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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
barium
strontium
powder
red fluorescence
activate
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
Application number
CN201910349356.9A
Other languages
Chinese (zh)
Other versions
CN109957403B (en
Inventor
乔学斌
王胜家
赵君亚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Normal University
Original Assignee
Jiangsu Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jiangsu Normal University filed Critical Jiangsu Normal University
Priority to CN201910349356.9A priority Critical patent/CN109957403B/en
Publication of CN109957403A publication Critical patent/CN109957403A/en
Application granted granted Critical
Publication of CN109957403B publication Critical patent/CN109957403B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/774Borates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50Wavelength conversion elements
    • H01L33/501Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502Wavelength conversion materials

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

A kind of Eu3+Activate fluoboric acid strontium barium red fluorescence powder and its preparation and application
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.
CN201910349356.9A 2019-04-28 2019-04-28 Eu (Eu)3+Activated barium strontium fluoborate red fluorescent powder and preparation and application thereof Active CN109957403B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910349356.9A CN109957403B (en) 2019-04-28 2019-04-28 Eu (Eu)3+Activated barium strontium fluoborate red fluorescent powder and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910349356.9A CN109957403B (en) 2019-04-28 2019-04-28 Eu (Eu)3+Activated barium strontium fluoborate red fluorescent powder and preparation and application thereof

Publications (2)

Publication Number Publication Date
CN109957403A true CN109957403A (en) 2019-07-02
CN109957403B CN109957403B (en) 2021-08-27

Family

ID=67026826

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910349356.9A Active CN109957403B (en) 2019-04-28 2019-04-28 Eu (Eu)3+Activated barium strontium fluoborate red fluorescent powder and preparation and application thereof

Country Status (1)

Country Link
CN (1) CN109957403B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103497761A (en) * 2013-09-26 2014-01-08 苏州大学 Eu<2+>-activated aluminum-barium fluoborate fluorescent powder as well as preparation method and application thereof
CN108753279A (en) * 2018-06-05 2018-11-06 湘南学院 A kind of europium ion Eu3+The red luminescent phosphor of activation and its preparation and application
CN108822836A (en) * 2018-06-08 2018-11-16 南通纺织丝绸产业技术研究院 A kind of Eu2+And Eu3+The fluorescent powder of europium ion mixing activation, preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103497761A (en) * 2013-09-26 2014-01-08 苏州大学 Eu<2+>-activated aluminum-barium fluoborate fluorescent powder as well as preparation method and application thereof
CN108753279A (en) * 2018-06-05 2018-11-06 湘南学院 A kind of europium ion Eu3+The red luminescent phosphor of activation and its preparation and application
CN108822836A (en) * 2018-06-08 2018-11-16 南通纺织丝绸产业技术研究院 A kind of Eu2+And Eu3+The fluorescent powder of europium ion mixing activation, preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ALEKEL, T 等: "THE PYROBORATE FLUORIDE BA5(B2O5)2F2", 《JOURNAL OF SOLID STATE CHEMISTRY》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
CN109957403B (en) 2021-08-27

Similar Documents

Publication Publication Date Title
CN112094647B (en) Narrow-band emission nitrogen oxide red fluorescent powder and preparation method thereof
CN101475802B (en) Multiple antimonate luminescent materials for white light LED and preparation thereof
CN105331364A (en) YAG:Mn red phosphor, preparation method and applications thereof
Yan et al. Color-tunable Al 6 Si 2 O 13: Eu 2+, Mn 2+ phosphor with high color rendering index based on energy transfer for warm white LEDs
CN103305216B (en) Borate red fluorescent powder and preparation method and application thereof
CN105219382A (en) Eu 2+-Eu 3+codoped fluoaluminate substrate fluorescent powder and synthetic method thereof and application
CN114540015A (en) Wide-spectrum yellow-green emitting nitrogen oxide fluorescent powder and preparation method thereof
CN109957403A (en) A kind of Eu3+Activate fluoboric acid strontium barium red fluorescence powder and its preparation and application
CN102373062B (en) Fluosilicate red fluorescent powder suitable for white-light LED (Light-Emitting Diode) and preparation method thereof
CN109957402B (en) Trivalent europium ion activated red-emitting fluorescent powder and preparation and application thereof
CN107629794A (en) A kind of europium ion Eu3+The bismuthino luminescent material of activation, preparation method and application
CN108034423B (en) Mn (manganese)2+Ion-doped silicate red fluorescent powder, preparation method and application
CN108276998B (en) Trivalent samarium ion doped barium gadolinium titanate red fluorescent powder and preparation method thereof
CN109957397A (en) A kind of Tb3+ activation fluoboric acid strontium barium green emitting phosphor and its preparation and application
CN105860971B (en) Rare earth ion doped zirconium niobate fluorescent powder and preparation method thereof
CN108048080A (en) A kind of LED alkaline earth transition Composite borate fluorescent powders and preparation method thereof
CN109777421B (en) Europium ion Eu3+Activated red fluorescent powder, preparation method and application
CN110184055B (en) Eu (Eu)3+Activated niobium tantalate red luminescent phosphor and preparation and application thereof
CN109294583B (en) Cerium ion doped barium gadolinium titanate blue fluorescent powder for white light LED and preparation method thereof
CN106867524B (en) A kind of preparation and application of alkaline earth aluminate blue fluorescent material
CN105419798A (en) Preparation method and application of orange-red antimonate fluorescent material
CN105419797B (en) A kind of orange red fluorescent powder of suitable near ultraviolet excitation and its preparation and application
CN105860965B (en) Rare earth ion doped red fluorescent powder and preparation method thereof
CN109988567A (en) A kind of Dy3+Activate fluoboric acid strontium barium yellow fluorescent powder and its preparation and application
CN116120924B (en) Eu 2+ Activated green luminous fluorescent powder and preparation method and application 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: 20190702

Assignee: Xuzhou Tianjiao kangren Biotechnology Co.,Ltd.

Assignor: Jiangsu Normal University

Contract record no.: X2022980020975

Denomination of invention: Preparation and application of a Eu3+activated strontium barium fluoroborate red phosphor

Granted publication date: 20210827

License type: Common License

Record date: 20221111

EE01 Entry into force of recordation of patent licensing contract
EC01 Cancellation of recordation of patent licensing contract

Assignee: Xuzhou Tianjiao kangren Biotechnology Co.,Ltd.

Assignor: Jiangsu Normal University

Contract record no.: X2022980020975

Date of cancellation: 20230625

EC01 Cancellation of recordation of patent licensing contract