CN106867524B - A kind of preparation and application of alkaline earth aluminate blue fluorescent material - Google Patents
A kind of preparation and application of alkaline earth aluminate blue fluorescent material Download PDFInfo
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- CN106867524B CN106867524B CN201710052663.1A CN201710052663A CN106867524B CN 106867524 B CN106867524 B CN 106867524B CN 201710052663 A CN201710052663 A CN 201710052663A CN 106867524 B CN106867524 B CN 106867524B
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- 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
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
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Abstract
The present invention relates to a kind of using near ultraviolet excitation and emits the preparation method and application of blue fluorescent material.Its chemical general formula is Ba8‑xCexAl2O11, wherein x is Ce3+The molar ratio of doping, 0.001≤x≤0.4.The present invention can use high temperature solid-state method or chemical synthesis, the fluorescent powder being prepared emits the blue-fluorescence near 450 nanometers under near ultraviolet excitation, it can be used as lamp use or plasma display fluorescent material, improve its incident photon-to-electron conversion efficiency and stability.
Description
Technical field
The invention belongs to the technical fields of materials chemistry, and in particular to a kind of preparation of alkaline earth aluminate blue fluorescent material
And application.
Background technique
In recent years, energy shortage and environmental pollution have been the two large problems that the whole mankind must face directly, and energy-saving and emission-reduction are
As the important topic currently faced.On the other hand, with the improvement of living standards, demand of the people to artificial light sources is also more next
It is higher.And the universal and use of artificial light sources is also the embodiment of a national economy and living standard, has data to show, in prosperity
Country, electric consumption on lighting accounts for the 20% of entire power consumption, and has also reached the 12% of total electricity consumption in China.It can be seen that making
With energy-efficient illuminator to carry out energy-saving and emission-reduction, have very big help, and its most important thing be exactly develop it is novel
Efficient fluorescent powder, this behave will be with great economic and social benefits.
White light LEDs obtain higher luminous efficiency with low energy consumption, are novel Energy -- Saving Illuminating Sources.In addition, wide at present
The general energy-saving lamp used, the chemical substance mercury in fluorescent tube all containing pollution environment, is easy to bring harm to environment.And white light
LED does not generate environmentally harmful chemical substance in production and use process, thus is known as a kind of " environmentally protective "
Lighting apparatus.And fluorescent powder is the important component of white light LEDs, outstanding fluorescent powder can improve LED colour rendering index,
The performance indicators such as luminous efficiency, service life.And fluorescent powder is usually to be made of host doped rare earth element, rare earth element because
Possess unique electronic structure for it, so that fluorescent powder has stronger absorbability, high transfer efficiency, especially visible
There are very strong emissivities in light region.Wherein using it is most wide be three primary colors fluorescent powder and ultraviolet or near ultraviolet LED combination,
Colour rendering is best；There are also the combinations for being exactly blue-ray LED and yellow fluorescent powder.
Ce is No. second element of group of the lanthanides, positive trivalent ion Ce3+Corresponding electron configuration is [Xe] 4f1.As trivalent
Rare earth ion, cerium ion and other rare earth ion are very different, and since its 5d energy level is very low, and 4f energy level is higher, therefore
Group-overlap, the 5d state so they have arrived after being excited occurs.Due to lacking shielding, 5d state is easy to be influenced by crystal field, therefore,
In different crystalline environments, electronics can generate the transmitting of different wave length, institute when returning 4f ground state from its minimum 5d track transition
With Ce3+The material of doping has received widespread attention.Utilize Ce3+Wide scope emit made of fluorescent powder, can be applied to
Ion FPD PDP, the phosphor of rare earth, the light conversion material for agricultural；Further, since Ce3+Transition be electricity
What dipole allowed, therefore the luminescent lifetime of cerium ion is very of short duration, generally adulterates Ce using the property in 10~1000 nanoseconds3+
Material fast scintillation crystal medically can also be made.
In addition, based on the requirement to sight protectio and color reproducibility, compared to outdoor road lamp, engineering illumination and scape
For seeing decoration mono-/multi- color LED, home lighting light source has higher requirements to white light LEDs luminous efficiency, colour temperature and colour rendering index.
Now widely used white light LEDs are to be generated using LED chip transmitting blue light excitation yellow fluorescent powder by yellow light and blue light
White light.This white light is not due to having red spectral components in emission spectrum, although color can be reduced by increasing yellow spectrum ratio
Temperature, but colour rendering index can not all be improved by adjusting yellow light and blue light ratio in any case.It is relatively low using this colour rendering index
Light source, will cause cross-color, i.e. the color of irradiated object appears to inconsistent with actual color.Thus it has been proposed that,
Three primary colors fluorescent powder is excited to obtain LED white light using near ultraviolet wavelength.This mode cooperates fluorescence relative to LED chip blue light
For the white light that powder generates, although certain luminous efficiency can be sacrificed, obtained white light coloration is preferable, including colour gamut and color range.
Since the photon energy of blue light is relatively high, compared to red and green emitting phosphor, the synthesis of blue colour fluorescent powder
Performance is poor, be mainly manifested in light decay is big, light lead to it is low.The blue fluorescent material for preparing white light currently used near ultraviolet LED is main
There is BaMg2Al16O27:Eu2+(BAM)、(Sr,Ba,Ca)5(PO4)3Cl:Eu2+And Sr4Al14025:Eu2+.BAM is using most extensively
Blue fluorescent material, emission peak wavelength has good excitation purity, luminous efficiency is also high, but BAM in 450nm or so
Heat resistanceheat resistant stability is poor, performance deterioration can occur in use, and luminescent color is easily increased with LED component operating temperature and floated
It moves.(Sr, Ba, Ca)5(PO4)3Cl:Eu2+It due to containing chlorine element in fluorescent powder, is difficult to control when synthesis, and generates useless containing chlorine
Gas is larger to environmental injury.Sr4Al14O25:Eu2+Emission peak is in 490nm or so, first is that launch wavelength and ideal blue are glimmering
Luminescent material 450-460nm difference is more, causes matched white light color saturation lower, second is that luminous efficiency is relatively low.Therefore, it visits
A kind of blue-fluorescence powder material of good combination property of rope undoubtedly has great meaning for the development and application that push near ultraviolet LED
Justice.
Summary of the invention
Meaning of the present invention is to provide a kind of white light LEDs that can be realized black light switching emission blue-fluorescence with glimmering
Luminescent material Ba8-xCexAl2O11Compound, and its application and preparation method for fluorescent material.It is to be solved by this invention
Technical problem is to improve luminous efficiency, chemical stability and the stability of photoluminescence of fluorescent material；Preparation process is difficult to control and produces
The problems such as raw chlorine contained exhaust gas is larger to environmental injury.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
On the one hand, the present invention provides a kind of material of black light switching emission blue-fluorescence, it is near 365 nanometers
Emit the blue-fluorescence near 450 nanometers under near ultraviolet excitation；The chemical general formula of the material is Ba8-xCexAl2O11, wherein
X is cerium ion Ce3+The molar ratio of doping, 0.001≤x≤0.4.
On the one hand, it is Ba that the present invention, which provides general formula,8-xCexAl2O11Compound be used for fluorescent material application, it is described
Fluorescent material is a kind of blue fluorescent material, Formula B a8-xCexAl2O11In, x is cerium ion Ce3+The molar ratio of doping, 0.001
≤x≤0.4；The blue fluorescent material is a kind of material of black light switching emission blue-fluorescence, near 365 nanometers
Near ultraviolet excitation under transmitting 450 nanometers near blue-fluorescence.
On the other hand, the present invention provides Formula B a8-xCexAl2O11The preparation method of compound can use high temperature solid-state
Method or chemical synthesis preparation.
Wherein, above-mentioned high temperature solid-state method preparation method includes the following steps:
By chemical formula Ba8-xCexAl2O11The stoichiometric ratio of middle each element, wherein 0.001≤x≤0.4, weighs contain respectively
There is cerium ion Ce3+Compound, contain barium ions Ba2+Compound, contain aluminium ion Al3+Compound, grinding, make sample
It is uniformly mixed；
The mixture that step (1) obtains is calcined 1~2 time in air atmosphere；The calcination temperature is 300~600 DEG C,
Calcination time is 1~15 hour；
The mixture that step (2) obtains is cooled to room temperature, again by step (1) method grinding and after mixing,
It calcines in air atmosphere, calcination temperature is 600~1000 DEG C, and calcination time is 1~12 hour；
The mixture natural cooling that step (3) is obtained, after ground and mixed is uniform, is calcined in air, and calcination temperature is
1000~1350 DEG C, calcination time is 1~12 hour, is then slowly cooled to room temperature, obtains a kind of realization black light conversion
Emit the material of blue-fluorescence.
Preferably, high temperature solid-state method preparation method includes:
By chemical formula Ba8-xCexAl2O11The stoichiometric ratio of middle each element, wherein 0.001≤x≤0.4, weighs contain respectively
There is cerium ion Ce3+Compound, contain barium ions Ba2+Compound, contain aluminium ion Al3+Compound, grinding, make sample
It is uniformly mixed；
The mixture that step (1) obtains is calcined 1~2 time in air atmosphere；The calcination temperature is 350~550 DEG C,
Calcination time is 2~10 hours；
The mixture that step (2) obtains is cooled to room temperature, again by step (1) method grinding and after mixing,
It calcines in air atmosphere, calcination temperature is 650~950 DEG C, and calcination time is 2~10 hours；
The mixture natural cooling that step (3) is obtained, after ground and mixed is uniform, is calcined in air, and calcination temperature is
1050~1300 DEG C, calcination time is 2~10 hours, is then slowly cooled to room temperature, obtains a kind of realization black light conversion
Emit the material of blue-fluorescence.
Wherein, above-mentioned chemical synthesis includes the following steps:
According to chemical formula Ba8-xCexAl2O11The stoichiometric ratio of middle each element, wherein 0.0001≤x≤0.4, weighs and contain
There is the compound of corresponding ion, respectively contains cerium ion Ce3+Compound, contain barium ions Ba2+Compound, contain aluminium
Ion A l3+Compound, they are dissolved separately in deionized water or dilute nitric acid solution, clear solution is obtained；Meanwhile it weighing
The complexing agent citric acid of 1.0~2.0wt% of each reactant quality, is respectively added in each solution, in 60~90 DEG C of temperature
Lower stirring a period of time；
Slowly the solution in step (1) containing required ion is mixed, 2~3 are stirred under the conditions of 60~100 DEG C of temperature
After hour, it is placed in baking oven and dries, obtain fluffy presoma；
Step (2) resulting presoma is placed in Muffle furnace and is calcined, temperature is 900~1200 DEG C, and the time is 2~12 small
When, room temperature is naturally cooled to, a kind of material for realizing black light switching emission blue-fluorescence is obtained.
In the present invention, Ba8-xCexAl2O11Preparation method in, in high temperature solid-state method and chemical synthesis, described contains
There is cerium ion Ce3+Compound be cerium oxide CeO2, cerous nitrate Ce (NO3)3·6H2One of O；Contain barium ions Ba2+Change
Conjunction object is barium nitrate Ba (NO3)2, barium carbonate BaCO3, barium hydroxide Ba (OH)2, barium oxalate C2BaO4One of；Containing aluminium from
Sub- Al3+Compound be aluminium oxide Al2O3, aluminum nitrate Al (NO3)3·9H2O, aluminium hydroxide Al (OH)3One of.
On the other hand, general formula provided by the invention is Ba8-xCexAl2O11Compound shown for white light LEDs, plasma
The fluorescent material of device.
Compared with prior art, technical solution of the present invention has the advantage that the present invention
(1) emit the indigo plant near 450 nanometers under a kind of near ultraviolet excitation that can be realized near 365 nanometers of the invention
Color fluorescent material has the features such as luminous efficiency is high, chemical stability and hair light and heat stability, can be effectively applied to white light
The fluorescent material of LED, while having the advantages that the light conversion material performance of synthesis is stable.
(2) preparation process for providing above-mentioned fluorescent powder is simple, and raw material sources are wide, and when synthesis, is not necessarily to special high temperature, high pressure
Equipment, simple process, production cost are low, and sample particle obtained is tiny and stable structure.
(3) present invention is in process of production without waste gas and waste liquid discharge (such as and Sr, Ba, Ca)5(PO4)3Cl:Eu2+Preparation
Compare, the discharge of no chlorine contained exhaust gas), to environment fanout free region, and fluorescent powder Ba8-xCexAl2O11It itself is also a kind of environmental-friendly
Inorganic material, harmful substance will not be decomposed to give off in use.
Detailed description of the invention
Fig. 1 is that the embodiment of the present invention 1 prepares sample Ba7.999Ce0.001Al2O11X-ray powder diffraction pattern；
Fig. 2 is that the embodiment of the present invention 1 prepares sample Ba7.999Ce0.001Al2O11Exciting light under the monitoring of 440 nano wave lengths
Spectrogram and the luminescent spectrum figure under the excitation of 346 nano wave lengths；
Fig. 3 is that the embodiment of the present invention 1 prepares sample Ba7.999Ce0.001Al2O11Decay of luminescence curve；
Fig. 4 is that the embodiment of the present invention 1 prepares sample Ba7.999Ce0.001Al2O11SEM figure；
Fig. 5 is that the embodiment of the present invention 6 prepares sample Ba7.93Ce0.07Al2O11X-ray powder diffraction pattern；
Fig. 6 is that the embodiment of the present invention 6 prepares sample Ba7.93Ce0.07Al2O11Excitation spectrum under the monitoring of 450 nano wave lengths
Figure and the luminescent spectrum figure under the excitation of 365 nano wave lengths；
Fig. 7 is that the embodiment of the present invention 6 prepares sample Ba7.93Ce0.07Al2O11Decay of luminescence curve；
Fig. 8 is that the embodiment of the present invention 6 prepares sample Ba7.93Ce0.07Al2O11SEM figure；
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1
According to chemical formula Ba7.999Ce0.001Al2O11The stoichiometric ratio of middle each element weighs barium carbonate BaCO respectively3:
6.314 gram, aluminium oxide Al2O3: 0.41 gram, cerium oxide CeO2: it 0.0007 gram, is placed in agate mortar and is added suitable anhydrous
Ethyl alcohol mixed grinding half an hour, it is to be mixed uniformly after, sample is placed in Muffle furnace and carries out precalcining.Precalcining condition are as follows:
Air atmosphere, 350 DEG C of calcination temperature, calcination time 2 hours.Then cooled to room temperature takes out sample for the original of precalcining
Material is fully ground with identical method again, is uniformly mixed, is calcined in air atmosphere, be sintered 2 hours again at 650 DEG C, cold
But it to room temperature, and is ground again, among air atmosphere, is sintered 2 hours, is cooled to room temperature, after taking-up at 1350 DEG C
It is fully ground and obtains sample.
It is the X-ray powder diffraction pattern that the present embodiment technical solution prepares sample referring to attached drawing 1；XRD test result is aobvious
Show, prepared sample crystallinity is preferable, without other miscellaneous phases.
It is the excitation spectrum by the sample of the present embodiment technical solution preparation under the monitoring of 440 nano wave lengths referring to attached drawing 2
Figure and the luminescent spectrum figure under the excitation of 346 nano wave lengths；As seen from the figure, the sample under the excitation of 346 nano wave length light
There is highest emission peak, and Ce in 440 nanometer wave strong points3+What ion was presented is broadband emission, there is wider halfwidth, obtained
Black light effectively can be converted to blue-fluorescence by material.
It is the decay of luminescence curve that technical solution of the embodiment of the present invention prepares sample, when can be calculated decaying referring to attached drawing 3
Between be 270.8 nanoseconds.
It is the SEM figure that technical solution of the embodiment of the present invention prepares sample referring to attached drawing 5.
Embodiment 2
According to chemical formula Ba7.995Ce0.005Al2O11The stoichiometric ratio of middle each element weighs barium carbonate BaCO respectively3:
6.31 grams, ANN aluminium nitrate nonahydrate Al (NO3)3·9H2O:3 grams, cerium oxide CeO2: it 0.0035 gram, is added in the agate mortar appropriate
After ethyl alcohol mixed grinding is uniform, precalcining is carried out in air atmosphere, after calcining furnace cooling in 4 hours at 450 DEG C, takes out sample
The raw material of precalcining is fully ground with identical method by product again, is calcined again in air atmosphere, and it is small that 3 are sintered at 800 DEG C
When, it is cooled to room temperature, takes out sample.Finally sample is fully ground and is mixed again, in air atmosphere, is sintered at 1300 DEG C
It 4 hours, is cooled to room temperature, is fully ground after taking-up and obtains sample.
The present embodiment technical solution prepares the X-ray powder diffraction pattern, exciting light spectrogram, fluorescence spectra, hair of sample
Optical attenuation curve, SEM figure are consistent with the sample prepared in embodiment 1.
Embodiment 3
According to chemical formula Ba7.993Ce0.007Al2O11The stoichiometric ratio of middle each element weighs barium nitrate Ba (NO respectively3)2:
4.18 grams, aluminium oxide Al2O3: 0.2 gram, cerium oxide CeO2: 0.0024 gram, suitable ethyl alcohol mixing is added in the agate mortar and grinds
After mill is uniform, precalcining is carried out in air atmosphere, after calcining 4 hours natural coolings at 500 DEG C, takes out sample for precalcining
Raw material be fully ground and mixed with identical method again, calcine in air atmosphere, be sintered 5 hours at 850 DEG C again, it is cold
But sample is taken out afterwards.Sample is finally subjected to third time grinding, mixing is placed in Muffle furnace, burns at 1250 DEG C in air atmosphere
It knot 6 hours, is cooled to room temperature, is fully ground after taking-up and obtains sample.
The present embodiment technical solution prepares the X-ray powder diffraction pattern, exciting light spectrogram, fluorescence spectra, hair of sample
Optical attenuation curve, SEM figure are consistent with the sample prepared in embodiment 1.
Embodiment 4
According to chemical formula Ba7.99Ce0.01Al2O11The stoichiometric ratio of middle each element weighs barium hydroxide Ba (OH) respectively2:
5.48 grams, aluminium hydroxide Al (OH)3: 0.63 gram, cerium oxide CeO2: 0.0068 gram, suitable no watery wine is added in the agate mortar
After smart mixed grinding is uniform, precalcining is carried out in air atmosphere, calcines 6 hours at 600 DEG C and waits Muffle furnaces natural cooling
Afterwards, it takes out sample the raw material of precalcining is fully ground and is mixed with identical method again, be calcined again in air atmosphere,
It is sintered 8 hours at 900 DEG C, takes out sample.Mixture is sufficiently mixed grinding uniformly again, among air atmosphere, 1200 DEG C
Lower sintering 8 hours, is cooled to room temperature, is fully ground after taking-up and obtains sample.
The present embodiment technical solution prepares the X-ray powder diffraction pattern, exciting light spectrogram, fluorescence spectra, hair of sample
Optical attenuation curve, SEM figure are consistent with the sample prepared in embodiment 1.
Embodiment 5
According to chemical formula Ba7.95Ce0.05Al2O11The stoichiometric ratio of middle each element weighs barium oxalate BaC respectively2O4:
7.17 grams, aluminium oxide Al2O3: 0.41 gram, cerium oxide CeO2: 0.035 gram, it is mixed that suitable dehydrated alcohol is added in the agate mortar
After closing grinding uniformly, precalcining is carried out in air atmosphere, after calcining furnace cooling in 10 hours at 600 DEG C, taking out sample will
The raw material of precalcining is fully ground and is mixed with identical method again, is calcined again in air atmosphere, is sintered 10 at 950 DEG C
Hour, cooled to room temperature takes out sample.Finally mixture is fully ground and is mixed again, is placed in Muffle furnace, in sky
It is sintered 10 hours at lower 1300 DEG C of gas atmosphere, is cooled to room temperature, is fully ground after taking-up and obtains sample.
The present embodiment technical solution prepares the X-ray powder diffraction pattern, exciting light spectrogram, fluorescence spectra, hair of sample
Optical attenuation curve, SEM figure are consistent with the sample prepared in embodiment 1.
Embodiment 6
According to chemical formula Ba7.93Ce0.07Al2O11The stoichiometric ratio of middle each element weighs barium nitrate Ba (NO respectively3)2:
2.07 grams, ANN aluminium nitrate nonahydrate Al (NO3)3·9H2O:0.75 grams, six nitric hydrate cerium Ce (NO3)3·6H2O:0.03 grams, and
The citric acid of the 1.8wt% of above each drug quality.By weighed barium nitrate Ba (NO3)2, aluminum nitrate Al (NO3)3·9H2O, nitre
Sour cerium Ce (NO3)3·6H2O is dissolved in together in suitable deionized water, and weighed citric acid is added, the magnetic under 80 DEG C of water-baths
Power stirring a period of time obtains clear solution, is finally placed in above-mentioned solution in baking oven after 80 DEG C are mixed 2 hours,
Set temperature is 80 DEG C, is dried 12 hours, natural cooling.Presoma is taken out, precursor is placed in Muffle furnace and is calcined, sintering temperature
It is 1100 DEG C, calcination time is 2 hours, is cooled to room temperature, takes out and be fully ground and obtain sample.
It is X-ray powder diffraction pattern and corresponding standard that the present embodiment technical solution prepares sample referring to attached drawing 5
PDF card；XRD test result shows that prepared sample crystallinity is fine, is phase pure material.
It is the excitation spectrum by the sample of the present embodiment technical solution preparation under the monitoring of 450 nano wave lengths referring to attached drawing 6
With the fluorescence spectra under the excitation of 365 nano wave lengths.As seen from the figure, obtained material equally can be effectively by black light
Be converted to blue light.
It is the decay of luminescence curve that technical solution of the embodiment of the present invention prepares sample, when can be calculated decaying referring to attached drawing 7
Between be 245.4 nanoseconds.
It is the SEM figure that technical solution of the embodiment of the present invention prepares sample referring to attached drawing 8.
Embodiment 7
According to chemical formula Ba7.9Ce0.1Al2O11The stoichiometric ratio of middle each element weighs barium hydroxide Ba (OH) respectively2:
2.7 grams, cerous nitrate Ce (NO3)3·6H2O:0.087 grams, aluminum nitrate Al (NO3)3·9H2O:1.5 grams, and above each drug matter
The citric acid of the 1.8wt% of amount.By weighed barium hydroxide Ba (OH)2, cerous nitrate Ce (NO3)3·6H2O, aluminum nitrate Al
(NO3)3·9H2O is dissolved separately in suitable deionized water, and 60 DEG C of magnetic agitations of weighed citric acid are added for a period of time
Clear solution is obtained, finally by above-mentioned solution after 60 DEG C are mixed 2 hours, is placed in baking oven, set temperature is 80 DEG C, is dried
12 hours, natural cooling took out presoma, precursor is placed in Muffle furnace and is calcined, and sintering temperature is 1100 DEG C, calcination time
It is 4 hours, is cooled to room temperature, takes out and be fully ground and obtain sample.
The present embodiment technical solution prepares the X-ray powder diffraction pattern, exciting light spectrogram, fluorescence spectra, hair of sample
Optical attenuation curve, SEM figure are consistent with the sample prepared in embodiment 6.
Embodiment 8
According to chemical formula Ba7.8Ce0.2Al2O11The stoichiometric ratio of middle each element weighs barium nitrate Ba (NO respectively3)2:
2.04 grams, aluminium hydroxide Al (OH)3: 0.156 gram, cerous nitrate Ce (NO3)3·6H2O:0.087 grams, and above each drug quality
1.8wt% citric acid.Weighed sample is dissolved separately in suitable dust technology, and 60 DEG C of weighed citric acid is added
Magnetic agitation obtains clear solution for a period of time, finally by above-mentioned solution after 60 DEG C are mixed 2 hours, places in baking oven,
Set temperature is 80 DEG C, is dried 12 hours, natural cooling, takes out presoma, and precursor is placed in Muffle furnace and is calcined, sintering temperature
Degree is 1150 DEG C, and calcination time is 5 hours, is cooled to room temperature, takes out and be fully ground and obtain sample.
The present embodiment technical solution prepares the X-ray powder diffraction pattern, exciting light spectrogram, fluorescence spectra, hair of sample
Optical attenuation curve, SEM figure are consistent with the sample prepared in embodiment 6.
Embodiment 9
According to chemical formula Ba7.7Ce0.3Al2O11The stoichiometric ratio of middle each element weighs barium oxalate BaC respectively2O4: 1.74
Gram, aluminium hydroxide Al (OH)3: 0.156 gram, cerous nitrate Ce (NO3)3·6H2O:0.13 grams, and above each drug quality
The citric acid of 1.8wt%.The above weighed sample is dissolved separately in suitable dust technology, magnetic agitation obtains for a period of time
Clear solution is placed in baking oven finally by above-mentioned solution after 60 DEG C are mixed 2 hours, and set temperature is 80 DEG C, and it is small to dry 12
When, natural cooling takes out presoma, precursor is placed in Muffle furnace and is calcined, and sintering temperature is 1200 DEG C, calcination time 6
Hour, it is cooled to room temperature, takes out and be fully ground and obtain sample.
The present embodiment technical solution prepares the X-ray powder diffraction pattern, exciting light spectrogram, fluorescence spectra, hair of sample
Optical attenuation curve, SEM figure are consistent with the sample prepared in embodiment 6.
Embodiment 10
According to chemical formula Ba7.6Ce0.4Al2O11The stoichiometric ratio of middle each element weighs barium carbonate BaCO respectively3: 3 grams,
Aluminium oxide Al2O3: 0.2 gram, cerium oxide CeO2: 0.14 gram, and the citric acid of the 1.8wt% of each drug quality above.Will more than
Weighed sample is dissolved separately in suitable dust technology, and magnetic agitation obtains clear solution for a period of time, finally will be above-mentioned molten
Liquid is placed in baking oven after 60 DEG C are mixed 2 hours, and set temperature is 80 DEG C, is dried 12 hours, natural cooling, takes out forerunner
Precursor is placed in Muffle furnace and calcines by body, and sintering temperature is 1200 DEG C, and calcination time is 8 hours, is cooled to room temperature, and takes out
And it is fully ground and obtains sample.
Technical solution in the present embodiment prepares the X-ray powder diffraction pattern, exciting light spectrogram, fluorescence spectrum of sample
Figure, decay of luminescence curve, SEM figure are consistent with the sample prepared in embodiment 6.
Claims (8)
1. general formula is Ba8-x Ce x Al2O11Compound be used for the application of fluorescent material, it is characterised in that: the fluorescent material is
A kind of blue fluorescent material, Formula B a8-x Ce x Al2O11In, 0.001≤x≤0.4, the blue fluorescent material is a kind of close
The material of ultraviolet light switching emission blue-fluorescence, the indigo plant under the near ultraviolet excitation near 365 nanometers near 450 nanometers of transmitting
Color fluorescence, the application are the fluorescent material for white light LEDs, plasma display.
2. a kind of Ba as described in claims 18-x Ce x Al2O11Preparation method, which is characterized in that use high temperature solid-state
Method or chemical synthesis preparation.
3. Ba as claimed in claim 28-x Ce x Al2O11Preparation method, it is characterised in that the high temperature solid-state method include such as
Lower step:
(1) chemical formula Ba is pressed8-xCexAl2O11The stoichiometric ratio of middle each element, wherein 0.001≤x≤0.4, weigh respectively containing
Cerium ion Ce3+Compound, contain barium ions Ba2+Compound, contain aluminium ion Al3+Compound, grinding keeps sample mixed
It closes uniform；
(2) mixture that step (1) obtains is calcined 1~2 time in air atmosphere；The calcination temperature is 300~600 DEG C,
Calcination time is 1~15 hour；
(3) mixture that step (2) obtains is cooled to room temperature, again by step (1) method grinding and after mixing, In
It is calcined under air atmosphere, calcination temperature is 600~1000 DEG C, and calcination time is 1~12 hour；
(4) the mixture natural cooling for obtaining step (3), after ground and mixed is uniform, is calcined in air, and calcination temperature is
1000~1350 DEG C, calcination time is 1~12 hour, is then slowly cooled to room temperature, obtains a kind of realization black light conversion
Emit the material of blue-fluorescence.
4. Ba as claimed in claim 38-x Ce x Al2O11Preparation method, it is characterised in that: the calcining temperature of the step (2)
Degree is 350~550 DEG C, and calcination time is 2~10 hours.
5. Ba as claimed in claim 38-x Ce x Al2O11Preparation method, it is characterised in that: the calcining temperature of the step (3)
Degree is 650~950 DEG C, and calcination time is 2~10 hours.
6. Ba as claimed in claim 38-x Ce x Al2O11Preparation method, it is characterised in that: the calcining temperature of the step (4)
Degree is 1050~1300 DEG C, and calcination time is 2~10 hours.
7. Ba as claimed in claim 28-x Ce x Al2O11Preparation method, it is characterised in that the chemical synthesis include such as
Lower step:
(1) according to chemical formula Ba8-xCexAl2O11The stoichiometric ratio of middle each element, wherein 0.0001≤x≤0.4, weigh containing
The compound of corresponding ion, respectively contains cerium ion Ce3+Compound, contain barium ions Ba2+Compound, containing aluminium from
Sub- Al3+Compound, they are dissolved separately in deionized water or dilute nitric acid solution, clear solution is obtained；Meanwhile it weighing each
The complexing agent citric acid of 1.0~2.0wt% of reactant quality, is respectively added in each solution, 60~90 DEG C at a temperature of stir
Mix a period of time；
(2) slowly the solution in step (1) containing required ion is mixed, 2~3 is stirred under the conditions of 60~100 DEG C of temperature
After hour, it is placed in baking oven and dries, obtain fluffy presoma；
(3) step (2) resulting presoma is placed in Muffle furnace and is calcined, temperature is 900~1200 DEG C, and the time is 2~12 small
When, room temperature is naturally cooled to, a kind of material for realizing black light switching emission blue-fluorescence is obtained.
8. the Ba as described in claims 3 or 7 are any8-x Ce x Al2O11Preparation method, it is characterised in that: described contains cerium
Ion Ce3+Compound be cerium oxide CeO2, cerous nitrate Ce (NO3)3•6H2One of O；Contain barium ions Ba2+Compound
For barium nitrate Ba (NO3)2, barium carbonate BaCO3, barium hydroxide Ba (OH)2, barium oxalate BaC2O4One of；Contain aluminium ion Al3+
Compound be aluminium oxide Al2O3, aluminum nitrate Al (NO3)3•9H2O, aluminium hydroxide Al (OH)3One of.
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| Title |
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| A phase equilibria study and thermodynamic assessment of the BaO-Al2O3 system;Rui Zhang et al.;《CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry》;20150813;第51卷;第42-50页 * |
| Site dependent thermoluminescence of long persistent phosphorescence of BaAl2O4:Ce3+;D. Jia et al.;《Optics Communications》;20020401;第24卷;第247-251页 * |
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