CN105778908A - Calcium-niobate-based self-activated light emitting material, preparation method and application - Google Patents
Calcium-niobate-based self-activated light emitting material, preparation method and application Download PDFInfo
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- CN105778908A CN105778908A CN201610223495.3A CN201610223495A CN105778908A CN 105778908 A CN105778908 A CN 105778908A CN 201610223495 A CN201610223495 A CN 201610223495A CN 105778908 A CN105778908 A CN 105778908A
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Abstract
The invention relates to a calcium-niobate-based self-activated light emitting material, a preparation method and application.The chemical formula of the light emitting material is Ca2-x-ySrxBayNb2O7, wherein x is larger than or equal to 0 and smaller than or equal to 0.1, and y is larger than or equal to 0 and smaller than or equal to 0.1.The light emitting material is prepared through a sol-gel method, the grain size is small, production cost and equipment requirements are low, and operation and industrial production are easy.The prepared material is excited by ultraviolet light to emit bright blue light, the light emitting color gamut is wide, the light emitting performance is good, the color rendering index is high, temperature stability is good, and the material can be widely applied to the fields of illumination and display.
Description
Technical field
The present invention relates to a kind of self-activate luminescence material, preparation method and applications, issue at ultraviolet excitation particularly to one
Niobic acid calcio self-activate luminescence material penetrating blue-fluorescence and preparation method thereof, material is particularly suited for preparing blue light and white light LEDs
Illuminating device, belongs to phosphor technical field.
Background technology
In recent years, along with blue (450～470nm), near ultraviolet (380～410nm) and deep ultraviolet (190～315nm) light emitting diode
(LED) appearance, occurs in that the white light being combined with light conversion phosphor by blue, near ultraviolet and deep ultraviolet LED chip and being made
LED.This novel solid light source, compared to traditional electric filament lamp, fluorescent lamp and high voltage mercury lamp, has efficient energy-saving, green
The plurality of advantages such as environmental protection, life-span length (more than 10000 hours), volume are little, have huge application prospect in illumination and display field,
It is expected to realize industrialization, substitute existing ligthing paraphernalia, becomes forth generation lighting source.
Most of luminescent material all has the centre of luminescence.The centre of luminescence of LED light conversion fluorescence powder material mainly by activate from
Son is constituted, such as Y3Al5O12: Ce3+(YAG:Ce), Y2O3: Eu2+、BaAl2Si2O8: Eu2+, Mn2+Deng, its luminescence comes from activator
The impurity energy level formed in host material after ion doping.Also have a kind of centre of luminescence to need not the doping of active ions, only by
The defect of crystal self just can be formed, and this luminescence caused by material lattice defect is referred to as self-activate luminescence.Visible, from
Activation luminescent material, compared with the luminescent material that rare earth/transition metal is adulterated, has relatively low manufacturing cost, simpler production work
Skill, gradually causes the extensive concern of people.Chinese invention patent (CN103468259B) discloses one and issues at ultraviolet excitation
The Vanadotungstic acid. barium self-activate luminescence material of blue green light, can be used for the fields such as illumination and display.Chinese invention patent
(CN104164236A) disclosing self-activation type vanadate phosphor, this material main peak under ultraviolet excitation is positioned at the width of 500nm
Band fluorescence, has application prospect in terms of LED and solaode.
Additionally, the main method preparing fluorescent material at present is solid state reaction.But, solid state sintering reaction needs higher temperature
(1300～1500 DEG C), energy resource consumption is relatively big, and cost is high；The fluorescent powder grain that reaction is formed is usually micron dimension, it is difficult to formed
Nano-particle, the later stage is size-reduced, grind the crystal grain distribution obtained also is difficult to uniformly.
Therefore, preparation technology is simple in exploitation, and production cost is low, and granularity is less, stablize, and fluorescence intensity height, color rendering properties is good
Self-activate luminescence material is significant.The present invention selects calcium niobate to prepare self-activate luminescence material, need not any dopant ion,
Cost, optimized production process can be reduced.Under ultraviolet excitation, stable luminescent property, excitation is high.
Summary of the invention
Crystallite dimension is little, luminous efficiency is high, good light stability, preparation method simple and environmental protection to present invention aim at providing one
High-performance niobic acid calcio self-activate luminescence material, preparation method and application, to overcome problems of the prior art.
To achieve these goals, the present invention realizes by the following technical solutions:
The niobic acid calcio self-activate luminescence material of the present invention, its chemical expression is Ca2-x-ySrxBayNb2O7, wherein, 0≤x≤
0.1；0≤y≤0.1.
It is also preferred that the left the span of described x is 0≤x≤0.05.
It is also preferred that the left the span of described y is 0≤y≤0.05.
The preparation method of niobic acid calcio self-activate luminescence material of the present invention, comprises the following steps that:
1, by by element chemistry metering than weigh containing niobium ion Nb5+Raw materials of compound join in enough dehydrated alcohol,
It is stirred at room temperature 5～15 minutes, generates ethanol niobium solution；
2, by stoichiometrically weigh containing calcium ion Ca2+, strontium ion Sr2+, barium ions Ba2+Raw materials of compound dissolve
After in deionized water, this solution is joined in the ethanol niobium solution described in step 1, add enough citric acids and fit
The ethylene glycol of amount, after being stirred at room temperature 10～24 hours, obtains thick clear solution；
3, the thick clear solution obtained in step 2 is dried under the temperature conditions of 50～120 DEG C, obtain fluffy forerunner
Body；
4, the presoma obtained in step 3 is placed in Muffle furnace, sinters 2～6 hours at 600～1000 DEG C in air atmosphere,
Naturally cool to room temperature, after grinding uniformly, i.e. obtain the niobic acid calcio self-activate luminescence material of a kind of powder.
Heretofore described containing niobium ion Nb5+, calcium ion Ca2+, strontium ion Sr2+, barium ions Ba2+Raw materials of compound
Selected from containing niobium ion Nb5+, calcium ion Ca2+, strontium ion Sr2+, barium ions Ba2+Oxide, chloride, hydroxide,
Carbonate, nitrate, oxalates, acetate.
The invention have the characteristics that
(1) the niobic acid calcio self-activate luminescence material that the present invention relates to, abundant raw material source, cheap, and preparation method
Simply, production cost is low.
(2) the niobic acid calcio self-activate luminescence material particle size that the present invention prepares is micro/nano level, and stability of material is good, luminescent properties
Excellent, there is higher color rendering index, the temperature stability under the conditions of room temperature to 300 DEG C is good, and physicochemical properties are stable.
(3) the niobic acid calcio self-activate luminescence material that the present invention prepares sends main peak under 200～300nm ultraviolet excitations and is positioned at
450nm, wavelength cover the broadband blue-fluorescence of 350～650nm.
(4) the niobic acid calcio self-activate luminescence material that the present invention prepares can be coated on ultraviolet leds chip, sends blue light；
Or be coated on ultraviolet leds chip with red fluorescence powder combination, send white light.
(5) the niobic acid calcio self-activate luminescence material that the present invention prepares can be used as light emitting diode, display device, three primary colours fluorescence
Lamp and the blue light emitting material of Field Emission Display.
Accompanying drawing explanation
Fig. 1 is Ca2Nb2O7Powder diffraction standard card (18-0301) and embodiment 1 sample Ca2Nb2O7X-ray powder spread out
Penetrate figure.
Fig. 2 is the electron scanning micrograph of embodiment 1 sample.
Fig. 3 is embodiment 1 sample Ca2Nb2O7Excitation spectrum (left, monitoring 450nm launch) and emission spectrum (right side,
250nm excites).
Fig. 4 is embodiment 1 sample Ca2Nb2O7Illuminant color coordinate diagram.
Fig. 5 is embodiment 2 sample Ca1.97Sr0.03Nb2O7Excitation spectrum (left, monitoring 450nm launch) and emission spectrum
(right, 250nm excites).
Fig. 6 is embodiment 3 sample Ca1.95Sr0.02Ba0.03Nb2O7Excitation spectrum (left, monitoring 450nm launch) and launch
Spectrum (right, 250nm excites).
Specific embodiments
Below by way of particular specific embodiment and combine accompanying drawing the present invention will be described in more detail.Should be understood that the present invention carries
To one or more method steps do not repel before and after described combination step, there is also other method step, or clear and definite at these
Other method step can also be inserted before the step mentioned；Should also be understood that these embodiments be merely to illustrate the present invention and need not
In limiting the scope of the present invention.And, except as otherwise noted, the numbering of various method steps is only the facility differentiating various method steps
Instrument, rather than for limiting the ordering of various method steps or limiting the enforceable scope of the present invention, the change of its relativeness or
Adjust, in the case of without essence change technology contents, when being also considered as the enforceable category of the present invention.
Embodiment 1
Ca2Nb2O7The preparation of sample:
(1) by the NbCl of 27.03g5Join in 30ml dehydrated alcohol, be stirred at room temperature 5 minutes, generate ethanol niobium molten
Liquid；
(2) by the Ca (NO of 26.52g3)2·4H2After O is dissolved in the deionized water of 150ml, its solution is joined step
(1), in the ethanol niobium solution described in, add the citric acid of 57.93g and the ethylene glycol of 33.6ml, be stirred at room temperature 15
After hour, obtain thick clear solution；
(3) the thick clear solution obtained in step (2) is dried under the temperature conditions of 100 DEG C, obtain fluffy presoma；
(4) presoma obtained in step (3) is placed in Muffle furnace, sinters 5 hours at 800 DEG C in air atmosphere, natural
It is cooled to room temperature, after grinding uniformly, i.e. obtains the Ca of powder2Nb2O7Self-activate luminescence material.
The niobic acid calcio self-activate luminescence material appearance that this embodiment is prepared is white, and X-ray powder diffraction (XRD) is tested
Show, as it is shown in figure 1, the diffraction maximum data of gained sample and Ca2Nb2O7The diffraction number of powder diffraction standard card (18-0301)
According to unanimously, and without dephasign, illustrate that gained sample is pure phase Ca2Nb2O7Structure.Scanning electron microscope (SEM) photo shows,
As in figure 2 it is shown, gained sample is flake, thickness is only tens nanometers, and width is only about 1 μm.Fig. 3 is the present embodiment
The excitation and emission spectra of sample.The excitation peak that monitoring 450nm launches is positioned at the ultraviolet light wave band of 200～300nm, with dark purple
The transmitting peak position of outer LED matches.Under ultraviolet excitation, sample sends main peak and is positioned at 450nm, wavelength covering 350～650
The broadband blue-fluorescence of nm.Fig. 4 is the chromaticity coordinates figure of the present embodiment sample, and the chromaticity coordinates of this sample luminescence is
(0.158,0.168), is positioned at blue region.
Embodiment 2
Ca1.97Sr0.03Nb2O7The preparation of sample:
(1) by the NbCl of 54.09g5Join in 60ml dehydrated alcohol, be stirred at room temperature 10 minutes, generate ethanol niobium molten
Liquid；
(2) by the Ca (NO of 52.25g3)2·4H2Sr (the NO of O and 0.64g3)2After being dissolved in the deionized water of 250ml,
Its solution is joined in the ethanol niobium solution described in step (1), add the citric acid of 115.86g and the second two of 66.89ml
Alcohol, after being stirred at room temperature 20 hours, obtains thick clear solution；
(3) the thick clear solution obtained in step (2) is dried under the temperature conditions of 120 DEG C, obtain fluffy presoma；
(4) presoma obtained in step (3) is placed in Muffle furnace, sinters 4 hours at 900 DEG C in air atmosphere, natural
It is cooled to room temperature, after grinding uniformly, i.e. obtains the Ca of powder1.97Sr0.03Nb2O7Self-activate luminescence material.
The niobic acid calcio self-activate luminescence material appearance that this embodiment prepares is white, XRD spectra result and embodiment 1 basic
Causing, grain morphology and size are similar to Example 1.Fig. 5 gives the excitation and emission spectra of this embodiment sample, spectrum
Shape, peak position, wavelength cover are basically identical with embodiment 1 sample, and only relative intensity is slightly above embodiment 1 sample.?
Under ultraviolet excitation, sample sends bright blue light.
Embodiment 3
Ca1.95Sr0.02Ba0.03Nb2O7The preparation of sample:
(1) by the NbCl of 108.18g5Join in 118ml dehydrated alcohol, be stirred at room temperature 15 minutes, generate ethanol niobium
Solution；
(2) by the Ca (NO of 103.43g3)2·4H2Sr (the NO of O, 0.85g3)2, the Ba (NO of 1.57g3)2It is dissolved in 400ml
Deionized water in after, its solution is joined in the ethanol niobium solution described in step (1), adds the citric acid of 271.72g
With the ethylene glycol of 134.33ml, after being stirred at room temperature 24 hours, obtain thick clear solution；
(3) the thick clear solution obtained in step (2) is dried under the temperature conditions of 70 DEG C, obtain fluffy presoma；
(4) presoma obtained in step (3) is placed in Muffle furnace, sinters 4 hours at 900 DEG C in air atmosphere, natural
It is cooled to room temperature, after grinding uniformly, i.e. obtains the Ca of powder1.95Sr0.02Ba0.03Nb2O7Self-activate luminescence material.
The niobic acid calcio self-activate luminescence material appearance that this embodiment prepares is white, XRD spectra result and embodiment 1 basic
Causing, grain morphology and size are similar to Example 1.Fig. 6 gives the excitation and emission spectra of this embodiment sample, spectrum
Shape, peak position, wavelength cover are basically identical with embodiment 1 sample, and relative intensity is 2.5 times of embodiment 1 sample.
Under ultraviolet excitation, sample sends bright blue light.
The above, the only explanation embodiment of the present invention, not any formal and substantial to present invention restriction, it should
Point out, for those skilled in the art, on the premise of without departing from the inventive method, the some improvement made and
Supplement and also should be regarded as protection scope of the present invention.All those skilled in the art, without departing from the spirit and scope of the present invention
In the case of, utilize a little change that disclosed above technology contents is made, the equivalent variations modified and develop, be this
Bright Equivalent embodiments；Meanwhile, any equivalent variations that above-described embodiment is done by all substantial technological according to the present invention change,
Modify and develop, all still fall within the scope of technical scheme.
Claims (4)
1. a niobic acid calcio self-activate luminescence material, it is characterised in that this material is with Ca2Nb2O7Self-activate luminescence for matrix
Material, its chemical expression is Ca2-x-ySrxBayNb2O7, wherein, 0≤x≤0.1；0≤y≤0.1；This material uses colloidal sol to coagulate
Prepared by glue method, ultraviolet light irradiate under send blue-fluorescence, can be used as light emitting diode, display device, three-color fluorescent lamp and
The blue light emitting material of Field Emission Display.
2. the preparation method of niobic acid calcio self-activate luminescence material as claimed in claim 1, it is characterised in that comprise the following steps:
1) by by element chemistry metering than weigh containing niobium ion Nb5+Raw materials of compound join in enough dehydrated alcohol,
It is stirred at room temperature 5～15 minutes, generates ethanol niobium solution；
2) by stoichiometrically weigh containing calcium ion Ca2+, strontium ion Sr2+, barium ions Ba2+Raw materials of compound dissolve
After in deionized water, this solution is joined step 1) described in ethanol niobium solution in, add enough citric acids and suitable
The ethylene glycol of amount, after being stirred at room temperature 10～24 hours, obtains thick clear solution；
3) by step 2) in the thick clear solution that obtains dry under the temperature conditions of 50～120 DEG C, obtain fluffy forerunner
Body；
4) by step 3) in the presoma that obtains be placed in Muffle furnace, sinter 2～6 hours at 600～1000 DEG C in air atmosphere,
Naturally cool to room temperature, after grinding uniformly, i.e. obtain the niobic acid calcio self-activate luminescence material of a kind of powder.
3. preparation method as claimed in claim 2, it is characterised in that step 1) in, described containing niobium ion Nb5+Change
Compound raw material is selected from containing niobium ion Nb5+Oxide, hydroxide, carbonate, nitrate, oxalates, acetate.
4. preparation method as claimed in claim 2, it is characterised in that step 2) in, described containing calcium ion Ca2+, strontium
Ion Sr2+, barium ions Ba2+Raw materials of compound selected from containing calcium ion Ca2+, strontium ion Sr2+, barium ions Ba2+Oxidation
Thing, chloride, hydroxide, carbonate, nitrate, oxalates, acetate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11203714B2 (en) | 2018-07-19 | 2021-12-21 | Qingdao University | Luminescent material and preparation method thereof |
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| CN101962542A (en) * | 2010-09-14 | 2011-02-02 | 南昌大学 | Niobate-based red fluorescent powder for white LED as well as preparation method and application thereof |
| CN103923653A (en) * | 2014-05-05 | 2014-07-16 | 青岛大学 | Red long-afterglow luminescent material and preparation method thereof |
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2016
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| CN1597097A (en) * | 2004-08-30 | 2005-03-23 | 南京大学 | Preparation method of high specific surface tantalate and niobate photo catalyst |
| JP2007217202A (en) * | 2006-02-14 | 2007-08-30 | Tohoku Univ | Method for producing complex metal oxide |
| CN101775289A (en) * | 2009-12-25 | 2010-07-14 | 上海师范大学 | Method for synthesizing bismuth-doped calcium niobate nano luminous material |
| CN101962542A (en) * | 2010-09-14 | 2011-02-02 | 南昌大学 | Niobate-based red fluorescent powder for white LED as well as preparation method and application thereof |
| CN103923653A (en) * | 2014-05-05 | 2014-07-16 | 青岛大学 | Red long-afterglow luminescent material and preparation method thereof |
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| ALAMANDA V. PRASADARAO ET AL.,: "Fabrication of Sr2Nb2O7 thin films by sol-gel processing", 《JOURNAL OF MATERIALS RESEARCH》 * |
| M.WIEGEL ET AL.,: "Luminescence and nonlinear optical properties of perovskite-like niobates and titanates", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11203714B2 (en) | 2018-07-19 | 2021-12-21 | Qingdao University | Luminescent material and preparation method thereof |
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