. each solution that step 2 is obtained is slowly mixed together, stirred 3~6 hours under conditions of being 60~100 DEG C in temperature, stand,
Fluffy presoma is obtained after drying；
4. presoma is fully ground, after being incubated 3~5h hours under conditions of being 400~600 DEG C in temperature, then 950 are warming up to
~1250 DEG C, calcined in air atmosphere, calcination time is 3~8h；
5. the product natural cooling that step 4 is obtained, obtains a kind of Mn4+The red fluorescence powder of ion doping.
In above-mentioned technical proposal, described Cs containing cesium ion+Compound be cesium nitrate CsNO3, cesium acetate C2H3CsO2, carbon
Sour caesium Cs2CO3In one kind；Described Ge containing germanium ion4+Compound be germanium oxide GeO2With germanium tetrachloride GeCl4In one
Kind；Described Sb containing antimony ion5+Compound be antimony acetate C6H9O6Sb and antimony trichloride SbCl3In one kind；Described contains manganese
Ion Mn4+Compound be four nitric hydrate manganese Mn (NO3)2·4H2O, manganese acetate Mn (CH3COO)2, manganese chloride MnCl2In one
Kind.
A preferred scheme described in step 4 is：Calcining heat is 1000~1200 DEG C, and calcination time is 3~6 hours.
Mn of the present invention4+The application of ion-activated red fluorescence powder, as red light source, with blue chip
Combination, obtains warm white.
Compared with prior art, technical solution of the present invention advantage is：
1. Mn prepared by the present invention4+The red fluorescence powder of ion doping, can effectively it be absorbed concurrently near ultraviolet and blue wave band
Penetrate the feux rouges of 620~750 nanometer ranges.
2. Mn prepared by the present invention4+The red fluorescence powder of ion doping has higher luminous efficiency, and because being inorganic salts,
So also having good chemical stability and heat endurance, it can be used as the red component of multiple bases energy-conservation fluorescence light source, to carry
High color rendering index (CRI) and reduction colour temperature.
3. Mn prepared by the present invention4+The red fluorescence powder of ion doping, not only have and comparable luminous of rare earth ion
Characteristic and abundant raw material, cost is low, has good application prospect in terms of rare earth element is substituted.
It is a kind of environment-friendly phosphor 4. the present invention discharges without waste gas and waste liquid.
Brief description of the drawings
Fig. 1 is the Cs prepared by the technical scheme of the embodiment of the present invention 13Ge1.999Mn0.001Sb3O13X-ray powder diffraction figure
Spectrum；
Fig. 2 is the Cs prepared by the technical scheme of the embodiment of the present invention 13Ge1.999Mn0.001Sb3O13SEM spectrum；
Fig. 3 is the Cs prepared by the technical scheme of the embodiment of the present invention 13Ge1.999Mn0.001Sb3O13Obtained under 656 nanometers of monitorings
Near ultraviolet to blue region exciting light spectrogram；
Fig. 4 is the Cs prepared by the technical scheme of the embodiment of the present invention 13Ge1.999Mn0.001Sb3O13Hair under being excited at 400 nanometers
Light spectrogram；
Fig. 5 is the Cs prepared by the technical scheme of the embodiment of the present invention 13Ge1.999Mn0.001Sb3O13Decay of luminescence curve；
Fig. 6 is the Cs prepared by the technical scheme of the embodiment of the present invention 53Ge1.984Mn0.016Sb3O13X-ray powder diffraction pattern；
Fig. 7 is the Cs prepared by the technical scheme of the embodiment of the present invention 53Ge1.984Mn0.016Sb3O13SEM spectrum；
Fig. 8 is the Cs prepared by the technical scheme of the embodiment of the present invention 53Ge1.984Mn0.016Sb3O13Obtained under 656 nanometers of monitorings
Near ultraviolet to blue region exciting light spectrogram；
Fig. 9 is the Cs prepared by the technical scheme of the embodiment of the present invention 53Ge1.984Mn0.016Sb3O13Hair under being excited at 400 nanometers
Light spectrogram；
Figure 10 is the Cs prepared by the technical scheme of the embodiment of the present invention 53Ge1.984Mn0.016Sb3O13Decay of luminescence curve.
Embodiment
Technical solution of the present invention is further described with reference to the accompanying drawings and examples.
Embodiment 1
Prepare Cs3Ge1.999Mn0.001Sb3O13
According to chemical formula Cs3Ge1.999Mn0.001Sb3O13, cesium nitrate CsNO is stoichiometrically weighed respectively3：2.924 gram, oxidation
Germanium GeO2：1.045 gram；Antimony acetate C6H9O6Sb：4.483 gram；Four nitric hydrate manganese Mn (NO3)2·4H2O：0.001 gram；Again by each
The 2.0wt% of reactant quality weighs corresponding citric acid respectively in raw material.Antimony acetate is first dissolved in appropriate ethylene glycol solution
In, stirring, obtain solution A；Remaining raw material is dissolved in together in appropriate dust technology again, stirs 3 hours, treat raw material especially
After germanium oxide is completely dissolved, then by the above-mentioned mixed liquor of the citric acid weighed addition, obtain solution B；Solution A is delayed while stirring
Slowly it is added in B solution, and is stirred in 75 DEG C of water-bath until gluey.The jelly of gained is aged a period of time, put
Heat drying 12 hours in 100 DEG C of baking oven, obtain fluffy presoma.Presoma is taken out and fully ground with agate mortar
It is even, then be placed in Muffle kiln roasting, during roasting prior to 500 DEG C at 3 hours of constant temperature, be then to slowly warm up to 1200 DEG C, calcining 7
Hour, natural cooling can obtain required Mn4+The red fluorescence powder of ion doping.
Referring to accompanying drawing 1, it is by Cs manufactured in the present embodiment3Ge1.999Mn0.001Sb3O13X-ray powder diffraction pattern,
XRD test results show that prepared sample crystallinity is preferable, are monophase materialses.
Referring to accompanying drawing 2, it is by Cs manufactured in the present embodiment3Ge1.999Mn0.001Sb3O13Scanning electron microscope (SEM) photograph, SEM test
As a result show, prepared material granule has slight reunion.
Referring to accompanying drawing 3, it is to launch exciting under 656 nanometers of light in monitoring by sample prepared by the present embodiment technical scheme
Spectrum, as seen from the figure, the emitting red light of the material excite source mainly the near ultraviolet between 270 ~ 480 nanometers to blue light region
Domain.
Referring to accompanying drawing 4, it is luminous light of the sample prepared by the present embodiment technical scheme in the case where 400 nano wave lengths excite
Spectrogram.As seen from the figure, the main center emission wavelength of the material is 656 nanometers of red light wave band.
Referring to accompanying drawing 5, it is the Cs prepared by the embodiment of the present invention3Ge1.999Mn0.001Sb3O13Decay of luminescence curve, meter
Calculation can obtain die-away time as 31 milliseconds.
The Cs that the present embodiment is provided3Ge1.999Mn0.001Sb3O13Fluorescent material is as red light source, for improving traditional Huang
The cool white light that indigo plant is mixed to get, for example, with commercial YAG：Ce-InGaN blue chips combine, and it is required warm can to obtain people
White light.
Embodiment 2
Prepare Cs3Ge1.998Mn0.002Sb3O13
According to chemical formula Cs3Ge1.998Mn0.002Sb3O13, cesium nitrate CsNO is weighed respectively3：2.924 gram；Germanium tetrachloride GeCl4：
2.142 gram（Appropriate absolute ethyl alcohol, balance peeling are first put into small beaker, then GeCl is slowly added dropwise with dropper4, obtain solution
A）；Antimony acetate C6H9O6Sb：4.483 gram；Manganese acetate Mn (CH3COO)2：0.002 gram；Reactant quality in each raw material is pressed again
2.0wt% weighs corresponding citric acid respectively.The citric acid weighed is all dissolved in appropriate deionized water, then by nitric acid
Caesium, manganese acetate are dissolved in citric acid solution together, obtain solution B；Meanwhile proper amount of glycol is taken in another beaker, will
The antimony acetate dissolving weighed, obtains solution C；Then solution A and C are slowly added into B solution with dropper, side edged stirs
Mix, after A and C solution are all mixed into B solution, the mixed liquor of gained is placed in stirring in 75 DEG C of water-bath until gluey.
The jelly of gained is aged a period of time, heat drying 12 hours in 100 DEG C of baking oven is placed on, obtains fluffy presoma.
Presoma is taken out and is fully ground with agate mortar even, then is placed in Muffle kiln roasting, during roasting prior to 500 DEG C at constant temperature 3
Hour, 1150 DEG C are then to slowly warm up to, is calcined 5 hours, natural cooling can obtain required Mn4+Ion doping it is red glimmering
Light powder.
The present embodiment technical scheme prepares the X-ray powder diffraction pattern of sample, scanning electron microscope (SEM) photograph, exciting light spectrogram, hair
Light spectrogram, decay of luminescence curve are similar to the sample prepared in embodiment 1.
Embodiment 3
Prepare Cs3Ge1.994Mn0.006Sb3O13
According to chemical formula Cs3Ge1.994Mn0.006Sb3O13, cesium acetate C is weighed respectively2H3CsO2：2.879 gram；Germanium tetrachloride GeCl4：
2.138 gram（Appropriate absolute ethyl alcohol, balance peeling are first put into small beaker, then GeCl is slowly added dropwise with dropper4, obtain solution
A）；Antimony trichloride SbCl3：3.422 gram；Manganese chloride MnCl2：0.005 gram；Press reactant quality in each raw material again 2.0wt% points
Also known as take corresponding citric acid.The citric acid weighed is all dissolved in appropriate deionized water and the dense salt of the 37% of 3ml is added dropwise
Acid, then cesium acetate, antimony trichloride, manganese chloride are dissolved in citric acid solution together, obtain solution B；Then solution A is used
Dropper is slowly added into B solution, stirring while adding, and after solution A is all mixed into B solution, the mixed liquor of gained is put
The stirring in 75 DEG C of water-bath is until gluey.The jelly of gained is aged a period of time, is placed in 100 DEG C of baking oven and heats
Dry 12 hours, obtain fluffy presoma.Presoma is taken out and is fully ground with agate mortar even, then is placed in Muffle furnace and roasts
Burn, during roasting prior to 500 DEG C at 3 hours of constant temperature, be then to slowly warm up to 1200 DEG C, calcine 8 hours, natural cooling can obtain
To required Mn4+The red fluorescence powder of ion doping.
The present embodiment technical scheme prepares the X-ray powder diffraction pattern of sample, scanning electron microscope (SEM) photograph, exciting light spectrogram, hair
Light spectrogram, decay of luminescence curve are similar to the sample prepared in embodiment 1.
Embodiment 4
Prepare Cs3Ge1.99Mn0.01Sb3O13
According to chemical formula Cs3Ge1.99Mn0.01Sb3O13, raw acetic acid caesium C is weighed respectively2H3CsO2：2.879 gram；Germanium oxide GeO2：
1.041 gram；Antimony acetate C6H9O6Sb：4.483 gram；Four nitric hydrate manganese Mn (NO3)2·4H2O：0.013 gram；Press again in each raw material
The 2.0wt% of reactant quality weighs corresponding citric acid respectively.First, proper amount of glycol is taken, by antimony acetate C6H9O6Sb dissolves
Obtain in ethylene glycol solution, obtain the solution A containing antimony ion；Then appropriate salpeter solution is taken again, and germanium oxide is put into wherein,
Again by cesium acetate after abundant dissolving, manganese nitrate is also placed in wherein, and stirring obtains solution B in 3 hours；Then solution A is slowly dripped
Add in solution B, stir when being added dropwise, add the citric acid that weighs up after A and B liquid is well mixed, and by the mixed liquor of gained
Stirring in 75 DEG C of water-bath is placed in until gluey.The jelly of gained is aged a period of time, is placed in 100 DEG C of baking oven and adds
Heated drying 12 hours, obtains fluffy presoma.Presoma is taken out and is fully ground with agate mortar even, then is placed in Muffle furnace
Roasting, during roasting prior to 500 DEG C at 3 hours of constant temperature, be then to slowly warm up to 1150 DEG C, calcine 6 hours, natural cooling
Obtain required Mn4+The red fluorescence powder of ion doping.
The present embodiment technical scheme prepares the X-ray powder diffraction pattern of sample, scanning electron microscope (SEM) photograph, exciting light spectrogram, hair
Light spectrogram, decay of luminescence curve are similar to the sample prepared in embodiment 1.
Embodiment 5
Prepare Cs3Ge1.984Mn0.016Sb3O13
According to chemical formula Cs3Ge1.984Mn0.016Sb3O13, oxide spinel caesium Cs is weighed respectively2CO3：2.444 gram；Germanium tetrachloride
GeCl4：2.127 gram（Appropriate absolute ethyl alcohol, balance peeling are first put into small beaker, then GeCl is slowly added dropwise with dropper4, obtain
Solution A）；Antimony trichloride SbCl3：3.422 gram；Manganese acetate Mn (CH3COO)2：0.014 gram；Reactant quality in each raw material is pressed again
2.0wt% weigh corresponding citric acid respectively.It need to carry out in glove box when weighing cesium carbonate, dissolve cesium carbonate after having claimed
Take out from glove box in appropriate watery hydrochloric acid, antimony trichloride, manganese acetate are added in the solution again then, stirring is straight
To dissolving, solution B is obtained；Solution A is slowly added dropwise into solution B, stirred when being added dropwise, is added after A and B liquid is well mixed
The citric acid weighed up, and the mixed liquor of gained is placed in stirring in 75 DEG C of water-bath until gluey.The jelly of gained is old
Change a period of time, be placed on heat drying 12 hours in 100 DEG C of baking oven, obtain fluffy presoma.Presoma is taken out and is used in combination
Agate mortar fully grinds even, then is placed in Muffle kiln roasting, during roasting prior to 500 DEG C at 3 hours of constant temperature, then slowly heating
To 1180 DEG C, calcine 7 hours, natural cooling can obtain required Mn4+The red fluorescence powder of ion doping.
Referring to accompanying drawing 6, it is the Cs prepared by the present embodiment technical scheme3Ge1.984Mn0.016Sb3O13X-ray powder spread out
Collection of illustrative plates is penetrated, XRD test results show that prepared sample crystallinity is preferable, are monophase materialses.
Referring to accompanying drawing 7, it is the scanning electron microscope (SEM) photograph that sample is prepared by the present embodiment technical scheme, and SEM test results are shown,
Prepared material granule particle diameter is at 1 ~ 3 micron, complete crystallization.
Referring to accompanying drawing 8, it is to launch exciting under 656 nanometers of light in monitoring by sample prepared by the present embodiment technical scheme
Spectrum, as seen from the figure, the emitting red light of the material excite source mainly the near ultraviolet between 270 ~ 480 nanometers to blue light region
Domain.
Referring to accompanying drawing 9, it is luminous light of the sample prepared by the present embodiment technical scheme in the case where 400 nano wave lengths excite
Spectrogram.As seen from the figure, the main center emission wavelength of the material is 656 nanometers of red light wave band.
Referring to accompanying drawing 10, it is the decay of luminescence curve that technical scheme of the embodiment of the present invention prepares sample, can be calculated and declines
Subtract the time as 34.4 milliseconds.
Embodiment 6
Prepare Cs3Ge1.978Mn0.022Sb3O13
According to chemical formula Cs3Ge1.978Mn0.022Sb3O13, oxide spinel caesium Cs is weighed respectively2CO3：2.444 gram；Germanium oxide GeO2：
1.034 gram；Antimony acetate C6H9O6Sb：4.483 gram；Manganese acetate Mn (CH3COO)2：0.019 gram；Reactant quality in each raw material is pressed again
2.0wt% weigh corresponding citric acid respectively.It need to carry out in glove box when weighing cesium carbonate, dissolve cesium carbonate after having claimed
Taken out again from glove box in the dust technology of excess, germanium oxide, manganese acetate are also placed in the solution, stirring is until solids
It is completely dissolved to obtain solution A；Proper amount of glycol is taken, by antimony acetate C6H9O6Sb dissolves to obtain the solution B containing antimony ion；By B solution
It is slowly added dropwise into solution A, stir when being added dropwise, adds the citric acid that weighs up after A and B liquid is well mixed, and by gained
Mixed liquor is placed in stirring in 75 DEG C of water-bath until gluey.The jelly of gained is aged a period of time, is placed on 100 DEG C of baking
Heat drying 12 hours in case, obtain fluffy presoma.Presoma is taken out and is fully ground with agate mortar even, then is placed in horse
Not kiln roasting, during roasting prior to 500 DEG C at 3 hours of constant temperature, be then to slowly warm up to 1100 DEG C, calcine 8 hours, it is naturally cold
But it can obtain required Mn4+The red fluorescence powder of ion doping.
The present embodiment technical scheme prepares the X-ray powder diffraction pattern of sample, scanning electron microscope (SEM) photograph, exciting light spectrogram, hair
Light spectrogram, decay of luminescence curve are consistent with the sample prepared in embodiment 5.
Embodiment 7
Prepare Cs3Ge1.974Mn0.026Sb3O13
According to chemical formula Cs3Ge1.974Mn0.026Sb3O13, raw acetic acid caesium C is weighed respectively2H3CsO2：2.897 gram；Germanium tetrachloride
GeCl4：2.117 gram（Appropriate absolute ethyl alcohol, balance peeling are first put into small beaker, then GeCl is slowly added dropwise with dropper4, obtain
Solution A）；Antimony acetate C6H9O6Sb：4.483 gram；Manganese acetate Mn (CH3COO)2：0.022 gram, then by reactant quality in each raw material
2.0wt% weigh corresponding citric acid respectively.First, proper amount of glycol is taken, antimony acetate is dissolved in ethylene glycol, obtains solution
B；Appropriate amount of deionized water is taken again, the citric acid claimed is dissolved, then adds cesium acetate and manganese acetate, and lasting stirring obtains solution
C；Now A and B solution are added dropwise in C solution, stirred when being added dropwise, the lemon weighed up is added after A, B and C liquid are well mixed
Lemon acid, and the mixed liquor of gained is placed in stirring in 75 DEG C of water-bath until gluey.When the jelly of gained is aged into one section
Between, heat drying 12 hours in 100 DEG C of baking oven are placed on, obtain fluffy presoma.Presoma is taken out and uses agate mortar
Fully grind even, then be placed in Muffle kiln roasting, during roasting prior to 500 DEG C at 3 hours of constant temperature, be then to slowly warm up to 1150
DEG C, calcine 6 hours, natural cooling can obtain required Mn4+The red fluorescence powder of ion doping.
The present embodiment technical scheme prepares the X-ray powder diffraction pattern of sample, scanning electron microscope (SEM) photograph, exciting light spectrogram, hair
Light spectrogram, decay of luminescence curve are consistent with the sample prepared in embodiment 5.
Embodiment 8
Prepare Cs3Ge1.97Mn0.03Sb3O13
According to chemical formula Cs3Ge1.97Mn0.03Sb3O13, raw material cesium nitrate CsNO is weighed respectively3：2.924 gram；Germanium oxide GeO2：
1.03 gram；Antimony acetate C6H9O6Sb：4.483 gram；Manganese acetate Mn (CH3COO)2：0.026 gram, then by reactant quality in each raw material
2.0wt% weigh corresponding citric acid respectively.First, proper amount of glycol is taken, antimony acetate is dissolved in ethylene glycol, obtains solution
A, then appropriate dust technology is taken, germanium oxide is first added to stirring in dust technology until being completely dissolved, then again by cesium nitrate, manganese acetate
Also dissolve into and solution B is obtained in solution, then solution A is added dropwise in B solution, it is stirring while adding, treat that the mixing of A and B liquid is equal
It is even to add the citric acid weighed up afterwards, and the mixed liquor of gained is placed in stirring in 75 DEG C of water-bath until gluey.By gained
Jelly ageing a period of time, heat drying 12 hours in 100 DEG C of baking oven are placed on, obtain fluffy presoma.By presoma
Take out and fully ground with agate mortar even, then be placed in Muffle kiln roasting, during roasting prior to 500 DEG C at 3 hours of constant temperature, then
1100 DEG C are to slowly warm up to, is calcined 4 hours, natural cooling can obtain required Mn4+The red fluorescence powder of ion doping.
The present embodiment technical scheme prepares the X-ray powder diffraction pattern of sample, scanning electron microscope (SEM) photograph, exciting light spectrogram, hair
Light spectrogram, decay of luminescence curve are consistent with the sample prepared in embodiment 5.Equally, fluorescent material the present embodiment provided
As red light source, combined with blue chip, obtain warm white.
Claims (6)
- A kind of 1. Mn4+The red fluorescence powder of ion doping, it is characterised in that its chemical formula is：Cs3Ge2Sb3O13:xMn4+, its In,xFor Mn4+The mol ratio of doping, 0.0005≤x≤0.015.
- A kind of 2. Mn according to claim 14+The red fluorescence powder of ion doping, it is characterised in that：The fluorescent material exists Wavelength is that 270~480 nanometers of near ultraviolet to blue light excites down, launches the red fluorescence that dominant wavelength is 620~750 nanometers.
- A kind of 3. Mn as claimed in claim 14+The preparation method of the red fluorescence powder of ion doping, it is characterised in that useization Gel method is learned, is comprised the following steps：（1）With Cs containing cesium ion+Compound, Ge containing germanium ion4+Compound, Sb containing antimony ion5+Compound and containing manganese from Sub- Mn4+Compound be raw material, by chemical formula Cs3Ge2-2xMn2xSb3O13Corresponding stoichiometric proportion, wherein, x Mn4+Rub That percent coefficient, 0.0005≤x≤0.015, weighs each raw material, the raw material weighed is dissolved separately in into corresponding solvent In, stir more than 3 hours；（2）Using citric acid as complexing agent, complexing agent is added respectively by 0.5~2.0wt% of reactant quality in each raw material, in temperature Spend to stir 0.5~5h under conditions of 60~90 DEG C；（3）By step（2）Obtained each solution is slowly mixed together, and is stirred 3~6 hours under conditions of being 60~100 DEG C in temperature, quiet Put, dry after obtain fluffy presoma；（4）Presoma is fully ground, after being incubated 3~5h hours under conditions of being 400~600 DEG C in temperature, then is warming up to 950 ~1250 DEG C, calcined in air atmosphere, calcination time is 3~8h；（5）By step（4）Obtained product natural cooling, obtains a kind of Mn4+The red fluorescence powder of ion doping.
- A kind of 4. Mn according to claim 34+The preparation method of the red fluorescence powder of ion doping, it is characterised in that：Institute The Cs containing cesium ion stated+Compound be cesium nitrate CsNO3, cesium acetate C2H3CsO2, cesium carbonate Cs2CO3In one kind；Described Ge containing germanium ion4+Compound be germanium oxide GeO2With germanium tetrachloride GeCl4In one kind；Described Sb containing antimony ion5+Change Compound is antimony acetate C6H9O6Sb and antimony trichloride SbCl3In one kind；Described Mn containing manganese ion4+Compound for four hydration Manganese nitrate Mn (NO3)2·4H2O, manganese acetate Mn (CH3COO)2, manganese chloride MnCl2In one kind.
- A kind of 5. Mn according to claim 34+The preparation method of the red fluorescence powder of ion doping, it is characterised in that：Step Suddenly（4）Described calcining heat is 1000~1200 DEG C, and calcination time is 3~6 hours.
- A kind of 6. Mn as claimed in claim 14+The application of ion-activated red fluorescence powder, it is characterised in that：As Red light source, combined with blue chip, obtain warm white.
Priority Applications (1)
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