CN107099291A - It is a kind of can be by the red fluorescence material of near ultraviolet excitation, preparation method and application - Google Patents
It is a kind of can be by the red fluorescence material of near ultraviolet excitation, preparation method and application Download PDFInfo
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- CN107099291A CN107099291A CN201710196254.9A CN201710196254A CN107099291A CN 107099291 A CN107099291 A CN 107099291A CN 201710196254 A CN201710196254 A CN 201710196254A CN 107099291 A CN107099291 A CN 107099291A
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- europium
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 230000005284 excitation Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- -1 rare-earth europium ion Chemical group 0.000 claims abstract description 33
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 24
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000010955 niobium Substances 0.000 claims description 63
- 239000010936 titanium Substances 0.000 claims description 53
- 238000001354 calcination Methods 0.000 claims description 46
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 40
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 31
- 239000011575 calcium Substances 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 21
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 14
- 229960000583 acetic acid Drugs 0.000 claims description 12
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012362 glacial acetic acid Substances 0.000 claims description 12
- 229910052758 niobium Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910001940 europium oxide Inorganic materials 0.000 claims description 11
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 11
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 11
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 9
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 5
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 229910019804 NbCl5 Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000003836 solid-state method Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000009877 rendering Methods 0.000 abstract description 4
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 abstract description 2
- 235000006484 Paeonia officinalis Nutrition 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 241000736199 Paeonia Species 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 12
- 238000000695 excitation spectrum Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 6
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- 244000170916 Paeonia officinalis Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
Can be by the red fluorescence material of near ultraviolet excitation, preparation method and application, its chemical formula the invention discloses a kind of：Ca5‑5xEu5xNb4Ti3O21, wherein x is rare-earth europium ion Eu3+Replace the mol ratio of Ca ions, and 0.0001≤x≤0.20.The present invention in exciting light in 350 420 nanometers of near ultraviolet region, can emission peak be located at the feux rouges of 615 rans, its luminous chromaticity coordinate value is x=0.625 0.655, and y=0.345 0.375 red, colourity is pure；The near ultraviolet semiconductor chips such as excitation wavelength and InAlGaN, InGaAs are matched very much, can be used as the peony component in multiple bases energy-conservation fluorescence light source LED and WLED, with modulated light source colour temperature and improve colour rendering index.Matrix stablizes corrosion-resistant, and luminous efficiency is high, Nonpoisonous, non-environmental-pollution；Preparation method is simply easily operated, not high to working condition and equipment requirement, and cost is low, without any pollution, suitable for industrialized production.
Description
Technical field
It can belong to luminous by the red fluorescence material of near ultraviolet excitation, preparation method and application the present invention relates to a kind of
Material and display technology field.
Background technology
White light LEDs are emerging green lighting techniques, with powerful development potentiality.With incandescent lamp compared with fluorescent lamp,
White light LEDs are more energy efficient：The energy consumption of white light LEDs is only the 1/8 of incandescent lamp, the 1/2 of electricity-saving lamp；Long lifespan：More than 100000 hours；Can
To be operated in fast state：If electricity-saving lamp, which frequently starts or turned off filament, will black breaking down quickly；Environmental protection：Discarded object
It is recyclable, do not pollute；It is easy to prepare：Solid encapsulation, is not afraid of vibration, does not need substantially to consider radiating etc..Now use
White LEDs mainly combine to be formed based on white light with blue-ray LED and YAG fluorescent powder：By red fluorescence powder and yellow fluorescence YAG：Ce
Mixing, and combined with InGaN blue chips and can obtain the required white light of people.Although LED has very big in terms of quality and quantity
Progress, but there is also some key issues, maximum defect is exactly that colour rendering index is relatively low, and colour rendering index is preferably only left 85
The right side, is proved by numerous studies, and the luminosity for being primarily due to LED red light regions is bad caused.Therefore, red fluorescence powder is increasingly
Receive the concern of researchers.
On the other hand, although have been developed that some red fluorescence powders at present, but it is most of be (to be less than 365 ultraviolet
Nanometer) under excite, its with blue chip (excitation area is typically at 380-470 nanometer) mismatch so can not stably meet
Application demand in WLEDs, therefore the red fluorescence powder that can be effectively excited by black light at this stage is fewer, and stability and
Luminous efficiency is not high, and common fluorescent material can also produce the toxic gases such as sulfide under uv irradiation in addition, and environment is made
Into harm, the cost that it is made trouble, producing process is spent is also higher.Therefore the good red fluorescence powder of research performance not only has
Certain theory significance, with more important practical application meaning.
The content of the invention
In view of the above-mentioned problems of the prior art, the present invention first purpose be to provide one kind can be by black light
Effectively excite, stability is good, luminous mass is high and the fluorescent material of free of contamination transmitting feux rouges, another object of the present invention is to
There is provided the preparation method of above-mentioned fluorescent material, it is ensured that simple to operate, cost is low and favorable repeatability, third object of the present invention
It is the application that above-mentioned fluorescent material is provided.
For to object above, the technical solution adopted by the present invention is：It is a kind of can be by the red fluorescence material of near ultraviolet excitation
Expect, chemical general formula is：Ca5-5xEu5xNb4Ti3O21, wherein x is europium ion Eu3+Replace the mol ratio of Ca ions, and 0.0001≤x
≤0.20。
It can be used present invention also offers a kind of above-mentioned by the preparation method of the red fluorescence material of near ultraviolet excitation
High temperature solid-state method, comprises the following steps：
(1) formula Ca is pressed5-5xEu5xNb4Ti3O21, the stoichiometric proportion of corresponding element, which is weighed, in 0.0001≤x≤0.20 contains
There is calcium ion Ca2+Compound, contain europium ion Eu3+Compound, contain niobium ion Nb5+Compound, contain titanium ion
Ti4+Compound for prepare raw material, the raw material weighed is ground respectively, be well mixed；
(2) mixture for obtaining step (1) is pre-sintered 1~2 time in air atmosphere, and sintering temperature is 900~1200
DEG C, sintering time is 1~10 hour；
(3) by after the mixture natural cooling of step (2), grinding is uniform, is calcined in air atmosphere, and calcining heat is
1200~1400 DEG C, calcination time is 1~15 hour, you can obtain red fluorescence material.
In the above method, described calcium ions Ca2+Compound be calcium carbonate CaCO3, calcium chloride CaCl2, calcium nitrate
Ca(NO3)2, one kind in calcium oxide CaO；Described contains europium ion Eu3+Compound be europium oxide Eu2O3, europium nitrate Eu
(NO3)3·6H2One kind in O；Described contains niobium ion Nb5+Compound be niobium pentaoxide Nb2O5, columbium pentachloride NbCl5
In one kind；Described contains titanium ion Ti4+Compound be titanium dioxide TiO2。
It is preferred that, the calcining heat of step (3) is 1250~1350 DEG C, and calcination time is 5~8 hours.
Present invention also offers it is another it is above-mentioned can by the preparation method of the red fluorescence material of near ultraviolet excitation, including
Following steps：
(1) chemical formula Ca is pressed5-5xEu5xNb4Ti3O21, the stoichiometric proportion of each element in 0.0001≤x≤0.20, respectively
Weigh：Contain calcium ion Ca2+Compound, contain europium ion Eu3+Compound, contain niobium ion Nb5+Compound, contain
Titanium ion Ti4+Compound be preparing raw material；
(2) step (1) is contained into calcium ion Ca2+Compound, contain europium ion Eu3+Compound, contain niobium ion Nb5+
Compound be dissolved separately in deionized water or be dissolved in nitric acid and diluted with deionized water；Titanium ion Ti will be contained4+
Compound mix and be dissolved into glacial acetic acid and then be added drop-wise to again in ethanol, regulation pH value stirs to be formed between 2-4
Bright colloidal sol；Ion mole 1.5 is added into various solution respectively again to 2 times of complexing agent, calcium ions Ca is respectively obtained2+
, europium ion Eu3+, niobium ion Nb5+, titanium ion Ti4+Solution, described complexing agent is one in citric acid, oxalic acid
Kind；
(3) above-mentioned various solution are mixed, temperature stands, dried to be stirred 1~5 hour under conditions of 50~100 DEG C,
Obtain fluffy presoma；
(4) presoma for obtaining step (3) is calcined in air atmosphere, and calcining heat is 400~750 DEG C, during calcining
Between be 1~10 hour；
(5) after the product of step (4) precalcining, natural cooling, grind and be well mixed, forged again in air atmosphere
Burn, calcining heat is 1100~1300 DEG C, and calcination time 1~10 hour obtains a kind of red fluorescence material.
It is preferred that, the calcining heat in step (5) is 1150~1250 DEG C, and calcination time is 3~6 hours.
It is preferred that, described calcium ions Ca2+Compound be calcium carbonate CaCO3, calcium nitrate Ca (NO3)2In one kind；
Described contains europium ion Eu3+Compound be europium oxide Eu2O3, europium nitrate Eu (NO3)3·6H2One kind in O；Described contains
There is niobium ion Nb5+Compound be niobium hydroxide Nb (OH)5；The described compound containing titanium elements is butyl titanate
C16H36O4The mol ratio of Ti, the butyl titanate and ethanol, glacial acetic acid is 1：5-15：0.5-1.5.
Finally, the invention provides it is above-mentioned can be by the application of the red fluorescence material of near ultraviolet excitation, the red is glimmering
Luminescent material in the case where 350-420 nanometers of near ultraviolet excitated light is excited, can emission peak be located at 615 rans feux rouges, can
To prepare illumination or display device using black light as excitation source；Also can be mixed with appropriate yellow fluorescent powder, coating and
It is packaged in outside InGaN diodes, preparation can send the LED of warm white.
The advantage of technical solution of the present invention is：
(1) present invention has effective light absorbs near ultraviolet and blue region, near for 350-420 nanometers in exciting light
In ultraviolet region, can emission peak be located at 615 rans feux rouges, its luminous chromaticity coordinate value be x=0.625-
0.655, y=0.345-0.375 red, colourity is pure；The near ultraviolet semiconductor core such as excitation wavelength and InAlGaN, InGaAs
Piece is matched very much, and white light LEDs can be prepared by being coated on blue-light LED chip, can be used as multiple bases energy-conservation fluorescence light source LED and
Peony component in WLED, with modulated light source colour temperature and raising colour rendering index.It can be also used for being excited by ultraviolet light and blue light
Other various lighting apparatus in.
(2) in this area, adulterate europium ion Eu in matrix3+When, europium ion Eu3+4f energy levels split in crystalline field
Split, and there is extremely big dependence to crystalline field, the 4f energy levels of division are influenceed by crystalline field is very big, are produced different
, abundant luminescent transition；Europium ion Eu3+Ground state be5D0Energy level, excitation state has7F0-4Different energy level, in different crystal
Among5D0→7F2With different intensity, therefore luminous intensity and color are all influenceed by different substrates, in addition europium ion
Eu3+4f energy levels resonance efficiency it is extremely low, it is difficult to find suitable matrix.The application is by europium ion Eu3+It is doped to
Ca5Nb4Ti3O21In, the red fluorescence powder of uniform granularity, better crystallinity degree is obtained, matrix stablizes corrosion-resistant, and transmitting feux rouges
Efficiency high, colourity is pure；It is environmentally friendly using process, the toxic gases such as sulfide will not be produced under uv irradiation；
(3) preparation technology of the present invention is simple, easily operated, not high to working condition and equipment requirement, and cost is low and can weigh
Renaturation is good；Production process is discharged without waste gas and waste liquid, is a kind of environment-friendly phosphor.
Brief description of the drawings
Fig. 1 prepares material C a by the present embodiment 14.25Eu0.75Nb4Ti3O21X ray diffracting spectrum；
Fig. 2 prepares sample Ca by the present embodiment 14.25Eu0.75Nb4Ti3O21Scanning electron microscopy spectrum；
Fig. 3 presses material C a prepared by the present embodiment 14.25Eu0.75Nb4Ti3O21What is obtained under the monitoring of 615 nano red lights swashs
Luminous spectrum；
Fig. 4 presses material C a prepared by the present embodiment 14.25Eu0.75Nb4Ti3O21Obtained in the case where 395 nanometers of black light is excited
Luminous collection of illustrative plates；
Fig. 5 prepares material C a by the present embodiment 54.75Eu0.25Nb4Ti3O21X ray diffracting spectrum；
Fig. 6 prepares sample Ca by the present embodiment 54.75Eu0.25Nb4Ti3O21Scanning electron microscopy spectrum；
Fig. 7 presses material C a prepared by the present embodiment 54.75Eu0.25Nb4Ti3O21Obtained in the case where 395 nanometers of black light is excited
Luminous collection of illustrative plates；
Fig. 8 presses material C a prepared by the present embodiment 54.75Eu0.25Nb4Ti3O21What is obtained under the monitoring of 615 nano red lights swashs
Luminous spectrum；
Embodiment
Technical solution of the present invention is further described with reference to the accompanying drawings and examples.
Embodiment 1:
According to chemical formula Ca4.25Eu0.75Nb4Ti3O21The stoichiometric proportion of middle each element, weighs calcium carbonate CaCO respectively3:
2.1250 gram；Europium oxide Eu2O3:0.6600 gram；Niobium pentaoxide Nb2O5:2.6580 gram；Titanium dioxide TiO2:1.1981 gram it is
The raw material of preparation, the raw material weighed is ground respectively, is well mixed；The first time pre-burning in air atmosphere of obtained mixture
Knot, sintering temperature is 900 DEG C, and sintering time is 10 hours；Sintered sample grinding is uniform, burns in air atmosphere for the second time
Knot, sintering temperature is 1200 DEG C, and sintering time is 1 hour；It is finally that sample ground and mixed is uniform, calcine in air atmosphere,
Calcining heat is 1400 DEG C, and calcination time is 1 hour, obtains red fluorescence powder.
It is the material C a prepared by the present embodiment technical scheme referring to accompanying drawing 14.25Eu0.75Nb4Ti3O21X-ray diffraction
Collection of illustrative plates, experiment confirms that the material of gained is pure phase, does not have impurity thing phase；
It is the material C a prepared by technical scheme of the embodiment of the present invention referring to accompanying drawing 24.25Eu0.75Nb4Ti3O21Scanning electricity
Gained sample particle better crystallinity degree is shown in the micro- collection of illustrative plates of son, figure；
It is the material C a prepared by the present embodiment technical scheme referring to accompanying drawing 34.25Eu0.75Nb4Ti3O21It is red at 615 nanometers
The excitation spectrum obtained under light detection, it can be seen that luminous excites source main at 395 nanometers, can be well matched with nearly purple
The light that outer diode chip for backlight unit is sent；
It is the material C a prepared by the present embodiment technical scheme referring to accompanying drawing 44.25Eu0.75Nb4Ti3O21In black light 395
Nanometer excites down obtained luminous collection of illustrative plates, it can be seen that the material mainly lights in red spectral band, and the centre of luminescence is located at 615 nanometers
Left and right.
Embodiment 2:
According to chemical formula Ca4.995Eu0.005Nb4Ti3O21The stoichiometric proportion of middle each element, weighs calcium chloride respectively
CaCl2::2.7722 gram；Europium nitrate Eu (NO3)3·6H2O:0.0112 gram；Columbium pentachloride NbCl5:5.4000 gram；Titanium dioxide
TiO2:1.1981 grams are the raw material prepared, and the raw material weighed is ground respectively, are well mixed；Obtained mixture is in air gas
Pre-sintered under atmosphere, sintering temperature is 1100 DEG C, and sintering time is 5 hours；Sintered sample grinding is uniform, in air atmosphere
Calcining, calcining heat is 1200 DEG C, and calcination time is 15 hours, obtains a kind of red fluorescence powder.
The main structural behaviour of sample, excitation spectrum, luminescent spectrum are similar to Example 1.
Embodiment 3:
According to chemical formula Ca4EuNb4Ti3O21The stoichiometric proportion of middle each element, weighs calcium oxide CaO respectively:1.1200
Gram；Europium oxide Eu2O3:0.8800 gram；Niobium pentaoxide Nb2O5:2.6580 gram；Titanium dioxide TiO2:1.1981 gram for prepare
Raw material, the raw material weighed is ground respectively, is well mixed；Obtained mixture is pre-sintered in air atmosphere, and sintering temperature is
1000 DEG C, sintering time is 8 hours；The sample grinding that pre-sintering is crossed is uniform, calcines in air atmosphere again, calcining heat is
1250 DEG C, calcination time is 8 hours, obtains a kind of red fluorescence powder.
The main structural behaviour of sample, excitation spectrum, luminescent spectrum are similar to Example 1.
Embodiment 4:
According to chemical formula Ca4.5Eu0.5Nb4Ti3O21The stoichiometric proportion of middle each element, weighs calcium oxide CaO respectively:
1.2600 gram；Europium oxide Eu2O3:0.4400 gram；Niobium pentaoxide Nb2O5:2.6580 gram；Titanium dioxide TiO2:1.1981 gram；Will
The raw material weighed is ground respectively, is well mixed；Obtained mixture is pre-sintered in air atmosphere, and sintering temperature is 1150 DEG C,
Sintering time is 6 hours；The sample grinding that pre-sintering is crossed is uniform, calcines in air atmosphere again, and calcining heat is 1350 DEG C,
Calcination time is 5 hours, obtains a kind of red fluorescence powder.
The main structural behaviour of sample, excitation spectrum, luminescent spectrum are similar to Example 1.
Embodiment 5:
According to chemical formula Ca4.75Eu0.25Nb4Ti3O21The stoichiometric proportion of middle each element, weighs calcium nitrate Ca respectively
(NO3)2:1.9487 gram；Europium nitrate Eu (NO3)3·6H2O:0.2788 gram；Niobium hydroxide Nb (OH)5:1.7790 gram；The fourth of metatitanic acid four
Ester C16H36O4Ti:2.5500 gram it is used as raw material.By calcium nitrate Ca (NO3)2It is dissolved in deionized water, the lemon of 3.4225 grams of addition
Acid, stirring is until fully transparent；By europium nitrate Eu (NO3)3·6H2O is dissolved in deionized water, adds 0.1801 gram of citric acid,
Stirring is until fully transparent；By niobium hydroxide Nb (OH)5It is placed in deionized water, the citric acid of 2.8821 grams of addition, stirring is straight
It is extremely fully transparent；By butyl titanate C16H36O4Ti and a small amount of glacial acetic acid are mixed, and are then added drop-wise to again in ethanol, are added
2.1616 grams of citric acid, regulation pH value is 2, and stirring forms vitreosol, butyl titanate used and ethanol, glacial acetic acid
Mol ratio is 1：10：1.
Above-mentioned solution is mixed, stirred 5 hours under conditions of temperature is 50 DEG C, stands, dry, obtain fluffy forerunner
Body；The precalcining in air atmosphere by obtained presoma, calcining heat is 750 DEG C, and calcination time is 1 hour, and what is obtained is pre-
The product of calcining；After natural cooling, grind and be well mixed, calcined in air atmosphere, calcining heat is 1300 DEG C, during calcining
Between be 1 hour, obtain red fluorescence powder.
It is to prepare material C a by this implementation technical scheme referring to accompanying drawing 54.75Eu0.25Nb4Ti3O21X-ray diffraction
Collection of illustrative plates, experiment confirms that the material of gained is pure phase, without others impurity thing phase；
It is that present invention implementation technical scheme prepares sample Ca referring to accompanying drawing 64.75Eu0.25Nb4Ti3O21Scanning electron microscopy
Collection of illustrative plates, gained sample particle better crystallinity degree；
It is the material C a prepared by the present embodiment technical scheme referring to accompanying drawing 74.75Eu0.25Nb4Ti3O21In black light
395 nanometers excite down obtained luminous collection of illustrative plates, it can be seen that the material mainly lights in red spectral band, and the centre of luminescence is located at 615
Ran；
It is the material C a prepared by the present embodiment technical scheme referring to accompanying drawing 84.75Eu0.25Nb4Ti3O21It is red at 615 nanometers
The excitation spectrum obtained under light detection, it can be seen that luminous excites source main at 395 nanometers, can be well matched with nearly purple
The light that outer diode chip for backlight unit is sent.
Embodiment 6：
According to chemical formula Ca4.9995Eu0.0005Nb4Ti3O21The stoichiometric proportion of middle each element, weighs calcium carbonate respectively
CaCO3:1.2499 gram；Europium oxide Eu2O3:0.0002 gram；Niobium hydroxide Nb (OH)5:1.7790 gram；Butyl titanate
C16H36O4Ti:2.5500 gram it is used as raw material.By calcium carbonate CaCO3Dust technology is dissolved in, the oxalic acid of 2.2508 grams of addition, stirring is straight
It is extremely fully transparent；By europium oxide Eu2O3Dust technology is dissolved in, the oxalic acid of 0.0002 gram of addition is stirred until fully transparent；By hydrogen
Niobium oxide Nb (OH)5It is placed in deionized water, the oxalic acid of 1.8008 grams of addition, stirring is until fully transparent；By butyl titanate
C16H36O4Ti and a small amount of glacial acetic acid are mixed, and are then added drop-wise to again in ethanol, and add 1.3506 grams of oxalic acid, adjust pH value
For 4, stirring forms vitreosol, and butyl titanate used and the mol ratio of ethanol, glacial acetic acid are 1：5：0.5.
Above-mentioned solution is mixed, temperature be 100 DEG C under conditions of stir 1 hour, stand, drying, obtain it is fluffy before
Drive body；The precalcining in air atmosphere by obtained presoma, calcining heat is 400 DEG C, and calcination time is 10 hours, is obtained
The product of precalcining；After natural cooling, grind and be well mixed, calcined in air atmosphere, calcining heat is 1100 DEG C, calcining
Time is 10 hours, and grinding obtains red fluorescence powder after cooling.
The main structural behaviour of sample, excitation spectrum, luminescent spectrum are similar to Example 5.
Embodiment 7:
According to chemical formula Ca4.1Eu0.9Nb4Ti3O21The stoichiometric proportion of middle each element, weighs calcium nitrate Ca (NO respectively3)2:
1.6820 gram；Europium nitrate Eu (NO3)3·6H2O:1.0035 gram；Niobium hydroxide Nb (OH)5:1.7790 gram；Butyl titanate
C16H36O4Ti:2.5500 gram it is used as raw material.By calcium carbonate CaCO3It is dissolved in deionized water, the oxalic acid of 1.6612 grams of addition, stirring
Until fully transparent；By europium oxide Eu2O3Deionized water is dissolved in, the oxalic acid of 0.3647 gram of addition is stirred until fully transparent；
By niobium hydroxide Nb (OH)5It is placed in deionized water, the oxalic acid of 1.6207 grams of addition, stirring is until fully transparent；By metatitanic acid four
Butyl ester C16H36O4Ti and a small amount of glacial acetic acid are mixed, and are then added drop-wise to again in ethanol, and the oxalic acid of 1.2155 grams of addition adjusts pH
It is worth for 3, stirring forms vitreosol, and butyl titanate used and the mol ratio of ethanol, glacial acetic acid are 1：15：1.5.
Above-mentioned solution is mixed, temperature be 100 DEG C under conditions of stir 1 hour, stand, drying, obtain it is fluffy before
Drive body；The precalcining in air atmosphere by obtained presoma, calcining heat is 550 DEG C, and calcination time is 8 hours, is obtained
The product of precalcining；After natural cooling, grind and be well mixed, calcined in air atmosphere, calcining heat is 1150 DEG C, calcining
Time is 6 hours, obtains red fluorescence powder.
The main structural behaviour of sample, excitation spectrum, luminescent spectrum are similar to Example 5.
Embodiment 8:
According to chemical formula Ca4EuNb4Ti3O21The stoichiometric proportion of middle each element, weighs calcium nitrate Ca (NO respectively3)2:
1.6410 gram；Europium nitrate Eu (NO3)3·6H2O:1.1150 gram；Niobium hydroxide Nb (OH)5:1.7790 gram；Butyl titanate
C16H36O4Ti:2.5500 gram it is used as raw material.By calcium carbonate CaCO3It is dissolved in deionized water, the oxalic acid of 1.8008 grams of addition, stirring
Until fully transparent；By europium oxide Eu2O3Deionized water is dissolved in, the oxalic acid of 0.4502 gram of addition is stirred until fully transparent；
By niobium hydroxide Nb (OH)5It is placed in deionized water, the oxalic acid of 1.8008 grams of addition, stirring is until fully transparent；By metatitanic acid four
Butyl ester C16H36O4Ti and a small amount of glacial acetic acid mix dissolving, are then added drop-wise to again in ethanol, the oxalic acid of 1.3506 grams of addition,
It is 3.5 to adjust pH value, and stirring forms vitreosol, and butyl titanate used and the mol ratio of ethanol, glacial acetic acid are 1：10：1.
Above-mentioned solution is mixed, stirred 4 hours under conditions of temperature is 80 DEG C, stands, dry, obtain fluffy forerunner
Body；The precalcining in air atmosphere by obtained presoma, calcining heat is 650 DEG C, and calcination time is 6 hours, and what is obtained is pre-
The product of calcining；After natural cooling, grind and be well mixed, calcined in air atmosphere, calcining heat is 1250 DEG C, during calcining
Between be 3 hours, obtain a kind of red fluorescence powder.
The main structural behaviour of sample, excitation spectrum, luminescent spectrum are similar to Example 5.
Claims (8)
1. a kind of can be by the red fluorescence material of near ultraviolet excitation, it is characterised in that：Its chemical general formula is：Ca5- 5xEu5xNb4Ti3O21, wherein x is europium ion Eu3+Replace the mol ratio of Ca ions, and 0.0001≤x≤0.20.
2. a kind of can be existed by the preparation method of the red fluorescence material of near ultraviolet excitation, its feature as claimed in claim 1
In using high temperature solid-state method, comprise the following steps：
(1) formula Ca is pressed5-5xEu5xNb4Ti3O21, the stoichiometric proportion of corresponding element is weighed containing calcium in 0.0001≤x≤0.20
Ion Ca2+Compound, contain europium ion Eu3+Compound, contain niobium ion Nb5+Compound, contain titanium ion Ti4+'s
Compound is the raw material prepared, and the raw material weighed is ground respectively, is well mixed；
(2) mixture for obtaining step (1) is pre-sintered 1~2 time in air atmosphere, and sintering temperature is 900~1200 DEG C, is burnt
The knot time is 1~10 hour；
(3) it will grind uniform after the mixture natural cooling of step (2), calcined in air atmosphere, calcining heat is 1200~
1400 DEG C, calcination time is 1~15 hour, you can obtain red fluorescence material.
3. according to claim 2 can be by the preparation method of the red fluorescence material of near ultraviolet excitation, it is characterised in that：
Described calcium ions Ca2+Compound be calcium carbonate CaCO3, calcium chloride CaCl2, calcium nitrate Ca (NO3)2, in calcium oxide CaO
One kind；Described contains europium ion Eu3+Compound be europium oxide Eu2O3, europium nitrate Eu (NO3)3·6H2One kind in O；
Described contains niobium ion Nb5+Compound be niobium pentaoxide Nb2O5, columbium pentachloride NbCl5In one kind；Described contains
Titanium ion Ti4+Compound be titanium dioxide TiO2。
4. according to claim 2 can be by the preparation method of the red fluorescence material of near ultraviolet excitation, it is characterised in that
The calcining heat of step (3) is 1250~1350 DEG C, and calcination time is 5~8 hours.
5. a kind of can be existed by the preparation method of the red fluorescence material of near ultraviolet excitation, its feature as claimed in claim 1
In comprising the following steps：
(1) chemical formula Ca is pressed5-5xEu5xNb4Ti3O21, the stoichiometric proportion of each element, is weighed respectively in 0.0001≤x≤0.20：
Contain calcium ion Ca2+Compound, contain europium ion Eu3+Compound, contain niobium ion Nb5+Compound, contain titanium ion
Ti4+Compound be preparing raw material；
(2) step (1) is contained into calcium ion Ca2+Compound, contain europium ion Eu3+Compound, contain niobium ion Nb5+Change
Compound is dissolved separately in deionized water or is dissolved in nitric acid and diluted with deionized water；Titanium ion Ti will be contained4+Change
Compound mixes and is dissolved into glacial acetic acid and then is added drop-wise to again in ethanol, and regulation pH value is between 2-4, and stirring forms transparent molten
Glue；Ion mole 1.5 is added into various solution respectively again to 2 times of complexing agent, calcium ions Ca is respectively obtained2+, europium
Ion Eu3+, niobium ion Nb5+, titanium ion Ti4+Solution, described complexing agent is one kind in citric acid, oxalic acid；
(3) above-mentioned various solution are mixed, temperature stands, dried, obtain to be stirred 1~5 hour under conditions of 50~100 DEG C
Fluffy presoma；
(4) presoma for obtaining step (3) is calcined in air atmosphere, and calcining heat is 400~750 DEG C, and calcination time is 1
~10 hours；
(5) after the product of step (4) precalcining, natural cooling, grind and be well mixed, calcined again in air atmosphere, forged
It is 1100~1300 DEG C to burn temperature, and calcination time 1~10 hour obtains a kind of red fluorescence material.
6. according to claim 5 can be by the preparation method of the red fluorescence material of near ultraviolet excitation, it is characterised in that：
Calcining heat in step (5) is 1150~1250 DEG C, and calcination time is 3~6 hours.
7. according to claim 5 can be by the preparation method of the red fluorescence material of near ultraviolet excitation, it is characterised in that：
Described calcium ions Ca2+Compound be calcium carbonate CaCO3, calcium nitrate Ca (NO3)2In one kind；Described contains europium ion
Eu3+Compound be europium oxide Eu2O3, europium nitrate Eu (NO3)3·6H2One kind in O；Described contains niobium ion Nb5+Change
Compound is niobium hydroxide Nb (OH)5；The described compound containing titanium elements is butyl titanate C16H36O4Ti, the metatitanic acid four
The mol ratio of butyl ester and ethanol, glacial acetic acid is 1：5-15：0.5-1.5.
8. a kind of as claimed in claim 1 can be by the application of the red fluorescence material of near ultraviolet excitation, it is characterised in that：Institute
Red fluorescence material is stated in the case where 350-420 nanometers of near ultraviolet excitated light is excited, can emission peak be located at 615 rans
Feux rouges, can prepare the illumination using black light as excitation source or display device；Also it can be mixed with appropriate yellow fluorescent powder,
Apply and be packaged in outside InGaN diodes, preparation can send the LED of warm white.
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