CN109957403A - A kind of Eu3+Activate fluoboric acid strontium barium red fluorescence powder and its preparation and application - Google Patents
A kind of Eu3+Activate fluoboric acid strontium barium red fluorescence powder and its preparation and application Download PDFInfo
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- CN109957403A CN109957403A CN201910349356.9A CN201910349356A CN109957403A CN 109957403 A CN109957403 A CN 109957403A CN 201910349356 A CN201910349356 A CN 201910349356A CN 109957403 A CN109957403 A CN 109957403A
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- 239000000843 powder Substances 0.000 title claims abstract description 82
- 239000002253 acid Substances 0.000 title claims abstract description 23
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 229910001632 barium fluoride Inorganic materials 0.000 claims abstract description 16
- 229910001422 barium ion Inorganic materials 0.000 claims abstract description 16
- 238000005286 illumination Methods 0.000 claims abstract description 14
- 230000005284 excitation Effects 0.000 claims abstract description 11
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims abstract description 10
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 claims abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 239000011737 fluorine Substances 0.000 claims abstract description 8
- JQJPDKFZMJLCQG-UHFFFAOYSA-N strontium;barium(2+);borate Chemical compound [Sr+2].[Ba+2].[O-]B([O-])[O-] JQJPDKFZMJLCQG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 5
- 238000003980 solgel method Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 229910052693 Europium Inorganic materials 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- -1 europium ion Chemical group 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 239000008139 complexing agent Substances 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 10
- 229910001427 strontium ion Inorganic materials 0.000 claims description 10
- 229910052788 barium Inorganic materials 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001940 europium oxide Inorganic materials 0.000 claims description 3
- 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 3
- 230000004913 activation Effects 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000000536 complexating effect Effects 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 241001025261 Neoraja caerulea Species 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000012769 display material Substances 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
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 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
- C09K11/774—Borates
-
- 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
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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
The invention discloses a kind of Eu3+Fluoboric acid strontium barium red fluorescence powder and its preparation and application are activated, the chemical general formula of the fluorescent powder is Ba3‑xEuxSr2B4O10F2, wherein x is Eu3+Replace Ba2+Molar ratio, 0.005≤x≤0.35；Preparation step is: (1) not fluorine-containing barium strontium borate precursor powder Ba is prepared using chemical sol-gel processes2‑xEuxSr2B4O10；(2) in the not fluorine-containing barium strontium borate precursor powder being prepared, barium fluoride and ammonium fluoride is added, is sufficiently mixed, and by mixture briquetting, prepared using solid sintering technology, obtains a kind of Eu3+Activate the red luminescent phosphor Ba of fluoboric acid strontium barium3‑xEuxSr2B4O10F2.Red fluorescence powder prepared by the present invention is pure phase, and particle is uniform, the feux rouges that central wavelength is 615 nanometers is issued under 395 nanometers of black light excitations, luminous intensity is high, and thermostabilization is good, can be used for preparing using black light as the illumination of excitation light source or display device.
Description
Technical field
The present invention relates to inorganic fluorescent materials and field of display technology, and in particular to a kind of Eu3+Activate fluoboric acid strontium barium red
Color fluorescent powder and its preparation and application.
Background technique
In recent years, innovation and development based on semiconductor, blue light and black light semiconductor chip are applied, illumination and
Display has obtained revolutionary development, and the white light emitting diode prepared based on rare-earth ion activated fluorescent powder realizes solid-state
Illumination forms the White-light LED illumination device of current mainstream commercialization, with traditional fluorescent lamp, energy-saving illumination and other light sources
It compares, fast-developing a new generation's illumination based on LED chip is many excellent with environmentally friendly, low in energy consumption, safety and high brightness
Point.
Current most important illumination is by blue-light semiconductor chip and yellow Y3Al5O12:Ce3+(YAG:Ce3+) fluorescent powder group
Close encapsulation realize, it is this illumination have many advantages, but it is this illumination also have the shortcomings that it is inevitable: illumination light-emitting
In red emission it is insufficient, colour temperature (CCT > 4500K) and colour rendering index (Ra < 80) are poor, this largely upper limit of these disadvantages
Its some application in general illumination is made.Therefore necessary using red luminescent phosphor in fluorescent powder, it is still, this
Red luminescent phosphor must have good launching efficiency in black light and blue light section.As a kind of most important red hair
The activator rare earth ion of light, Eu3+Characteristic emission derive from5D0,1,2-7FJThe transition of (J=4 ..., 0), that activates is red
Luminescent material is to be applied to light-emitting LED first choice.
LED is mainly Y with business red fluorescence powder at present2O2S:Eu3+, which is thio object, because of its preparation
It needs to use sulfide in the process as raw material, and need to be calcined under protective atmosphere or reducing atmosphere, prevented in sulphur and air
Oxygen reaction, preparation method is extremely complex；Sulfide systems efficiency is lower, and poor chemical stability is also easy to produce H2S gas and corrode
LED chip.
Summary of the invention
An object of the present invention is to provide a kind of Eu3+Fluoboric acid strontium barium red fluorescence powder is activated, luminous efficiency is high.
The second object of the present invention is to provide above-mentioned Eu3+Activate the preparation method of fluoboric acid strontium barium red fluorescence powder, step
Simply, reproducible and environmental friendly.
The third object of the present invention is to provide above-mentioned Eu3+Activate the application of fluoboric acid strontium barium red fluorescence powder.
To achieve the above object, The technical solution adopted by the invention is as follows: a kind of Eu3+Activate fluoboric acid strontium barium red fluorescence
Powder, chemical general formula Ba3-xEuxSr2B4O10F2, x is europium ion Eu3+Replace barium ions Ba2+Molar ratio, x value range is
0.005≤x≤0.35。
The fluorescent powder mesostroma is Ba3Sr2B4O10F2, trivalent europium ion Eu3+For activator.
The present invention also provides above-mentioned Eu3+Activate the preparation method of fluoboric acid strontium barium red fluorescence powder, including two steps:
First, not fluorine-containing barium strontium borate precursor B a is prepared using chemical sol-gel processes2-xEuxSr2B4O10；
Second, in the not fluorine-containing barium strontium borate presoma being prepared, barium fluoride BaF is added2With ammonium fluoride NH4F,
It is sufficiently mixed, and by mixture briquetting, is prepared using solid sintering technology, obtain a kind of Eu3+Activate fluoboric acid strontium barium red fluorescence
Powder Ba3-xEuxSr2B4O10F2, x is europium ion Eu3+Replace barium ions Ba2+Molal quantity, 0.005≤x≤0.35.
Further, not fluorine-containing barium strontium borate precursor B a is prepared using chemical sol-gel processes2-xEuxSr2B4O10's
Specific step is as follows:
(1) chemical formula Ba is pressed2-xEuxSr2B4O10, the stoichiometric ratio of Ba, Eu, Sr, weigh and contain in 0.005≤x≤0.35
There is barium ions Ba2+Compound, contain europium ion Eu3+Compound, contain strontium ion Sr2+Compound, and co-dissolve in
In dilute nitric acid solution, clear solution is obtained, adds 1~1.5 times of the complexing agent citric acid or oxalic acid of reactant integral molar quantity,
It is stirred under the conditions of 60~90 DEG C；
(2) chemical formula Ba is pressed2-xEuxSr2B4O10, the stoichiometric ratio of B element, weighs containing boron in 0.005≤x≤0.35
Ion B3+Compound, be dissolved in dilute nitric acid solution, obtain clear solution, add 1~1.5 times of reactant mole
Complexing agent citric acid or oxalic acid stir under the conditions of 60~90 DEG C；
(3) solution that step (1) and step (2) are prepared is slowly mixed together, stirs 1 under the conditions of 50~100 DEG C of temperature
It after~5 hours, stands, drying obtains fluffy powder；
(4) powder that step (3) obtains is placed in Muffle furnace and is calcined, temperature is 350~700 DEG C, and the time is 3~10 small
When, room temperature is naturally cooled to, obtains precursor powder material after grinding uniformly.
Preferably, the solid sintering technology comprises the concrete steps that: calcining in air atmosphere, calcination temperature is 750~950
DEG C, calcination time is 1~10 hour.
It is furthermore preferred that calcination temperature is 800~900 DEG C, calcination time is 4~6 hours.
Preferably, the barium fluoride BaF2With ammonium fluoride NH4The usage amount of F is respectively precursor powder Ba2- xEuxSr2B4O10, the half of strontium ion mole in 0.005≤x≤0.35.
Preferably, described to contain barium ions Ba2+Compound be one of barium monoxide, barium nitrate, barium carbonate；It is described
Contain strontium ion Sr2+Compound be one of strontium oxide strontia, strontium nitrate, strontium carbonate；Described contains europium ion Eu3+'s
Compound is europium oxide or europium nitrate；Described contains boron ion B3+Compound be boron oxide or boric acid.
Preferably, drying temperature described in step (3) is 100~200 DEG C.
The present invention also provides above-mentioned Eu3+Activate the application of fluoboric acid strontium barium red fluorescence powder.
The red fluorescence powder issues the feux rouges that central wavelength is 615 nanometers under 395 nanometers of black light excitations, can be used for
Preparation can be used as light emitting diode, display material, three primary colours fluorescence using black light as the illumination of excitation light source or display device
In lamp and Field Emission Display.
Compared with prior art, the invention has the following beneficial effects:
(1) with existing red fluorescence powder such as Y2O2S:Eu3+,Y2O3:Eu3+It compares, red fluorescence powder prepared by the present invention
For pure phase, particle is uniform, has very strong launching efficiency near ultraviolet and blue light section, which is near ultraviolet and blue-ray LED core
The radiation wavelength of piece is more suitable for preparation according near ultraviolet and blue-ray LED diode chip for backlight unit and prepares White-light LED illumination equipment；
(2) in Ba3Sr2B4O10F2There are two kinds of ions of Ba and Sr, cation crystallographic site has strong disturb in matrix
It is dynamic, realize Eu3+The forbidden transition of ion is thoroughly broken, and has been obtained the red of pure coloration and has been shone, has there is good luminous efficiency；
(3) matrix is made of the polyhedron containing F ion, and lattice is rigidly bigger than pure-oxide lattice, is obtained
Eu3+The red luminescence phosphor of activation has good thermal stability.
Detailed description of the invention
Fig. 1 is that the embodiment of the present invention 1 prepares Ba2.75Eu0.25Sr2B4O10F2The X-ray powder diffraction pattern of fluorescent powder；
Fig. 2 is that the embodiment of the present invention 1 prepares Ba2.75Eu0.25Sr2B4O10F2The SEM of fluorescent powder schemes；
Fig. 3 is that the embodiment of the present invention 1 prepares Ba2.75Eu0.25Sr2B4O10F2Fluorescent powder obtains under 615 nanometers of light detection
Exciting light spectrogram；
Fig. 4 is that the embodiment of the present invention 1 prepares Ba2.75Eu0.25Sr2B4O10F2Hair of the fluorescent powder under 395 nanometers of light excitation
Light spectrogram；
Fig. 5 is that the embodiment of the present invention 1 prepares Ba2.75Eu0.25Sr2B4O10F2The decay of luminescence curve of fluorescent powder
Fig. 6 is that the embodiment of the present invention 4 prepares Ba2.65Eu0.35Sr2B4O10F2The SEM of fluorescent powder schemes；
Fig. 7 is that the embodiment of the present invention 4 prepares Ba2.65Eu0.35Sr2B4O10F2Fluorescent powder obtains under 615 nanometers of light detection
Exciting light spectrogram；
Fig. 8 is that the embodiment of the present invention 4 prepares Ba2.65Eu0.35Sr2B4O10F2Hair of the fluorescent powder under 395 nanometers of light excitation
Light spectrogram；
Fig. 9 is that the embodiment of the present invention 4 prepares Ba2.65Eu0.35Sr2B4O10F2The decay of luminescence curve of fluorescent powder.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments.
Embodiment 1:Ba2.75Eu0.25Sr2B4O10F2
By chemical formula Ba1.75Eu0.25Sr2B4O10F2The stoichiometric ratio of middle Ba, Eu, Sr element, weighs: barium carbonate respectively
BaCO3: 2.76 grams, strontium carbonate SrCO3: 2.36 grams, europium nitrate Eu (NO3)3·6H2It O:0.89 grams, is dissolved in dilute nitric acid solution,
Clear solution is obtained, 3.52 grams of complexing agent oxalic acid is added, is stirred under the conditions of 90 DEG C.Then chemical formula is pressed
Ba1.75Eu0.25Sr2B4O10F2The stoichiometric ratio of middle B element weighs boric acid H3BO3: it 1.98 grams, is dissolved in dilute nitric acid solution,
Clear solution is obtained, 3.6 grams of complexing agent oxalic acid is added, is stirred under the conditions of 90 DEG C.Two kinds of solution are slowly mixed together, at 100 DEG C
Under the conditions of stir 1 hour after stand, then dried under the conditions of 200 DEG C, obtain fluffy powder；The powder is placed in Muffle furnace
Middle calcining, temperature are 700 DEG C, and the time is 3 hours, naturally cool to room temperature, obtain precursor powder material after grinding uniformly
Ba1.75Eu0.25Sr2B4O10。
By precursor powder derived above, 1.4 grams of barium fluoride BaF2With 0.3 gram of ammonium fluoride NH4F is sufficiently mixed, and will be mixed
Object briquetting, is calcined in air atmosphere, and calcination temperature is 950 DEG C, and calcination time is 1 hour；Molecular formula, which can be obtained, is
Ba2.75Eu0.25Sr2B4O10F2Red luminescent phosphor.
Referring to attached drawing 1, it is 1 technical solution of embodiment preparation Ba2.75Eu0.25Sr2B4O10F2The x-ray powder of fluorescent powder
Diffracting spectrum, the results showed that, it is single-phase for preparing material.
Referring to attached drawing 2, it is to prepare Ba by 1 technical solution of embodiment2.75Eu0.25Sr2B4O10F2The SEM of fluorescent powder schemes, should
Material crystalline is functional, uniform particle sizes；
Referring to attached drawing 3, it is to prepare Ba by 1 technical solution of embodiment2.75Eu0.25Sr2B4O10F2Fluorescent powder emits in monitoring
The exciting light spectrogram obtained under 576 nanometers of light, there it can be seen that the excitation source of emitting red light is mainly at 200~500 nanometers
Between it is ultraviolet to blue region, can be well matched with and ultraviolet excite to blue-light LED chip；
Referring to attached drawing 4, it is to prepare Ba by 1 technical solution of embodiment2.75Eu0.25Sr2B4O10F2With near ultraviolet in fluorescent powder
395 nanometers of light excite what is obtained to shine, and center emission wavelength is 615 nanometers, and coloration is pure；
Referring to attached drawing 5, it is the decay of luminescence curve that 615 nanometers of fluorescent powder are prepared by 1 technical solution of embodiment, luminous
Service life is 1.32 milliseconds, is suitable for the application of luminous lighting.
Embodiment 2:Ba2.85Eu0.15Sr2B4O10F2
By chemical formula Ba1.85Eu0.15Sr2B4O10The stoichiometric ratio of middle Ba, Eu, Sr element, weighs: barium carbonate respectively
BaCO3: 2.19 grams, strontium carbonate SrCO3: 1.77 grams, europium nitrate Eu (NO3)3·6H2O:0.404 grams, it is dissolved in dilute nitric acid solution
In, clear solution is obtained, 3.21 grams of complexing agent oxalic acid is added, is stirred under the conditions of 80 DEG C.Then chemical formula is pressed
Ba1.85Eu0.15Sr2B4O10The stoichiometric ratio of middle B element weighs boric acid H3BO3: it 1.48 grams, is dissolved in dilute nitric acid solution, obtains
To clear solution, 3.24 grams of complexing agent oxalic acid are added, is stirred under the conditions of 80 DEG C.Two kinds of solution are slowly mixed together, in 85 DEG C of items
After being stirred 3 hours under part, stands, then dried under the conditions of 160 DEG C, obtain fluffy powder；The powder is placed in Muffle furnace
Middle calcining, temperature are 700 DEG C, and the time is 3 hours, naturally cool to room temperature, obtain precursor powder after grinding uniformly
Ba1.85Eu0.15Sr2B4O10。
By precursor powder derived above, 1.4 grams of barium fluoride BaF2With 0.3 gram of ammonium fluoride NH4F is sufficiently mixed, and will be mixed
Object briquetting, is calcined in air atmosphere, and calcination temperature is 800 DEG C, and calcination time is 6 hours；Molecular formula, which can be obtained, is
Ba2.85Eu0.15Sr2B4O10F2Red luminescent phosphor.
Its main structural behaviour, excitation spectrum, luminescent spectrum are similar to Example 1.
Embodiment 3:Ba2.995Eu0.005Sr2B4O10F2
By chemical formula Ba1.995Eu0.005Sr2B4O10The stoichiometric ratio of middle Ba, Eu, Sr element, weighs: barium monoxide respectively
BaO:2.33 grams, SrO:2.34 grams of strontium oxide strontia, europium nitrate Eu (NO3)3·6H2It O:0.0014 grams, is dissolved in dilute nitric acid solution,
Clear solution is obtained, 4.671 grams of complexing agent oxalic acid is added, is stirred under the conditions of 75 DEG C.Then chemical formula is pressed
Ba1.995Eu0.005Sr2B4O10The stoichiometric ratio of middle B element weighs boric acid H3BO3: it 4.68 grams, is dissolved in dilute nitric acid solution,
Clear solution is obtained, 1.17 grams of complexing agent oxalic acid is added, is stirred under the conditions of 80 DEG C.Two kinds of solution are slowly mixed together, at 90 DEG C
Under the conditions of stir 2 hours after, stand, then dried under the conditions of 180 DEG C, obtain fluffy powder；The powder is placed in Muffle
It is calcined in furnace, temperature is 650 DEG C, and the time is 5 hours, naturally cools to room temperature, and a kind of be formulated is obtained after grinding uniformly and is
Ba1.995Eu0.005Sr2B4O10Precursor powder.
By precursor powder derived above, 1.75 grams of barium fluoride BaF2With 0.37 gram of ammonium fluoride NH4F is sufficiently mixed, and will be mixed
Object briquetting is closed, is calcined in air atmosphere, calcination temperature is 900 DEG C, and calcination time is 4 hours；Molecular formula, which can be obtained, is
Ba2.995Eu0.005Sr2B4O10F2Red luminescent phosphor.
Its main structural behaviour, excitation spectrum, luminescent spectrum are similar to Example 1.
Embodiment 4:Ba2.65Eu0.35Sr2B4O10F2
By chemical formula Ba1.65Eu0.35Sr2B4O10The stoichiometric ratio of middle Ba, Eu, Sr element, weighs: barium carbonate respectively
BaCO3: 2.15 grams, strontium carbonate SrCO3: 2.11 grams, europium oxide Eu2O3: it 0.308 gram, is dissolved in dilute nitric acid solution, obtains
Bright solution is added 7.2 grams of complexing agent citric acid, stirs under the conditions of 60 DEG C.Then chemical formula Ba is pressed1.65Eu0.35Sr2B4O10Middle B
The stoichiometric ratio of element weighs boric acid B2O3: it 0.7 gram, is dissolved in dilute nitric acid solution, obtains clear solution, complexing agent is added
It 3.8 grams of citric acid, is stirred under the conditions of 60 DEG C.Both the above solution is slowly mixed together, after being stirred 5 hours under the conditions of 50 DEG C,
It stands, is then dried under the conditions of 100 DEG C, obtain fluffy powder；The powder is placed in Muffle furnace and is calcined, temperature 350
DEG C, the time is 10 hours, naturally cools to room temperature, and it is Ba that a kind of be formulated is obtained after grinding uniformly1.65Eu0.35Sr2B4O10Forerunner
Body powder.
By precursor powder derived above, 0.87 gram of barium fluoride BaF2With 0.18 gram of ammonium fluoride NH4F is sufficiently mixed, and will be mixed
Object briquetting is closed, is calcined in air atmosphere, calcination temperature is 750 DEG C, and calcination time is 10 hours；Molecular formula, which can be obtained, is
Ba2.65Eu0.35Sr2B4O10F2Red luminescent phosphor.
For the X-ray powder diffraction figure of the fluorescent powder as attached drawing 1, it is single-phase for preparing material.
Referring to attached drawing 6, it is the SEM figure that fluorescent powder is prepared by 4 technical solution of embodiment, and the material crystalline is functional,
Uniform particle sizes；
Referring to attached drawing 7, it is to prepare fluorescent powder by 4 technical solution of embodiment to obtain under 615 nanometers of light of monitoring transmitting
Exciting light spectrogram, there it can be seen that the excitation source of emitting red light is mainly ultraviolet to blue light region between 200~500 nanometers
Domain can be well matched with ultraviolet to blue-light LED chip excitation；
Referring to attached drawing 8, it is to prepare in fluorescent powder to obtain with 395 nanometers of excitations of black light by 4 technical solution of embodiment
Shine, center emission wavelength be 615 nanometers, coloration is pure；
Referring to attached drawing 9, it is the decay of luminescence curve that 615 nanometers of fluorescent powder are prepared by 4 technical solution of embodiment, luminous
Service life is 0.95 millisecond, is suitable for the application of luminous lighting.
Embodiment 5:Ba2.8Eu0.2Sr2B4O10F2
By chemical formula Ba1.8Eu0.2Sr2B4O10The stoichiometric ratio of middle Ba, Eu, Sr element, weighs: barium carbonate respectively
BaCO3: 2.13 grams, strontium carbonate SrCO3: 1.77 grams, europium nitrate Eu (NO3)3·6H2It O:0.53 grams, is dissolved in dilute nitric acid solution,
Clear solution is obtained, 2.4 grams of complexing agent oxalic acid is added, is stirred under the conditions of 90 DEG C.Then chemical formula Ba is pressed1.8Eu0.2Sr2B4O10
The stoichiometric ratio of middle B element weighs boric acid H3BO3: it 1.48 grams, is dissolved in dilute nitric acid solution, obtains clear solution, be added
It 2.59 grams of complexing agent oxalic acid, is stirred under the conditions of 75 DEG C.Two kinds of solution are slowly mixed together, after being stirred 3 hours under the conditions of 90 DEG C,
It stands, is then dried under the conditions of 180 DEG C, obtain fluffy powder；The powder is placed in Muffle furnace and is calcined, temperature 550
DEG C, the time is 6 hours, naturally cools to room temperature, and it is Ba that a kind of be formulated is obtained after grinding uniformly1.8Eu0.2Sr2B4O10Presoma
Dusty material.
By precursor powder derived above, 1.05 grams of barium fluoride BaF2With 0.22 gram of ammonium fluoride NH4F is sufficiently mixed, and will be mixed
Object briquetting is closed, is calcined in air atmosphere, calcination temperature is 800 DEG C, and calcination time is 5 hours；Molecular formula, which can be obtained, is
Ba2.8Eu0.2Sr2B4O10F2Red luminescent phosphor.
Its main structural behaviour, excitation spectrum, luminescent spectrum are similar to Example 4.
Claims (9)
1. a kind of Eu3+Activate fluoboric acid strontium barium red fluorescence powder, which is characterized in that its chemical general formula is Ba3-xEuxSr2B4O10F2,
Wherein x is europium ion Eu3+Replace barium ions Ba2+Molar ratio, x value range be 0.005≤x≤0.35.
2. a kind of Eu described in claim 13+Activate the preparation method of fluoboric acid strontium barium red fluorescence powder, which is characterized in that packet
Include two steps:
First, not fluorine-containing barium strontium borate precursor powder Ba is prepared using chemical sol-gel processes2-xEuxSr2B4O10；
Second, in the not fluorine-containing barium strontium borate precursor powder being prepared, barium fluoride and ammonium fluoride is added, it is sufficiently mixed
It closes, and by mixture briquetting, is prepared using solid sintering technology, obtain a kind of Eu3+Activate fluoboric acid strontium barium red fluorescence powder Ba3- xEuxSr2B4O10F2, x is europium ion Eu3+Replace barium ions Ba2+Molal quantity, 0.005≤x≤0.35.
3. the preparation method of Eu3+ activation fluoboric acid strontium barium red fluorescence powder according to claim 2, which is characterized in that make
Not fluorine-containing barium strontium borate precursor powder Ba is prepared with chemical sol-gel processes2-xEuxSr2B4O10Specific step is as follows:
(1) chemical formula Ba is pressed2-xEuxSr2B4O10, the stoichiometric ratio of Ba, Eu, Sr, weigh containing barium in 0.005≤x≤0.35
Ion Ba2+Compound, contain europium ion Eu3+Compound, contain strontium ion Sr2+Compound, and co-dissolve is in dilute nitre
In acid solution, clear solution is obtained, 1~1.5 times of the complexing agent citric acid or oxalic acid of reactant integral molar quantity are added, 60
It is stirred under the conditions of~90 DEG C；
(2) chemical formula Ba is pressed2-xEuxSr2B4O10, the stoichiometric ratio of B element, weighs containing boron ion in 0.005≤x≤0.35
B3+Compound, be dissolved in dilute nitric acid solution, obtain clear solution, add 1~1.5 times of complexing of reactant mole
Agent citric acid or oxalic acid stir under the conditions of 60~90 DEG C；
(3) solution that step (1) and step (2) are prepared is slowly mixed together, it is small that 1~5 is stirred under the conditions of 50~100 DEG C of temperature
Shi Hou is stood, and drying obtains fluffy powder；
(4) powder that step (3) obtains being placed in Muffle furnace and is calcined, temperature is 350~700 DEG C, and the time is 3~10 hours,
Room temperature is naturally cooled to, obtains precursor powder material after grinding uniformly.
4. Eu according to claim 23+Activate the preparation method of fluoboric acid strontium barium red fluorescence powder, which is characterized in that institute
State comprising the concrete steps that for solid sintering technology: being calcined in air atmosphere, calcination temperature be 750~950 DEG C, calcination time be 1~
10 hours.
5. Eu according to claim 43+Activate the preparation method of fluoboric acid strontium barium red fluorescence powder, which is characterized in that forge
Burning temperature is 800~900 DEG C, and calcination time is 4~6 hours.
6. Eu according to claim 23+Activate the preparation method of fluoboric acid strontium barium red fluorescence powder, which is characterized in that institute
The usage amount of the barium fluoride and ammonium fluoride stated is respectively the half of strontium ion mole in precursor powder.
7. Eu according to claim 33+Activate the preparation method of fluoboric acid strontium barium red fluorescence powder, which is characterized in that institute
That states contains barium ions Ba2+Compound be one of barium monoxide, barium nitrate, barium carbonate；Described contains strontium ion Sr2+
Compound be one of strontium oxide strontia, strontium nitrate, strontium carbonate；Described contains europium ion Eu3+Compound be europium oxide or
Europium nitrate；Described contains boron ion B3+Compound be boron oxide or boric acid.
8. Eu according to claim 33+Activate the preparation method of fluoboric acid strontium barium red fluorescence powder, which is characterized in that step
Suddenly drying temperature described in (3) is 100~200 DEG C.
9. Eu described in claim 13+Activate fluoboric acid strontium barium red fluorescence powder in preparation using black light as excitation light source
Application in terms of illumination or display device.
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| CN111410955A (en) * | 2020-05-18 | 2020-07-14 | 唐山学院 | Preparation method of red fluorescent powder |
| CN113046067A (en) * | 2021-03-18 | 2021-06-29 | 唐山学院 | Eu (Eu)3+/K+Codoped sodium barium fluoborate-based red phosphor and preparation method thereof |
| CN116875303A (en) * | 2023-06-02 | 2023-10-13 | 常熟理工学院 | Aluminate-based red luminescent material and preparation method and application thereof |
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