CN106544021B - The borate fluorescent powder and preparation method thereof that a kind of cerium, terbium are co-doped with - Google Patents
The borate fluorescent powder and preparation method thereof that a kind of cerium, terbium are co-doped with Download PDFInfo
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- CN106544021B CN106544021B CN201610907464.XA CN201610907464A CN106544021B CN 106544021 B CN106544021 B CN 106544021B CN 201610907464 A CN201610907464 A CN 201610907464A CN 106544021 B CN106544021 B CN 106544021B
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- H01L33/48—Semiconductor 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
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Abstract
The present invention relates to the borate fluorescent powders and preparation method thereof that a kind of cerium, terbium are co-doped with, and belong to field of light emitting materials.The chemical general formula of the fluorescent powder is：Ba2‑nSrnY5‑x‑y‑mLmCexTbyB5O17, wherein it is one or more in L Gd, La, Lu and Sc；Described x, n, m, y are molar fraction, and value range is respectively：0<X≤0.6,0≤n≤0.5,0≤m≤3,0<y≤3；The fluorescent powder belongs to rhombic system, space group Pbcn.The fluorescent powder is by building Ce3+‑Tb3+Energy transmission system obtains fluorescent powder tunable from blue light to green emission under near ultraviolet excitated, and external quantum efficiency is high, and thermal stability is excellent, potential applied to ultraviolet/near ultraviolet LED chip base white light LEDs as a kind of high-efficiency blue-green fluorescent powder.The present invention also provides the preparation method of above-mentioned fluorescent powder, this method preparation process is simple, pollution-free, easily operated.
Description
Technical field
The invention belongs to field of light emitting materials, and in particular to the borate fluorescent powder and its preparation side that a kind of cerium, terbium are co-doped with
Method.
Background technology
White light emitting diode (white light-emitting diodes, WLEDs) with its long lifespan, low energy consumption, nothing
The remarkable advantages such as pollution, efficient, small have broad application prospects in illumination and display field, are referred to as a new generation
Lighting source.
Currently, realizing that the major programme of white light LEDs is fluorescent powder switch technology, which has two kinds of realization methods：(1) blue
Light LED+ can be by yellow fluorescent powder (or red/green fluorescent powder) that blue-ray LED effectively excites.Indigo plant of this method due to LED
Light directly participates in the synthesis of white light, so the color of device changes, color weight with the coating layer thickness and driving voltage of fluorescent powder
Existing power is poor.Currently, most widely used is YAG:Ce3+Yellow fluorescent powder, light conversion efficiency is very high, but because of its luminescent spectrum
Predominantly greenish-yellow ingredient, red color components are insufficient, cause the colour rendering index of the white light LEDs of encapsulation it is relatively low (<80).(2) ultraviolet/close purple
The red, green, blue three primary colors fluorescent powder that outer LED+ can effectively be excited by ultraviolet/near ultraviolet LED.Because human eye is insensitive to ultraviolet light,
The color for the white light LEDs that this scheme obtains only is determined by red, green, blue three primary colors fluorescent powder, therefore color stable, reappears power
By force, it is the developing direction of white light LEDs.But at present can be with UV LED chip good match, efficient and thermal stability is good
Fluorescent powder also lacks very much.
Currently, widely used Ce in the market3+-Tb3+It is mainly LaPO to be co-doped with green emitting phosphor4:Ce3+,Tb3+.Its outer amount
Sub- efficiency is up to 90%, but its maximum excitation wavelength is located at 250-290nm, can not be excited by near ultraviolet chip, therefore can not make
For LED fluorescent powders.
Ba2Y5B5O17：Ce3+It is a kind of efficient blue-emitting phosphor, launch wavelength 445nm, internal quantum efficiency is more than
80%, external quantum efficiency 60% or so, but the fluorescent powder thermal stability is poor, and at 150 DEG C, luminous intensity only shines at room temperature
40% or so of intensity limits its potential application value.Tb3+(the Ba in this system2Y5B5O17：Tb3+) launch wavelength 543nm
Green light, but excitation spectrum cannot effectively be excited in 200~300nm by existing near ultraviolet chip.
Invention content
The invention solves blue in the prior art, synthetic technological condition existing for green emitting phosphor is not easy to control, thermostabilization
The technical problem that property is poor, luminous efficiency is low provides a kind of cerium, the borate fluorescent powder and preparation method thereof that terbium is co-doped with.
In order to solve the above-mentioned technical problem, technical scheme of the present invention is specific as follows：
The borate fluorescent powder that a kind of cerium, terbium are co-doped with, the chemical general formula of the fluorescent powder are：Ba2-nSrnY5-x-y- mLmCexTbyB5O17, wherein it is one or more in L Gd, La, Lu and Sc；Described x, n, m, y are molar fraction, value
Range is respectively：0<X≤0.6,0≤n≤0.5,0≤m≤3,0<y≤3；The fluorescent powder belongs to rhombic system, and space group is
Pbcn。
In the above-mentioned technical solutions, the molar fraction of described x, y are 0.001≤x≤0.3,0.001≤y≤2.
The present invention also provides a kind of preparation methods for the borate fluorescent powder that cerium, terbium are co-doped with, and include the following steps：
(1) according to chemical formula Ba2-nSrnY5-x-y-mLmCexTbyB5O17The stoichiometric ratio of middle each element, weigh respectively containing
Ba2+Compound, contain Y3+Compound, contain Ce3+Compound, contain Tb3+Compound, contain B3+Compound,
Contain Sr2+Compound, contain La3+Compound, contain Gd3+Compound, contain Lu3+Compound and contain Sc3+
Compound, grind and be uniformly mixed in the agate mortar, obtain mixture；
(2) by said mixture under reducing gas atmosphere or in air, 350 DEG C~600 DEG C are pre-sintered, when sintering
Between be 1~6 hour；It is 1000 DEG C~1300 DEG C that sintering temperature is warming up under reducing gas atmosphere, and sintering time is 2~24 small
When, after sintering products therefrom natural cooling, grind the borate fluorescent powder being co-doped with to get cerium, terbium.
In the above-mentioned technical solutions, the reducing gas is CO or H2。
In the above-mentioned technical solutions, described to contain Ba2+Compound be the oxide containing corresponding ion, carbonate, nitre
It is one or more in hydrochlorate and halide；
It is described to contain Y3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one
Kind is a variety of；
It is described to contain Ce3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one
Kind is a variety of；
It is described to contain Tb3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one
Kind is a variety of；
It is described to contain Sr2+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one
Kind is a variety of；
It is described to contain La3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one
Kind is a variety of；
It is described to contain Gd3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one
Kind is a variety of；
It is described to contain Lu3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one
Kind is a variety of；
It is described to contain Sc3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one
Kind is a variety of.
In the above-mentioned technical solutions, described to contain B3+Compound be H3BO3。
The beneficial effects of the invention are as follows：
1, the borate fluorescent powder that cerium provided by the invention, terbium are co-doped with, in the case where 260~360nm is purple light excited, transmitting
The bluish-green transmitting ratio tunable opticals of 445nm-543nm, can be combined with black light chip and prepare white light LEDs.The fluorescent powder is by mixing
It is miscellaneous to overcome fluorescent powder Ba2Y5B5O17：Ce3+The problem of thermal stability difference, by energy transmission by Tb3+Excitation spectrum by 200
~300nm red shifts solve the problems, such as unmatched near ultraviolet chip to 250~360nm.
2, the borate fluorescent powder that cerium provided by the invention, terbium are co-doped with, passes through Ce3+、Tb3+It is co-doped with, builds Ce3+→Tb3+Have
The energy transmission of effect has expanded light emitting ionic Tb3+Effective excites scope in UV light region, realizes Tb3+Excitation spectrum
By the red shift of 200~300nm to 250~360nm, meanwhile, Tb3+Be entrained in and do not reduce quantum efficiency in the case of, and greatly
The thermal stability for improving material, at 150 DEG C, luminous intensity is more than the 90% of luminous intensity at room temperature.Both can with it is current
Black light chip emission matches, and has good temperature characterisitic, makes it at a temperature of LED operation, remains efficient
Rate.
3, the borate fluorescent powder that cerium provided by the invention, terbium are co-doped with, external quantum efficiency are up to 60%, internal quantum efficiency
75% or so, there is good thermal stability.By Sr, Gd, La, Lu, the doping of Sc plasmas is not changing its crystal structure
Under the conditions of, regulate and control the excitation spectrum range and emissive porwer of fluorescent powder, enable preferably near ultraviolet LED chip and fluorescence
The emission spectrum matching of mercury vapour in lamp, can be as a kind of white light LEDs based on black light LED chip or three primary colours fluorescence
Blue-green fluorescent powder in lamp.
4, the borate fluorescent powder that cerium provided by the invention, terbium are co-doped with passes through the controllable fluorescent powder blue green light of the value of x, y
Transmitting ratio.
5, the preparation method for the borate fluorescent powder that cerium provided by the invention, terbium are co-doped with, preparation process is simple, no dirt
Dye, it is easily operated.
Description of the drawings
Invention is further described in detail with reference to the accompanying drawings and detailed description.
Fig. 1 is the XRD spectrums of fluorescent powder prepared by the embodiment of the present invention 4；
Fig. 2 is the excitation spectrum of fluorescent powder prepared by the embodiment of the present invention 4；
Fig. 3 is the emission spectrum of fluorescent powder prepared by the embodiment of the present invention 1,3,4；
Fig. 4 is Ce of the present invention3+-Tb3+The principle of luminosity figure of energy transmission；
Fig. 5 is the cie color coordinate diagram of fluorescent powder prepared by the embodiment of the present invention 1,2,3,4,5.
Specific implementation mode
The present invention invention thought be：The borate fluorescent powder Ba that a kind of cerium provided by the invention, terbium are co-doped with2- nSrnY5-x-y-mLmCexTbyB5O17, being that a kind of luminous efficiency is high, thermal stability is good is suitable for the bluish-green of near ultraviolet/ultraviolet excitation
Color fluorescent powder.In this system, rare earth ion Tb3+Stronger peak value can be launched under the ultraviolet excitation of 250~300nm to exist
The narrowband green light of 543nm or so, Tb3+It is not absorbed substantially in the regions 300~350nm.Rare earth ion Ce3+Can 200~
Under the ultraviolet excitation of 380nm, launch peak value 443nm or so strong blue violet light.We pass through Ce3+And Tb3+It is co-doped with, it is real
Ce is showed3+→Tb3+Energy transmission so that Tb3+Ion emits 543nm green lights, and then obtain under 200~360nm excitations
It is a kind of to be suitable for the ultraviolet novel blue-green fluorescent powder near ultraviolet excitation.By Sr, Gd, La, the elements such as Lu, Sc and its contain
The change of amount can adjust crystal field environment, improve luminous intensity, and suitably adjust excitation spectrum.Principle schematic is shown in attached drawing 4.
The borate fluorescent powder that cerium provided by the invention, terbium are co-doped with, the chemical general formula of the fluorescent powder are：Ba2- nSrnY5-x-y-mLmCexTbyB5O17, wherein it is one or more in L Gd, La, Lu and Sc；Described x, n, m, y be mole point
Number, value range are respectively：0<X≤0.6,0≤n≤0.5,0≤m≤3,0<y≤3；The fluorescent powder belongs to rhombic system,
Space group is Pbcn.The molar fraction of described x, y are preferably 0.001≤x≤0.3,0.001≤y≤2.Due to L ionic radius,
The property differences such as electronegativity, the influence to crystalline field is also different, therefore the preferable value range of the m is due to the difference of L ions
It is different.The fluorescent powder wavelength be 260~360nm ultraviolet excitation under, obtain emission peak 445nm blue light and
The green light of 543nm, and blue green light emissive porwer can be tuned by Doped ions.
The preparation method for the borate fluorescent powder that cerium provided by the invention, terbium are co-doped with is as follows：
(1) according to chemical formula Ba2-nSrnY5-x-y-mLmCexTbyB5O17The stoichiometric ratio of middle each element, weigh respectively containing
Ba2+Compound, contain Y3+Compound, contain Ce3+Compound, contain Tb3+Compound, contain B3+Compound,
Contain Sr2+Compound, contain La3+Compound, contain Gd3+Compound, contain Lu3+Compound and contain Sc3+
Compound, grind and be uniformly mixed in the agate mortar, obtain mixture；
(2) by said mixture under reducing gas atmosphere or in air, 350 DEG C~600 DEG C are pre-sintered, when sintering
Between be 1~6 hour；It is 1000 DEG C~1300 DEG C that sintering temperature is warming up under reducing gas atmosphere, and sintering time is 2~24 small
When, after sintering products therefrom natural cooling, grind the borate fluorescent powder being co-doped with to get cerium, terbium.
It is described to contain Ba2+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one
Kind is a variety of；It is described to contain Y3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one
Kind is a variety of；It is described to contain Ce3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in
It is one or more；It is described to contain Tb3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in
It is one or more；It is described to contain Sr2+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide
In it is one or more；It is described to contain La3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halogenation
It is one or more in object；It is described to contain Gd3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halogen
It is one or more in compound；It is described to contain Lu3+Compound be the oxide containing corresponding ion, carbonate, nitrate and
It is one or more in halide；It is described to contain Sc3+Compound be the oxide containing corresponding ion, carbonate, nitrate
With it is one or more in halide.It is described to contain B3+Compound be preferably H3BO3.The reducing gas is CO or H2。
Change calcination temperature and calcination time according to different ions and the different compounds of selection to control to obtain required material
The crystalline phase of material.
The preparation method for the borate fluorescent powder that cerium, the terbium of the above-mentioned offer of the present invention are co-doped with is high temperature solid-state method.However, should
The synthetic method of fluorescent powder is not limited thereto, wherein the wet chemistry methods such as sol-gal process, combustion method, emulsion method can synthesize
The fluorescent powder.
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
With the pure BaCO of analysis in embodiment3, SrCO3, top pure grade H3BO3, high-purity Y2O3, CeO2, Tb4O7, La2O3, Lu2O3,
Gd2O3, Sc2O3Make raw material, prepares various embodiments of the present invention fluorescent powder.
Embodiment 1 (comparative example)
Ba2Y4.95Ce0.05B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Y2O3：0.5589 gram, CeO2：0.0086
Gram.Ground and mixed is uniform in the agate mortar, is put into corundum crucible, and capping is placed in high temperature furnace, under reducing atmosphere or empty
It in gas, is pre-sintered at 450 DEG C, sintering time is 4 hours, in carbon monoxide CO or hydrogen H2It is warming up under reducing atmosphere
It is sintered 10 hours at 1200 DEG C, after natural cooling, appropriate grinding obtains fluorescent powder Ba2Y4.95Ce0.05B5O17.Its crystal structure
Similar to Example 4, the excitation spectrum of the present embodiment is shown in attached drawing 4 (a), and 3 curve 1 of attached drawing is the emission spectrum of the present embodiment, attached
Fig. 5 data points 1 are the chromaticity coordinates of the present embodiment.
Embodiment 2
Ba2Y4.65Ce0.05Tb0.3B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Y2O3：0.5250 gram, CeO2：0.0086
Gram, Tb4O7：0.0561 gram.Ground and mixed is uniform in the agate mortar, is put into corundum crucible, and capping is placed in high temperature furnace,
It under reducing atmosphere or in air, is pre-sintered at 450 DEG C, sintering time is 4 hours, in carbon monoxide CO or hydrogen H2Also
It is warming up at 1200 DEG C and is sintered 10 hours under Primordial Qi atmosphere, after natural cooling, appropriate grinding obtains fluorescent powder
Ba2Y4.65Ce0.05Tb0.3B5O17.Its crystal structure, excitation spectrum are similar to Example 4, and 3 curve 2 of attached drawing is the hair of the present embodiment
Spectrum is penetrated, 5 data point 2 of attached drawing is the chromaticity coordinate of the present embodiment.
Embodiment 3
Ba2Y4.45Ce0.05Tb0.5B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Y2O3：0.5025 gram, CeO2：0.0086
Gram, Tb4O7：0.0935 gram.Ground and mixed is uniform in the agate mortar, is put into corundum crucible, and capping is placed in high temperature furnace,
It under reducing atmosphere or in air, is pre-sintered at 450 DEG C, sintering time is 4 hours, in carbon monoxide CO or hydrogen H2Also
It is warming up at 1200 DEG C and is sintered 10 hours under Primordial Qi atmosphere, after natural cooling, appropriate grinding obtains fluorescent powder
Ba2Y4.45Ce0.05Tb0.5B5O17.Its crystal structure, excitation spectrum, emission spectrum are similar to Example 4, but the present embodiment Ce3+'s
Transmitting is better than embodiment 4, Tb3+Transmitting be weaker than embodiment 4,5 data point 3 of attached drawing is the chromaticity coordinate of the present embodiment.
Embodiment 4
Ba2Y3.95Ce0.05Tb1B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Y2O3：0.4460 gram, CeO2：0.0086
Gram, Tb4O7：0.1869 gram.Ground and mixed is uniform in the agate mortar, is put into corundum crucible, and capping is placed in high temperature furnace,
It under reducing atmosphere or in air, is pre-sintered at 450 DEG C, sintering time is 4 hours, in carbon monoxide CO or hydrogen H2Also
It is warming up at 1200 DEG C and is sintered 10 hours under Primordial Qi atmosphere, after natural cooling, appropriate grinding obtains fluorescent powder
Ba2Y3.95Ce0.05Tb1B5O17.Attached drawing 1,2 is the XRD spectrum and excitation spectrum of the present embodiment, and attached drawing 4 (c) is the present embodiment
Emission spectrum, 5 data point 4 of attached drawing are the chromaticity coordinates of the present embodiment.
Embodiment 5
Ba2Y3.45Ce0.05Tb1.5B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Y2O3：0.3895 gram, CeO2：0.0086
Gram, Tb4O7：0.2804 gram.Ground and mixed is uniform in the agate mortar, is put into corundum crucible, and capping is placed in high temperature furnace,
It under reducing atmosphere or in air, is pre-sintered at 450 DEG C, sintering time is 4 hours, in carbon monoxide CO or hydrogen H2Also
It is warming up at 1200 DEG C and is sintered 10 hours under Primordial Qi atmosphere, after natural cooling, appropriate grinding obtains fluorescent powder
Ba2Y3.45Ce0.05Tb1.5B5O17.Its crystal structure, excitation spectrum are similar to Example 4, but the present embodiment Ce3+Transmitting and Tb3 +Transmitting be weaker than embodiment 4,5 data point 5 of attached drawing is the chromaticity coordinate of the present embodiment.
Embodiment 6
Ba2Y2.95Ce0.05Tb2B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Y2O3：0.3331 gram, CeO2：0.0086
Gram, Tb4O7：0.3738 gram.Ground and mixed is uniform in the agate mortar, is put into corundum crucible, and capping is placed in high temperature furnace,
It under reducing atmosphere or in air, is pre-sintered at 450 DEG C, sintering time is 4 hours, in carbon monoxide CO or hydrogen H2Also
It is warming up at 1200 DEG C and is sintered 10 hours under Primordial Qi atmosphere, after natural cooling, appropriate grinding obtains fluorescent powder
Ba2Y2.95Ce0.05Tb2B5O17.Its crystal structure, excitation spectrum and emission spectrum are similar to Example 4, but the present embodiment Ce3+'s
Transmitting and Tb3+Transmitting be weaker than embodiment 4.
Embodiment 7
Ba2Y1.95Ce0.05Tb3B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Y2O3：0.2202 gram, CeO2：0.0086
Gram, Tb4O7：0.5608 gram.Ground and mixed is uniform in the agate mortar, is put into corundum crucible, and capping is placed in high temperature furnace,
It under reducing atmosphere or in air, is pre-sintered at 450 DEG C, sintering time is 4 hours, in carbon monoxide CO or hydrogen H2Also
It is warming up at 1200 DEG C and is sintered 10 hours under Primordial Qi atmosphere, after natural cooling, appropriate grinding obtains fluorescent powder
Ba2Y1.95Ce0.05Tb3B5O17.Its crystal structure, excitation spectrum and emission spectrum are similar to Example 4, but the present embodiment Ce3+'s
Transmitting and Tb3+Transmitting be weaker than embodiment 4.
Embodiment 8
Ba1.5Sr0.5Y3.95Ce0.05Tb1B5O17Preparation
Stoichiometrically weigh BaCO3：0.2960 gram, SrCO3：0.0738 gram, H3BO3：0.3092 gram, Y2O3：
0.4460 gram, CeO2：0.0086 gram, Tb4O7：0.1869 gram.Ground and mixed is uniform in the agate mortar, is put into corundum crucible,
Capping, is placed in high temperature furnace,2Under reducing atmosphere or in air, it is pre-sintered at 450 DEG C, sintering time is 4 hours,
Carbon monoxide CO or hydrogen H2It is warming up at 1000 DEG C and is sintered 24 hours under reducing atmosphere, after natural cooling, appropriate grinding is
Obtain fluorescent powder Ba1.5Sr0.5Y3.95Ce0.05Tb1B5O17.Its crystal structure, excitation spectrum and emission spectrum are similar to Example 4,
But the present embodiment Ce3+Transmitting and Tb3+Transmitting enhance 10% compared with embodiment 4.
Embodiment 9
Ba2Y0.95Lu3Ce0.05Tb1B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, Lu2O3:0.5969 gram, H3BO3：0.3092 gram, Y2O3：
0.1073 gram, CeO2：0.0086 gram, Tb4O7：0.1869 gram.Ground and mixed is uniform in the agate mortar, is put into corundum crucible,
Capping, is placed in high temperature furnace, under reducing atmosphere or in air, is pre-sintered at 350 DEG C, and sintering time is 6 hours, one
Carbonoxide CO or hydrogen H2It is warming up at 1210 DEG C and is sintered 7 hours under reducing atmosphere, after natural cooling, appropriate grinding obtains
Fluorescent powder Ba2Y0.95Lu3Ce0.05Tb1B5O17.Its crystal structure, excitation spectrum and emission spectrum are similar to Example 4, and this reality
Apply a Ce3+Transmitting and Tb3+Transmitting enhance 20% compared with embodiment 4.
Embodiment 10
Ba2Y1.95Gd2Ce0.05Tb1B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, Gd2O3:0.3625 gram, H3BO3：0.3092 gram, Y2O3：
0.2202 gram, CeO2：0.0086 gram, Tb4O7：0.1869 gram.Ground and mixed is uniform in the agate mortar, is put into corundum crucible,
Capping, is placed in high temperature furnace, under reducing atmosphere or in air, is pre-sintered at 600 DEG C, and sintering time is 1 hour, one
Carbonoxide CO or hydrogen H2It is warming up at 1190 DEG C and is sintered 8 hours under reducing atmosphere, after natural cooling, appropriate grinding obtains
Fluorescent powder Ba2Y1.95Gd2Ce0.05Tb1B5O17.Its crystal structure, excitation spectrum and emission spectrum are similar to Example 4, and this reality
Apply a Ce3+Transmitting and Tb3+Transmitting enhance 15% compared with embodiment 4.
Embodiment 11
Ba2Y2.95Sc1Ce0.05Tb1B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, Sc2O3:0.0689 gram, H3BO3：0.3092 gram, Y2O3：
0.3331 gram, CeO2：0.0086 gram, Tb4O7：0.1869 gram.Ground and mixed is uniform in the agate mortar, is put into corundum crucible,
Capping, is placed in high temperature furnace, under reducing atmosphere or in air, is pre-sintered at 500 DEG C, and sintering time is 3 hours, one
Carbonoxide CO or hydrogen H2It is warming up at 1000 DEG C and is sintered 20 hours under reducing atmosphere, after natural cooling, suitably grind to obtain the final product
To fluorescent powder Ba2Y2.95Sc1Ce0.05Tb1B5O17.Its crystal structure, excitation spectrum and emission spectrum are similar to Example 4, and this
Embodiment Ce3+Transmitting and Tb3+Transmitting compared with embodiment 4 enhance.
Embodiment 12
Ba2Y1.95Lu1La0.5Gd0.5Ce0.05Tb1B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, La2O3:0.0815 gram, H3BO3：0.3092 gram, Y2O3：
0.2202 gram, Lu2O3：0.1990 gram, Gd2O3:0.0906 gram of CeO2：0.0086 gram, Tb4O7：0.1869 gram.In the agate mortar
Ground and mixed is uniform, is put into corundum crucible, capping, be placed in high temperature furnace, under reducing atmosphere or in air, at 500 DEG C into
Row is pre-sintered, and sintering time is 3 hours, in carbon monoxide CO or hydrogen H2It is warming up under reducing atmosphere at 1000 DEG C and is sintered 20
Hour, after natural cooling, appropriate grinding obtains fluorescent powder Ba2Y1.95Lu1La0.5Gd0.5Ce0.05Tb1B5O17.Its crystal structure,
Excitation spectrum and emission spectrum are similar to Example 4, and the present embodiment Ce3+Transmitting and Tb3+Transmitting enhanced.
Embodiment 13
Ba2Y2.45Sc0.5La1Ce0.05Tb1B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, Sc2O3:0.0345 gram, H3BO3：0.3092 gram, Y2O3：
0.2766 gram, La2O3：0.1629 gram, CeO2：0.0086 gram, Tb4O7：0.1869 gram.Ground and mixed is uniform in the agate mortar,
It is put into corundum crucible, is capped, is placed in high temperature furnace, under reducing atmosphere or in air, is pre-sintered at 500 DEG C, be sintered
Time is 3 hours, in carbon monoxide CO or hydrogen H2It is warming up at 1240 DEG C and is sintered 8 hours under reducing atmosphere, natural cooling
Afterwards, appropriate grinding obtains fluorescent powder Ba2Y2.45Sc0.5La1Ce0.05Tb1B5O17.Its crystal structure, excitation spectrum and emission spectrum
It is similar to Example 4, and the present embodiment Ce3+Transmitting and Tb3+Transmitting enhanced.
Embodiment 14
Ba2Y0.95Lu2La0.5Gd0.3Sc0.2Ce0.05Tb1B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, La2O3:0.0815 gram, H3BO3：0.3092 gram, Y2O3：
0.1073 gram, Lu2O3：0.3979 gram, Gd2O3:0.0544 gram, Sc2O3:0.0138 gram, CeO2：0.0086 gram, Tb4O7：0.1869
Gram.Ground and mixed is uniform in the agate mortar, is put into corundum crucible, and capping is placed in high temperature furnace, under reducing atmosphere or empty
It in gas, is pre-sintered at 500 DEG C, sintering time is 3 hours, in carbon monoxide CO or hydrogen H2It is warming up under reducing atmosphere
It is sintered 2 hours at 1300 DEG C, after natural cooling, appropriate grinding obtains fluorescent powder
Ba2Y0.95Lu2La0.5Gd0.3Sc0.2Ce0.05Tb1B5O17.Its crystal structure, excitation spectrum and emission spectrum are similar to Example 4,
And the present embodiment Ce3+Transmitting and Tb3+Transmitting enhanced.
Embodiment 15
Ba2Y4.998Ce0.001Tb0.001B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Y2O3：0.5643 gram, CeO2：0.0002
Gram, Tb4O7：0.0002 gram.Ground and mixed is uniform in the agate mortar, is put into corundum crucible, and capping is placed in high temperature furnace,
It under reducing atmosphere or in air, is pre-sintered at 450 DEG C, sintering time is 4 hours, in carbon monoxide CO or hydrogen H2Also
It is warming up at 1200 DEG C and is sintered 10 hours under Primordial Qi atmosphere, after natural cooling, appropriate grinding obtains fluorescent powder
Ba2Y4.998Ce0.001Tb0.001B5O17.Its crystal structure, excitation spectrum and emission spectrum are similar to Example 4, but the present embodiment
Ce3+Transmitting and Tb3+Transmitting be weaker than embodiment 4.
Embodiment 16
Ba2Y4.4Ce0.5Tb0.1B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Y2O3：0.4968 gram, CeO2：0.0861
Gram, Tb4O7：0.0187 gram.Ground and mixed is uniform in the agate mortar, is put into corundum crucible, and capping is placed in high temperature furnace,
It under reducing atmosphere or in air, is pre-sintered at 450 DEG C, sintering time is 4 hours, in carbon monoxide CO or hydrogen H2Also
It is warming up at 1200 DEG C and is sintered 10 hours under Primordial Qi atmosphere, after natural cooling, appropriate grinding obtains fluorescent powder
Ba2Y4.4Ce0.5Tb0.1B5O17.Its crystal structure, excitation spectrum and emission spectrum are similar to Example 4, but the present embodiment Ce3+'s
Transmitting and Tb3+Transmitting be weaker than embodiment 4.
Embodiment 17
Ba2Y4.1Ce0.6Tb0.3B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Y2O3：0.4629 gram, CeO2：0.1033
Gram, Tb4O7：0.0561 gram.Ground and mixed is uniform in the agate mortar, is put into corundum crucible, and capping is placed in high temperature furnace,
It under reducing atmosphere or in air, is pre-sintered at 450 DEG C, sintering time is 4 hours, in carbon monoxide CO or hydrogen H2Also
It is warming up at 1200 DEG C and is sintered 10 hours under Primordial Qi atmosphere, after natural cooling, appropriate grinding obtains fluorescent powder
Ba2Y4.1Ce0.6Tb0.3B5O17.Its crystal structure, excitation spectrum and emission spectrum are similar to Example 4, but the present embodiment Ce3+'s
Transmitting and Tb3+Transmitting be weaker than embodiment 4.
Contain Ba described in above-described embodiment2+Compound, contain Y3+Compound, contain Ce3+Compound, contain
There is Tb3+Compound, contain B3+Compound, contain Sr2+Compound, contain La3+Compound, contain Gd3+Chemical combination
Object contains Lu3+Compound and contain Sc3+Compound may be replaced by the arbitrary substance or its group of above-mentioned restriction
It closes, gained sample can also obtain technique effect similar with sample prepared by above-described embodiment, no longer repeat one by one here.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (6)
1. the borate fluorescent powder that a kind of cerium, terbium are co-doped with, which is characterized in that the chemical general formula of the fluorescent powder is：Ba2- nSrnY5-x-y-mLmCexTbyB5O17, wherein it is one or more in L Gd, La, Lu and Sc；Described x, n, m, y be mole point
Number, value range are respectively：0<X≤0.6,0≤n≤0.5,0≤m≤3,0<y≤3；The fluorescent powder belongs to rhombic system,
Space group is Pbcn.
2. the borate fluorescent powder that cerium according to claim 1, terbium are co-doped with, which is characterized in that the molar fraction of described x, y
For 0.001≤x≤0.3,0.001≤y≤2.
3. a kind of preparation method for the borate fluorescent powder that cerium described in claim 1, terbium are co-doped with, which is characterized in that including with
Lower step：
(1) according to chemical formula Ba2-nSrnY5-x-y-mLmCexTbyB5O17The stoichiometric ratio of middle each element is weighed respectively containing Ba2+
Compound, contain Y3+Compound, contain Ce3+Compound, contain Tb3+Compound, contain B3+Compound, contain
Sr2+Compound, contain La3+Compound, contain Gd3+Compound, contain Lu3+Compound and contain Sc3+Change
Object is closed, grinds and is uniformly mixed in the agate mortar, obtain mixture；
(2) by said mixture under reducing gas atmosphere or in air, 350 DEG C~600 DEG C are pre-sintered, and sintering time is
1~6 hour；It is 1000 DEG C~1300 DEG C that sintering temperature is warming up under reducing gas atmosphere, and sintering time is 2~24 hours,
After products therefrom natural cooling being sintered, the borate fluorescent powder being co-doped with to get cerium, terbium is ground.
4. the preparation method for the borate fluorescent powder that the cerium, terbium described in claim 3 are co-doped with, which is characterized in that the also Primordial Qi
Body is CO or H2。
5. the preparation method for the borate fluorescent powder that the cerium, terbium described in claim 3 are co-doped with, which is characterized in that described to contain Ba2+
Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in it is one or more；
It is described to contain Y3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one kind or
It is a variety of；
It is described to contain Ce3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one kind or
It is a variety of；
It is described to contain Tb3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one kind or
It is a variety of；
It is described to contain Sr2+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one kind or
It is a variety of；
It is described to contain La3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one kind or
It is a variety of；
It is described to contain Gd3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one kind or
It is a variety of；
It is described to contain Lu3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one kind or
It is a variety of；
It is described to contain Sc3+Compound be the oxide containing corresponding ion, carbonate, nitrate and halide in one kind or
It is a variety of.
6. the preparation method for the borate fluorescent powder that the cerium, terbium described in claim 3 are co-doped with, which is characterized in that described to contain B3+
Compound be H3BO3。
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| Ab Initio Structure Determination and Photoluminescent Properties of an Efficient, Thermally Stable Blue Phosphor, Ba2Y5B5O17:Ce3+;Martin Hermus等;《CHEMISTRY OF MATERIALS》;20160116;第28卷(第4期);全文 * |
| Novel Emitting-Color Tunable Phosphors Ba3Y2(BO3)4:Ce3+,Tb3+ with Efficient Energy Transfer for Near-UV Light-Emitting Diodes;Bing Han等;《JOURNAL OF THE AMERICAN CERAMIC SOCIETY》;20130131;第96卷(第1期);全文 * |
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