CN106867524A - 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
- Publication number
- CN106867524A CN106867524A CN201710052663.1A CN201710052663A CN106867524A CN 106867524 A CN106867524 A CN 106867524A CN 201710052663 A CN201710052663 A CN 201710052663A CN 106867524 A CN106867524 A CN 106867524A
- Authority
- CN
- China
- Prior art keywords
- compound
- fluorescent material
- preparation
- blue
- ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000004645 aluminates Chemical class 0.000 title description 3
- 239000000126 substance Substances 0.000 claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 238000003836 solid-state method Methods 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims description 35
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 14
- 229910001422 barium ion Inorganic materials 0.000 claims description 14
- -1 cerium ion Chemical group 0.000 claims description 14
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical group [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 5
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 5
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 5
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 claims description 4
- 229940094800 barium oxalate Drugs 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 6
- 230000005611 electricity Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 12
- 238000002189 fluorescence spectrum Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000009877 rendering Methods 0.000 description 5
- 206010001497 Agitation Diseases 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- 239000005084 Strontium aluminate Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
- C09K11/7721—Aluminates
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention relates to a kind of utilization near ultraviolet excitation and launch the preparation method and application of blue fluorescent material.Its chemical general formula is Ba8‑xCexAl2O11, wherein x is Ce3+The mol ratio of doping, 0.001≤x≤0.4.The present invention can use high temperature solid-state method or chemical synthesis, the fluorescent material for preparing launches the blue-fluorescence of 450 nms under near ultraviolet excitation, can be used as lamp or plasma display fluorescent material, improve its electricity conversion and stability.
Description
Technical field
The invention belongs to the technical field of materials chemistry, and in particular to a kind of preparation of alkaline earth aluminate blue fluorescent material
And application.
Background technology
In recent years, energy shortage and environmental pollution has been the two large problems that the whole mankind must face directly, and energy-saving and emission-reduction are
As the important topic for currently facing.On the other hand, with the improvement of living standards, people are also more next to the demand of artificial light sources
It is higher.And the popularization of artificial light sources and using the embodiment for being also a national economy and living standard, there is data to show, in prosperity
Country, electric consumption on lighting accounts for the 20% of whole power consumption, and has also reached the 12% of total electricity consumption in China.As can be seen here, make
With the illuminator of efficient energy-saving to carrying out energy-saving and emission-reduction, with very big help, and its most important thing is exactly to develop new
Efficient fluorescent material, this behave is by with great economic and social benefit.
White light LEDs obtain luminous efficiency higher with low energy consumption, are novel Energy -- Saving Illuminating Sources.Additionally, wide at present
The general electricity-saving lamp for using, all easily harm is brought in its fluorescent tube containing the chemical substance mercury of pollution environment to environment.And white light
LED produces environmentally harmful chemical substance during production and use, not, thus is known as a kind of " environmental protection "
Lighting apparatus.And fluorescent material is the important component of white light LEDs, outstanding fluorescent material can improve LED colour rendering index,
The performance indications such as luminous efficiency, service life.And fluorescent material is usually to be made up of host doped rare earth element, rare earth element because
Possess the electronic structure of uniqueness for it so that fluorescent material has stronger absorbability, conversion efficiency high, particularly 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, its
Colour rendering is best；Also it is exactly the combination of blue-ray LED and yellow fluorescent powder.
Ce is No. second element of group of the lanthanides, its 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 because its 5d energy levels are very low, and 4f energy levels are higher, therefore
Generation group-overlap, so 5d states of having been arrived after they are excited.Due to lacking shielding, 5d states are easily influenceed by crystal field, therefore,
In different crystalline environments, electronics can produce the transmitting of different wave length, institute when returning 4f ground state from its minimum 5d tracks transition
With Ce3+The material of doping is of great interest.Using Ce3+The wide scope fluorescent material that is made of transmitting, can apply to
Ion FPD PDP, the phosphor of rare earth, for the light-converting material of agricultural；Further, since Ce3+Transition be electricity
What dipole was allowed, therefore the luminescent lifetime of cerium ion is very of short duration, typically in 10~1000 nanoseconds, using the property, adulterate Ce3+
Material can also be made fast scintillation crystal medically.
In addition, based on the requirement to sight protectio and color reproducibility, compared to outdoor road lamp, engineering illumination and scape
See for decoration single 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 excite yellow fluorescent powder using LED chip transmitting blue light, are produced by gold-tinted and blue light
Raw white light.This white light in emission spectrum due to not having red spectral components, although can be by increasing the reduction of yellow spectrum ratio
Colour temperature, but regulation gold-tinted and blue light ratio cannot all improve colour rendering index in any case.Using this colour rendering index than relatively low
Light source, can cause cross-color, i.e. irradiated object color appear to it is inconsistent with actual color.For this someone carries
Go out, excite three primary colors fluorescent powder using near ultraviolet wavelength to obtain LED white lights.This mode coordinates relative to LED chip blue light
For the white light that fluorescent material is produced, although can sacrifice certain luminous efficiency, but obtained white light colourity is preferably, including colour gamut and color
Rank.
Because the photon energy of blue light is higher, compared to red and green emitting phosphor, the synthesis of blue colour fluorescent powder
Poor-performing, is mainly manifested in that light decay is big, light leads to 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 extensive
Blue fluorescent material, in 450nm or so, with good excitation, luminous efficiency is also high, but BAM for its emission peak wavelength
Heat resistanceheat resistant stability is poor, and performance degradation can occur in use, and glow color is easily raised and floated with LED component operating temperature
Move.(Sr, Ba, Ca)5(PO4)3Cl:Eu2+Due to containing chlorine element, being difficult to control to during synthesis in fluorescent material, and the chloride of generation is given up
Gas is larger to environmental injury.Sr4Al14O25:Eu2+In 490nm or so, one is launch wavelength glimmering with preferable blueness to emission peak
Luminescent material 450-460nm differences are more, cause matched somebody with somebody white light color saturation relatively low, and two is relatively low luminous efficiency.Therefore, visit
A kind of blue-fluorescence powder material of good combination property of rope, development and application for promoting near ultraviolet LED undoubtedly have great meaning
Justice.
The content of the invention
Meaning of the present invention is to provide a kind of white light LEDs that can realize black light switching emission blue-fluorescence with glimmering
Luminescent material Ba8-xCexAl2O11Compound, and its application for fluorescent material and preparation method.It is to be solved by this invention
Technical problem is to improve the luminous efficiency of fluorescent material, chemical stability and stability of photoluminescence；Preparation technology is difficult to control to and produces
The problems such as raw chlorine contained exhaust gas are larger to environmental injury.
To solve above technical problem, the technical solution adopted by the present invention is：
On the one hand, the present invention provides a kind of material of black light switching emission blue-fluorescence, and it is in 365 nms
Launch the blue-fluorescence of 450 nms under near ultraviolet excitation；The chemical general formula of the material is Ba8-xCexAl2O11, wherein
X is cerium ion Ce3+The mol ratio of doping, 0.001≤x≤0.4.
On the one hand, it is Ba that the present invention provides formula8-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 mol ratio of doping, 0.001
≤x≤0.4；Described blue fluorescent material is a kind of material of black light switching emission blue-fluorescence, in 365 nms
Near ultraviolet excitation under launch the blue-fluorescence of 450 nms.
On the other hand, the present invention provides Formula B a8-xCexAl2O11The preparation method of compound, can use high temperature solid-state
It is prepared by method or chemical synthesis.
Wherein, above-mentioned high temperature solid-state method preparation method comprises the following steps：
By chemical formula Ba8-xCexAl2O11The stoichiometric proportion 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 well mixed；
The mixture that step (1) is obtained is calcined 1~2 time in air atmosphere；The calcining heat is 300~600 DEG C,
Calcination time is 1~15 hour；
The mixture that step (2) is obtained is cooled to room temperature, after being ground and be well mixed by the method for step (1) again,
Calcine in air atmosphere, calcining heat is 600~1000 DEG C, calcination time is 1~12 hour；
The mixture natural cooling that step (3) is obtained, after ground and mixed is uniform, calcines in atmosphere, and calcining heat is
1000~1350 DEG C, calcination time is 1~12 hour, is then slowly cooled to room temperature, obtains one kind and realizes that black light is changed
Launch the material of blue-fluorescence.
Preferably, high temperature solid-state method preparation method includes：
By chemical formula Ba8-xCexAl2O11The stoichiometric proportion 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 well mixed；
The mixture that step (1) is obtained is calcined 1~2 time in air atmosphere；The calcining heat is 350~550 DEG C,
Calcination time is 2~10 hours；
The mixture that step (2) is obtained is cooled to room temperature, after being ground and be well mixed by the method for step (1) again,
Calcine in air atmosphere, calcining heat is 650~950 DEG C, calcination time is 2~10 hours；
The mixture natural cooling that step (3) is obtained, after ground and mixed is uniform, calcines in atmosphere, and calcining heat is
1050~1300 DEG C, calcination time is 2~10 hours, is then slowly cooled to room temperature, obtains one kind and realizes that black light is changed
Launch the material of blue-fluorescence.
Wherein, above-mentioned chemical synthesis comprises the following steps：
According to chemical formula Ba8-xCexAl2O11The stoichiometric proportion of middle each element, wherein 0.0001≤x≤0.4, weighs and contain
There is the compound of corresponding ion, respectively contain cerium ion Ce3+Compound, contain barium ions Ba2+Compound, contain aluminium
Ion A l3+Compound, during they are dissolved separately in into deionized water or dilute nitric acid solution, obtain clear solution；Meanwhile, weigh
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；
Lentamente the solution of ion containing needed in step (1) is mixed, 2~3 are stirred under 60~100 DEG C of temperature conditionss
After hour, it is placed in baking oven and dries, obtains fluffy presoma；
Presoma obtained by step (2) is placed in Muffle furnace and is calcined, temperature is 900~1200 DEG C, the time is 2~12 small
When, room temperature is naturally cooled to, obtain a kind of material for realizing black light switching emission blue-fluorescence.
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 kind in O；Contain barium ions Ba2+Change
Compound is barium nitrate Ba (NO3)2, barium carbonate BaCO3, barium hydroxide Ba (OH)2, barium oxalate C2BaO4In one kind；Containing aluminium from
Sub- Al3+Compound be aluminium oxide Al2O3, aluminum nitrate Al (NO3)3·9H2O, aluminium hydroxide Al (OH)3In one kind.
On the other hand, the formula that the present invention is provided is Ba8-xCexAl2O11Compound be used for white light LEDs, plasma and show
The fluorescent material of device.
Compared with prior art, technical solution of the present invention has advantages below to the present invention：
(1) indigo plant of 450 nms is launched under a kind of near ultraviolet excitation that can realize 365 nms of the invention
Color fluorescent material, it is high with luminous efficiency, chemical stability and hair light and heat stability the features such as, white light can be efficiently applied to
The fluorescent material of LED, while having the advantages that the light-converting material stable performance of synthesis.
(2) preparation process is simple of above-mentioned fluorescent material is provided, raw material sources are wide, and during synthesis, without special high temperature, high pressure
Equipment, process is simple, low production cost, obtained sample particle is tiny and Stability Analysis of Structures.
(3) present invention in process of production without waste gas and waste liquid discharge (as and Sr, Ba, Ca)5(PO4)3Cl:Eu2+Preparation
Compare, the discharge without chlorine contained exhaust gas), to environment fanout free region, and fluorescent material Ba8-xCexAl2O11Itself it is also a kind of environment-friendly
Inorganic material, will not in use decompose to give off harmful substance.
Brief description of the drawings
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 in the case where 346 nano wave lengths are excited；
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 in the case where 365 nano wave lengths are excited；
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 proportion of middle each element, weighs barium carbonate BaCO respectively3：
6.314 grams, aluminium oxide Al2O3：0.41 gram, cerium oxide CeO2：0.0007 gram, it is placed in agate mortar and adds and be appropriate anhydrous
Ethanol mixed grinding half an hour, it is to be mixed it is uniform after, sample is placed in carries out precalcining in Muffle furnace.Precalcining condition is：
Air atmosphere, 350 DEG C of calcining heat, calcination time 2 hours.Then room temperature is naturally cooled to, sample is taken out by the original of precalcining
Material is fully ground with identical method again, is well mixed, and is calcined again in air atmosphere, is sintered 2 hours at 650 DEG C, cold
But to room temperature, and it is ground again, among air atmosphere, is sintered 2 hours at 1350 DEG C, room temperature is cooled to, after taking-up
It is fully ground and obtains sample.
It is X-ray powder diffraction pattern that the present embodiment technical scheme prepares sample referring to accompanying drawing 1；XRD test results show
Show, prepared sample crystallinity is preferable, without other dephasigns.
It is excitation spectrum of the sample prepared by the present embodiment technical scheme under the monitoring of 440 nano wave lengths referring to accompanying drawing 2
Figure and the luminescent spectrum figure in the case where 346 nano wave lengths are excited；As seen from the figure, the sample under the exciting 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 halfwidth wider, obtained
Black light effectively can be converted to blue-fluorescence by material.
It is decay of luminescence curve that embodiment of the present invention technical scheme prepares sample, when can be calculated decay referring to accompanying drawing 3
Between be 270.8 nanoseconds.
It is SEM figures that embodiment of the present invention technical scheme prepares sample referring to accompanying drawing 5.
Embodiment 2
According to chemical formula Ba7.995Ce0.005Al2O11The stoichiometric proportion of middle each element, weighs barium carbonate BaCO respectively3：
6.31 grams, ANN aluminium nitrate nonahydrate Al (NO3)3·9H2O：3 grams, cerium oxide CeO2：0.0035 gram, added in agate mortar appropriate
After ethanol mixed grinding is uniform, precalcining is carried out in air atmosphere, after calcining furnace cooling in 4 hours at 450 DEG C, take out sample
Again be fully ground the raw material of precalcining with identical method by product, is calcined again in air atmosphere, 3 is sintered at 800 DEG C small
When, room temperature is cooled to, take out sample.Finally sample is fully ground and is mixed again, in air atmosphere, is sintered at 1300 DEG C
4 hours, room temperature is cooled to, is fully ground after taking-up and obtains sample.
The present embodiment technical scheme prepares X-ray powder diffraction pattern, exciting light spectrogram, fluorescence spectra, the hair of sample
Optical attenuation curve, SEM figures are consistent with the sample prepared in embodiment 1.
Embodiment 3
According to chemical formula Ba7.993Ce0.007Al2O11The stoichiometric proportion 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, add appropriate ethanol to mix in agate mortar and grind
After mill is uniform, precalcining is carried out in air atmosphere, after calcining 4 hours natural coolings at 500 DEG C, take out sample by precalcining
Raw material be fully ground and mixed with identical method again, calcined again in air atmosphere, at 850 DEG C sinter 5 hours, it is cold
But sample is taken out afterwards.Most sample carries out third time grinding at last, is placed in Muffle furnace after mixing, is burnt at 1250 DEG C in air atmosphere
Knot 6 hours, is cooled to room temperature, is fully ground after taking-up and obtains sample.
The present embodiment technical scheme prepares X-ray powder diffraction pattern, exciting light spectrogram, fluorescence spectra, the hair of sample
Optical attenuation curve, SEM figures are consistent with the sample prepared in embodiment 1.
Embodiment 4
According to chemical formula Ba7.99Ce0.01Al2O11The stoichiometric proportion 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, added in agate mortar appropriate without watery wine
After smart mixed grinding is uniform, precalcining is carried out in air atmosphere, at 600 DEG C calcine 6 hours and etc. Muffle furnace natural cooling
Afterwards, take out sample the raw material of precalcining is fully ground and is mixed with identical method again, calcined again in air atmosphere,
Sintered 8 hours at 900 DEG C, take out sample.Compound 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 scheme prepares X-ray powder diffraction pattern, exciting light spectrogram, fluorescence spectra, the hair of sample
Optical attenuation curve, SEM figures are consistent with the sample prepared in embodiment 1.
Embodiment 5
According to chemical formula Ba7.95Ce0.05Al2O11The stoichiometric proportion of middle each element, weighs barium oxalate BaC respectively2O4：
7.17 grams, aluminium oxide Al2O3：0.41 gram, cerium oxide CeO2：0.035 gram, appropriate absolute ethyl alcohol is added to mix in 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, and 10 are sintered at 950 DEG C
Hour, room temperature is naturally cooled to, take out sample.Finally compound is fully ground and is mixed again, is placed in Muffle furnace, in sky
Sintered 10 hours at lower 1300 DEG C of gas atmosphere, be cooled to room temperature, be fully ground after taking-up and obtain sample.
The present embodiment technical scheme prepares X-ray powder diffraction pattern, exciting light spectrogram, fluorescence spectra, the hair of sample
Optical attenuation curve, SEM figures are consistent with the sample prepared in embodiment 1.
Embodiment 6
According to chemical formula Ba7.93Ce0.07Al2O11The stoichiometric proportion of middle each element, weighs barium nitrate Ba (NO respectively3)2：
2.07 grams, ANN aluminium nitrate nonahydrate Al (NO3)3·9H2O：0.75 gram, six nitric hydrate cerium Ce (NO3)3·6H2O：0.03 gram, and
The citric acid of the 1.8wt% of each drug quality of the above.Barium nitrate Ba (the NO that will be weighed3)2, aluminum nitrate Al (NO3)3·9H2O, nitre
Sour cerium Ce (NO3)3·6H2O is dissolved in appropriate deionized water together, and adds the citric acid for weighing, the magnetic under 80 DEG C of water-baths
Power stirring a period of time obtains settled solution, after most above-mentioned solution is mixed 2 hours in 80 DEG C at last, is positioned in baking oven,
Design 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 it is 1100 DEG C, calcination time is 2 hours, is cooled to room temperature, takes out and is fully ground and obtains sample.
It is X-ray powder diffraction pattern and corresponding standard that the present embodiment technical scheme prepares sample referring to accompanying drawing 5
PDF cards；XRD test results show that prepared sample crystallinity is phase pure material very well.
It is excitation spectrum of the sample prepared by the present embodiment technical scheme under the monitoring of 450 nano wave lengths referring to accompanying drawing 6
With excited in 365 nano wave lengths under fluorescence spectra.As seen from the figure, obtained material equally can effectively by black light
Be converted to blue light.
It is decay of luminescence curve that embodiment of the present invention technical scheme prepares sample, when can be calculated decay referring to accompanying drawing 7
Between be 245.4 nanoseconds.
It is SEM figures that embodiment of the present invention technical scheme prepares sample referring to accompanying drawing 8.
Embodiment 7
According to chemical formula Ba7.9Ce0.1Al2O11The stoichiometric proportion of middle each element, weighs barium hydroxide Ba (OH) respectively2：
2.7 grams, cerous nitrate Ce (NO3)3·6H2O：0.087 gram, aluminum nitrate Al (NO3)3·9H2O：1.5 grams, and each medicine matter above
The citric acid of the 1.8wt% of amount.The barium hydroxide Ba (OH) that will be weighed2, cerous nitrate Ce (NO3)3·6H2O, aluminum nitrate Al
(NO3)3·9H2O is dissolved separately in appropriate deionized water, and adds the 60 DEG C of magnetic agitations of citric acid for weighing for a period of time
Settled solution is obtained, after most above-mentioned solution is mixed 2 hours in 60 DEG C at last, is placed in baking oven, design 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 scheme prepares X-ray powder diffraction pattern, exciting light spectrogram, fluorescence spectra, the hair of sample
Optical attenuation curve, SEM figures are consistent with the sample prepared in embodiment 6.
Embodiment 8
According to chemical formula Ba7.8Ce0.2Al2O11The stoichiometric proportion 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 gram, and each drug quality above
1.8wt% citric acid.The sample that will be weighed is dissolved separately in appropriate dust technology, and adds 60 DEG C of the citric acid for weighing
Magnetic agitation obtains settled solution for a period of time, after most above-mentioned solution is mixed 2 hours in 60 DEG C at last, in placement baking oven,
Design temperature is 80 DEG C, is dried 12 hours, natural cooling, takes out presoma, and precursor is placed in into calcining in Muffle furnace, sintering temperature
It is 1150 DEG C to spend, and calcination time is 5 hours, is cooled to room temperature, takes out and is fully ground and obtains sample.
The present embodiment technical scheme prepares X-ray powder diffraction pattern, exciting light spectrogram, fluorescence spectra, the hair of sample
Optical attenuation curve, SEM figures are consistent with the sample prepared in embodiment 6.
Embodiment 9
According to chemical formula Ba7.7Ce0.3Al2O11The stoichiometric proportion 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 gram, and each drug quality of the above
The citric acid of 1.8wt%.The sample weighed by more than is dissolved separately in appropriate dust technology, and magnetic agitation is obtained for a period of time
Settled solution, after most above-mentioned solution is mixed 2 hours in 60 DEG C at last, places in baking oven, and design temperature is 80 DEG C, dries 12 small
When, natural cooling takes out presoma, precursor is placed in Muffle furnace and is calcined, and sintering temperature is 1200 DEG C, and calcination time is 6
Hour, room temperature is cooled to, take out and be fully ground and obtain sample.
The present embodiment technical scheme prepares X-ray powder diffraction pattern, exciting light spectrogram, fluorescence spectra, the hair of sample
Optical attenuation curve, SEM figures are consistent with the sample prepared in embodiment 6.
Embodiment 10
According to chemical formula Ba7.6Ce0.4Al2O11The stoichiometric proportion 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.By more than
The sample for weighing is dissolved separately in appropriate dust technology, and magnetic agitation obtains settled solution for a period of time, most above-mentioned molten at last
After liquid is mixed 2 hours in 60 DEG C, place in baking oven, design temperature is 80 DEG C, is dried 12 hours, natural cooling, takes out forerunner
Body, precursor is placed in Muffle furnace and is calcined, and sintering temperature is 1200 DEG C, and calcination time is 8 hours, is cooled to room temperature, is taken out
And be fully ground and obtain sample.
Technical scheme in the present embodiment prepares X-ray powder diffraction pattern, exciting light spectrogram, the fluorescence spectrum of sample
Figure, decay of luminescence curve, SEM figure are consistent with the sample prepared in embodiment 6.
Claims (10)
1. formula is Ba8-xCexAl2O11Compound be used for fluorescent material application, it is characterised in that：Described fluorescent material is
A kind of blue fluorescent material, Formula B a8-xCexAl2O11In, x is cerium ion Ce3+The mol ratio of doping, 0.001≤x≤0.4.
2. formula as claimed in claim 1 is Ba8-xCexAl2O11Compound be used for the application of fluorescent material, its feature exists
In described blue fluorescent material is a kind of material of black light switching emission blue-fluorescence, in the nearly purple of 365 nms
Outer light excites the blue-fluorescence of 450 nms of lower transmitting.
3. a kind of Ba as described in claims 1 to 2 are any8-xCexAl2O11Preparation method, it is characterised in that use high temperature
It is prepared by solid phase method or chemical synthesis.
4. Ba as claimed in claim 38-xCexAl2O11Preparation method, it is characterised in that described high temperature solid-state method include such as
Lower step：
(1) by chemical formula Ba8-xCexAl2O11The stoichiometric proportion 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, make sample mix
Close uniform；
(2) mixture that step (1) is obtained is calcined 1~2 time in air atmosphere；The calcining heat is 300~600 DEG C,
Calcination time is 1~15 hour；
(3) mixture that step (2) is obtained is cooled to room temperature, after being ground and be well mixed by the method for step (1) again,
Calcined under air atmosphere, calcining heat is 600~1000 DEG C, calcination time is 1~12 hour；
(4) the mixture natural cooling for obtaining step (3), after ground and mixed is uniform, calcines in atmosphere, and calcining heat is
1000~1350 DEG C, calcination time is 1~12 hour, is then slowly cooled to room temperature, obtains one kind and realizes that black light is changed
Launch the material of blue-fluorescence.
5. Ba as claimed in claim 48-xCexAl2O11Preparation method, it is characterised in that：The calcining temperature of described step (2)
It is 350~550 DEG C to spend, and calcination time is 2~10 hours.
6. Ba as claimed in claim 48-xCexAl2O11Preparation method, it is characterised in that：The calcining temperature of described step (3)
It is 650~950 DEG C to spend, and calcination time is 2~10 hours.
7. Ba as claimed in claim 48-xCexAl2O11Preparation method, it is characterised in that：The calcining temperature of described step (4)
It is 1050~1300 DEG C to spend, and calcination time is 2~10 hours.
8. Ba as claimed in claim 38-xCexAl2O11Preparation method, it is characterised in that described chemical synthesis include such as
Lower step：(1) according to chemical formula Ba8-xCexAl2O11The stoichiometric proportion of middle each element, wherein 0.0001≤x≤0.4, weighs
Compound containing corresponding ion, respectively contains cerium ion Ce3+Compound, contain barium ions Ba2+Compound, contain
Aluminium ion Al3+Compound, during they are dissolved separately in into deionized water or dilute nitric acid solution, obtain clear solution；Meanwhile, claim
The complexing agent citric acid of 1.0~2.0wt% of each reactant quality is taken, is respectively added in each solution, in 60~90 DEG C of temperature
Degree lower stirring a period of time；
(2) lentamente the solution of ion containing needed in step (1) is mixed, 2~3 is stirred under 60~100 DEG C of temperature conditionss
After hour, it is placed in baking oven and dries, obtains fluffy presoma；
(3) presoma obtained by step (2) is placed in Muffle furnace and is calcined, temperature is 900~1200 DEG C, the time is 2~12 small
When, room temperature is naturally cooled to, obtain a kind of material for realizing black light switching emission blue-fluorescence.
9. the Ba as described in claims 4 or 8 are any8-xCexAl2O11Preparation method, it is characterised in that：Described contains cerium
Ion Ce3+Compound be cerium oxide CeO2, cerous nitrate Ce (NO3)3·6H2One kind in O；Contain barium ions Ba2+Compound
It is barium nitrate Ba (NO3)2, barium carbonate BaCO3, barium hydroxide Ba (OH)2, barium oxalate C2BaO4In one kind；Contain aluminium ion Al3+
Compound be aluminium oxide Al2O3, aluminum nitrate Al (NO3)3·9H2O, aluminium hydroxide Al (OH)3In one kind.
10. formula as claimed in claim 1 is Ba8-xCexAl2O11Compound be used for the application of fluorescent material, its feature exists
In：Described application is the fluorescent material for white light LEDs, plasma display.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710052663.1A CN106867524B (en) | 2017-01-22 | 2017-01-22 | A kind of preparation and application of alkaline earth aluminate blue fluorescent material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710052663.1A CN106867524B (en) | 2017-01-22 | 2017-01-22 | A kind of preparation and application of alkaline earth aluminate blue fluorescent material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106867524A true CN106867524A (en) | 2017-06-20 |
| CN106867524B CN106867524B (en) | 2019-11-05 |
Family
ID=59158248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710052663.1A Active CN106867524B (en) | 2017-01-22 | 2017-01-22 | A kind of preparation and application of alkaline earth aluminate blue fluorescent material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106867524B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116023934A (en) * | 2022-11-01 | 2023-04-28 | 吉林化工学院 | Blue fluorescent powder for plant light supplementing and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419799A (en) * | 2015-12-23 | 2016-03-23 | 江苏师范大学 | Preparation method and application of material for converting near ultraviolet light to emit red fluorescence |
-
2017
- 2017-01-22 CN CN201710052663.1A patent/CN106867524B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419799A (en) * | 2015-12-23 | 2016-03-23 | 江苏师范大学 | Preparation method and application of material for converting near ultraviolet light to emit red fluorescence |
Non-Patent Citations (2)
| Title |
|---|
| D. JIA ET AL.: "Site dependent thermoluminescence of long persistent phosphorescence of BaAl2O4:Ce3+", 《OPTICS COMMUNICATIONS》 * |
| RUI ZHANG ET AL.: "A phase equilibria study and thermodynamic assessment of the BaO-Al2O3 system", 《CALPHAD: COMPUTER COUPLING OF PHASE DIAGRAMS AND THERMOCHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116023934A (en) * | 2022-11-01 | 2023-04-28 | 吉林化工学院 | Blue fluorescent powder for plant light supplementing and preparation method thereof |
| CN116023934B (en) * | 2022-11-01 | 2023-11-03 | 吉林化工学院 | Blue fluorescent powder for plant light supplementing and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106867524B (en) | 2019-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111196925A (en) | Mn4+Doped red fluorescent material and preparation method thereof | |
| CN105419799B (en) | Preparation method and application of material for converting near ultraviolet light to emit red fluorescence | |
| CN102585831B (en) | Europium-ion-excited fluoromolybdate red fluorescent powder and preparation method and application thereof | |
| CN102585819B (en) | Lanthanum boron tungstate red fluorescent powder and preparation method thereof | |
| WO2013074158A1 (en) | Green and yellow aluminate phosphors | |
| CN106833636B (en) | It can be by near ultraviolet and blue light activated red fluorescence powder, preparation method and application | |
| CN106635017B (en) | Titanate-based red fluorescent powder and preparation method thereof | |
| CN103122244B (en) | Eu<2+> activated silicate white light fluorescent powder and preparation method thereof | |
| Zhu et al. | Luminescence characteristics of SrZnSO: M (M= Bi3+, Mn2+ and Tb3+) phosphors | |
| CN104073255A (en) | Zirconium silicate salt blue fluorescent powder, preparation method and application thereof | |
| CN103305216A (en) | Borate red fluorescent powder and preparation method and application thereof | |
| CN103275713A (en) | Rare earth molybdate red phosphor, and preparation method and application thereof | |
| CN103254895A (en) | Aluminosilicate green fluorescent powder and preparation method thereof | |
| CN103396796B (en) | Antimonate long-afterglow fluorescent powder and preparation method thereof | |
| CN105368450A (en) | Double-perovskite tungstate white light phosphor and preparation method thereof | |
| CN102942928B (en) | Zirconate-base red phosphor, method for preparing same and application | |
| EP2565253B1 (en) | Silicate luminescent material and production method thereof | |
| CN108276998B (en) | Trivalent samarium ion doped barium gadolinium titanate red fluorescent powder and preparation method thereof | |
| CN106867524B (en) | A kind of preparation and application of alkaline earth aluminate blue fluorescent material | |
| CN113549458B (en) | High-color-rendering trivalent Eu ion-doped red fluorescent material based on apatite structure and preparation method thereof | |
| CN105860971B (en) | Rare earth ion doped zirconium niobate fluorescent powder and preparation method thereof | |
| CN108587621A (en) | A kind of ultraviolet or near ultraviolet excitated white light LEDs Color tunable silicate fluorescent powder and preparation method thereof | |
| CN104804731B (en) | Magnesium silicate potassium blue-green fluorescent powder that a kind of Eu2+ activates and its preparation method and application | |
| CN109294583B (en) | Cerium ion doped barium gadolinium titanate blue fluorescent powder for white light LED and preparation method thereof | |
| CN105524615A (en) | Niobate red phosphor for white-light LEDs and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20170620 Assignee: Jiangsu Jingjin Environmental Protection Technology Co.,Ltd. Assignor: Jiangsu Normal University Contract record no.: X2023320000066 Denomination of invention: Preparation and application of a kind of alkaline earth aluminate blue fluorescent material Granted publication date: 20191105 License type: Common License Record date: 20230116 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Jiangsu Jingjin Environmental Protection Technology Co.,Ltd. Assignor: Jiangsu Normal University Contract record no.: X2023320000066 Date of cancellation: 20230625 |
|
| EC01 | Cancellation of recordation of patent licensing contract |