CN107033896A - A kind of blue fluorescent powder for white-light LED and preparation method and application - Google Patents
A kind of blue fluorescent powder for white-light LED and preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of blue fluorescent powder for white-light LED and preparation method and application, belong to luminescent material technical field.Solve Ba in the prior art2Lu5B5O17：Ce3+Crystal phase structure is unstable, and synthetic technological condition is whard to control, the technical problem that heat endurance is poor, luminous efficiency is low.The chemical formula of fluorescent material of the present invention is：Ba2‑mAmLu5‑x‑nLnCexB5O17, wherein, A is one kind in Ca, Sr, and L is the one or more in Y, La, Gd, Sc, Yb, Er, and x, m, n are molar fraction, and span is respectively：0<X≤0.6,0≤m≤1,0≤n≤2.Fluorescent material prepared by the present invention can be well by 200~380nm ultraviolet and near ultraviolet excitation, and fluorescent material quantum efficiency is high, and good heat stability, technique simple and flexible is reproducible, potential to be applied in ultraviolet/near ultraviolet LED chip base white light LEDs.
Description
Technical field
The present invention relates to luminescent material technical field, and in particular to a kind of blue fluorescent powder for white-light LED and its preparation side
Method and application.
Background technology
In recent years, as the whole world of the semiconductor lighting cause of light emitting diode (LED) is risen, white light LEDs and various coloured silks
Color LED causes people as light source of new generation and greatly paid close attention to.Compared with traditional incandescent lamp, fluorescent lamp, this forth generation
Lighting source has many merits such as durable in use, pollution-free, performance is stable, the response time is short, efficiency is high.
At present, the major programme for realizing white light LEDs is to use fluorescent material switch technology.Most ripe approach be blue-ray LED+
The yellow fluorescent powder (or red/green fluorescent material) that can be effectively excited by blue-ray LED.Because blue chip is under high electric current,
The luminous intensity of blue spectrum is more increased than gold-tinted fast, thus causes the problems such as white light LEDs color drift, colour temperature change.Such as
Current most widely used YAG:Ce3+Yellow fluorescent powder is mainly greenish-yellow composition because of its luminescent spectrum, and the deficiency of red color components is led
Cause encapsulation white light LEDs colour rendering index it is relatively low (<80).
Another scheme is the red, green, blue three using ultraviolet/near ultraviolet LED+can effectively be excited by ultraviolet/near ultraviolet LED
Primary colours fluorescent material synthesizes white light LEDs.Because human eye is insensitive to ultraviolet light, the colors of the white light LEDs that this scheme is obtained only by it is red,
Green, blue three primary colors fluorescent powder is determined, therefore color stable, is reappeared power by force, is the developing direction of white light LEDs.
In recent years, emerged with the advantage of domestic cultural industry, formd the market demand huge to high-end illumination, it is senior
Hotel, museum, hospital, school etc. propose higher requirement to source mass.Therefore, near ultraviolet excitated fluorescent material is broken through
Technical bottleneck, it is of great advantage to seizing high-end illumination market.But, at present can with ultraviolet/near ultraviolet LED chip good match,
The efficiency high and good fluorescent material of heat endurance also lacks very much.
At present, the widely used blue colour fluorescent powder of in the market is mainly BaMgAl10O17：Eu2+, its calcination temperature height need to
More than 1500 DEG C, most preferably excite position in 310nm, be not the optimal selection of LED blue colour fluorescent powders therefore.
Ba2Lu5B5O17：Ce3+It is a kind of efficient blue-emitting phosphor, luminescent properties are excellent, with Ba2Y5B5O17：Ce3+
With identical structure (as shown in Figure 1), but because components do match easily unbalance synthesis technique is difficult to control to, so no one obtains so far
Its stable pure phase is obtained, simultaneously because there is dephasign generation to reduce Ce in material3+Absorption so that the luminous intensity of fluorescent material
Weaken significantly, and more dephasign even makes to excite, emission spectrum changes.
The content of the invention
In consideration of it, the purpose of the present invention is by controlling rational sintering process, selection matching combinations of reactants, to solve
Ba in the prior art2Lu5B5O17：Ce3+Fluorescent material crystal phase structure is unstable, synthetic technological condition is whard to control, heat endurance is poor,
There is provided a kind of blue fluorescent powder for white-light LED and preparation method and application for the low technical problem of luminous efficiency.
In order to solve the above-mentioned technical problem, technical scheme is specific as follows：
A kind of blue fluorescent powder for white-light LED, the chemical general formula of the fluorescent material is：Ba2-mAmLu5-x-nLnCexB5O17, formula
In, A is one kind in Ca, Sr, and L is Y, La, Gd, Sc, Yb, Er one or more, and x, m, n are molar fraction, value model
Enclose respectively：0<X≤0.6,0≤m≤1,0≤n≤2.
Preferably, described x, m, n span are respectively：0.01≤x≤0.6,0<M≤1,0<n≤2.
It is further preferred that described x, m, n span are respectively：0.01≤x≤0.3,0<M≤0.5,0<n≤1.
A kind of preparation method of above-mentioned blue fluorescent powder for white-light LED, comprises the following steps：
(1) according to chemical formula Ba2-mAmLu5-x-nLnCexB5O17The stoichiometric proportion of middle each element, is weighed containing Ba respectively2+
Compound, contain Ca2+Compound, contain Sr2+Compound, contain Lu3+Compound, contain Ce3+Compound, contain
There is Y3+Compound, contain La3+Compound, contain Gd3+Compound, contain Sc3+Compound, contain Yb3+Chemical combination
Thing, contain Er3+Compound and contain B3+Compound, grind and be well mixed, obtain mixture；
(2) by said mixture in 400 DEG C~550 DEG C 2~8h of pre-sintering；Sintering temperature is warming up under reducing gas atmosphere
Spend for 1100 DEG C~1250 DEG C, sintering time is 4~20h, after sintering products therefrom natural cooling, grinding produces white light LEDs
Use blue colour fluorescent powder.
Preferably, the reducing gas is CO or H2。
Preferably, it is described to contain Ba2+Compound to contain Ba2+Oxide, carbonate, nitrate and the halogen of ion
One or more in compound；
It is described to contain Ca2+Compound to contain Ca2+Oxide, carbonate, nitrate and halide in one kind or
It is a variety of；
It is described to contain Sr2+Compound to contain Sr2+Oxide, 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
Plant or a variety of；
It is described to contain Ce3+Compound to contain Ce3+Oxide, carbonate, nitrate and halide in one kind or
It is a variety of；
It is described to contain Y3+Compound to contain Y3+Oxide, carbonate, nitrate and halide in one kind or many
Kind；
It is described to contain La3+Compound to contain La3+Oxide, carbonate, nitrate and halide in one kind or
It is a variety of；
It is described to contain Gd3+Compound to contain Gd3+Oxide, carbonate, nitrate and halide in one kind or
It is a variety of；
It is described to contain Sc3+Compound to contain Sc3+Oxide, carbonate, nitrate and halide in one kind or
It is a variety of；
It is described to contain Yb3+Compound to contain Yb3+Oxide, carbonate, nitrate and halide in one kind or
It is a variety of；
It is described to contain Er3+Compound to contain Er3+Oxide, carbonate, nitrate and halide in one kind or
It is a variety of.
Preferably, it is described to contain B3+Compound be H3BO3。
Preferably, it is described it is pre-sintered after, pre-sintered product is first cooled down, grind it is abundant after, then be sintered.
A kind of application of the above-mentioned blue fluorescent powder for white-light LED in ultraviolet/near ultraviolet LED chip base white light LEDs.
Compared with prior art, beneficial effects of the present invention：
In fluorescent material Ba2-mAmLu5-x-nLnCexB5O17In, due to spies such as each element ionic radius, electronegativity, charge polarities
Sex differernce is very big, if coordination matching imbalance or calcination improper process control, easily cause mismatch, prevent each material from consolidating completely
It is molten and produce lattice defect, generate impurity crystalline phase.These lattice defects add the absorption of fluorescent material mesostroma, so as to reduce
Ce in material3+Absorption so that the luminous intensity of fluorescent material weakens.The present invention is by containing A, the different qualities reaction such as L
Thing, which is combined, causes its balanced Matching, while controlling reaction process (calcination temperature, calcination time), effectively stablizes lattice, suppresses
The generation of dephasign, is finally obtained the Ba of stable pure phase2-mAmLu5-x-nLnCexB5O17Crystal, its parent lattice belongs to orthorhombic
System, space group is Pbcn.And the light-emitting phosphor efficiency high, heat endurance are good, preparation process more energy-conserving and environment-protective, technique are produced
Simply, it is pollution-free, it is easy to operate.Especially Ba2Lu5B5O17：Ce3+.After testing, fluorescent material calcination temperature of the invention exists
About 1200 DEG C；In the case where 348nm is excited, emission peak is located at 435nm strong blue light, and external quantum efficiency compares BaMgAl10O17：Eu2+
(standard specimen) is high by 8% or so；Transmitting halfwidth is 100nm, is BaMgAl10O17：Eu2+Two times of the halfwidth (50nm) of (standard specimen).
The present invention successfully prepares Ba first in the world2Lu5B5O17：Ce3+。
The fluorescent material Ba of the present invention2-mAmLu5-x-nLnCexB5O17Beneficial to the raising of LED light spectrum widening and colour rendering, in purple
Possess huge application potential in outside/near ultraviolet LED chip base white light LEDs.
Brief description of the drawings
Fig. 1 is the XRD spectrums and standard card PDF NO.00-056-0113 of fluorescent material in the embodiment of the present invention 3；
Curve 1,2,3 is respectively fluorescent material exciting under 348nm shooting conditions in the embodiment of the present invention 3,8,6 in Fig. 2
With emission spectrum；
Fig. 3 is fluorescent material and BaMgAl in the embodiment of the present invention 310O17：Eu2+(standard specimen) under the same conditions excite with
Emission spectrum.
Embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are retouched with reference to embodiment
State, but it is to be understood that these descriptions are intended merely to further illustrate the features and advantages of the present invention rather than special to the present invention
The limitation that profit is required.
The present invention is by containing A, and the different qualities combinations of reactants such as L causes its balanced Matching, while controlling reaction process
(calcination temperature, calcination time) effectively stablizes lattice, it is suppressed that the generation of dephasign, is finally obtained pure Ba2- mAmLu5-x-nLnCexB5O17Crystal.The blue fluorescent powder for white-light LED Ba of the present invention2-mAmLu5-x-nLnCexB5O17, it is a kind of knot
Structure is purely stablized, luminous efficiency is high, the blue colour fluorescent powder suitable for ultraviolet/near ultraviolet excitation of good heat stability.Rare earth from
Sub- Ce3+Peak value can be launched in 435nm, halfwidth is strong for 100nm's under 200~380nm ultraviolet/near ultraviolet excitation
Blue violet light.In the case where 348nm is excited, external quantum efficiency compares BaMgAl10O17：Eu2+(standard specimen) is high by 8% or so.Calcination temperature is 1200
About DEG C.
The chemical general formula of blue fluorescent powder for white-light LED of the present invention is：Ba2-mAmLu5-x-nLnCexB5O17, wherein, A is
One kind in Ca, Sr, L is the one or more in La, Gd, Sc, Yb, Er, and x, m, n are molar fraction, and span is respectively：
0<X≤0.6,0≤m≤1,0≤n≤2, preferably 0.01≤x≤0.3,0<M≤0.5,0<n≤1.Due to A, L ionic radius,
The property differences such as electronegativity, the influence to crystalline field is also different, thus m, n preferable span because A, L ion difference and
It is different.The fluorescent material of the present invention exists in wavelength under 200~380nm ultraviolet/near ultraviolet excitation, to obtain emission peak
435nm blue light.
The preparation method of the blue fluorescent powder for white-light LED of the present invention, is comprised the following steps that：
(1) according to chemical formula Ba2-mAmLu5-x-nLnCexB5O17The stoichiometric proportion of middle each element, is weighed containing Ba respectively2+
Compound, contain Ca2+Compound, contain Sr2+Compound, contain Sc3+Compound, contain Lu3+Compound, contain
There is Ce3+Compound, contain Y3+Compound, contain La3+Compound, contain Gd3+Compound, contain Yb3+Chemical combination
Thing, contain Er3+Compound and contain B3+Compound, grind and be well mixed in agate mortar, obtain mixture；
In step (1), it is preferred that contain Ba2+、Ca2+、Sr2+Compound be the oxide containing corresponding ion, carbonic acid
One or more in salt, nitrate and halide；Contain Lu3+、Y3+、Ce3+、La3+、Gd3+、Sc3+、Yb3+、Er3+Compound
For the one or more in the oxide containing corresponding ion, carbonate, nitrate and halide；Contain B3+Compound it is preferred
For H3BO3.Reducing gas is preferably CO or H2；
(2) by said mixture in 400 DEG C~550 DEG C 2~8h of pre-sintering, sintering atmosphere is not particularly limited；Cooling takes
Going out, after being fully ground, sintering temperature is warming up under reducing gas atmosphere for 1100 DEG C~1250 DEG C, sintering time is 4~
20h, after sintering products therefrom natural cooling, grinding produces blue fluorescent powder for white-light LED；
In step (2), according to different ions and the combination of the different compounds of selection change calcination temperature and calcination time with
Control obtains the crystalline phase of material requested.
The preparation method of the blue fluorescent powder for white-light LED of the above-mentioned offer of the present invention is high temperature solid-state method.However, the fluorescence
The synthetic method of powder is not limited thereto.Wherein, can to synthesize this glimmering for the wet chemistry method such as sol-gal process, combustion method, emulsion method
Light 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, CaCO3, top pure grade H3BO3, high-purity Y2O3, Lu2O3, CeO2, La2O3,
Gd2O3, Sc2O3, Yb2O3, Er2O3Make raw material, prepare various embodiments of the present invention fluorescent material.
Embodiment 1
Ba2Lu4.99Ce0.01B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.9928 gram, CeO2：
0.0017 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible, is capped, is placed in high temperature furnace, pre- at 400 DEG C
8h is sintered, cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or hydrogen H2Under reducing atmosphere, sintered at 1100 DEG C
After 20h, natural cooling, appropriate grinding obtains fluorescent material Ba2Lu4.99Ce0.01B5O17.Its crystal structure is similar to Example 3,
But excite and be weaker than embodiment 3 with emissive porwer.
Embodiment 2
Ba1.9Ca0.1Lu4.98Ce0.02B5O17Preparation
Stoichiometrically weigh BaCO3：0.3749 gram, CaCO3:0.0100 gram, H3BO3：0.3092 gram, Lu2O3：
0.9948 gram, CeO2：0.0034 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible, is capped, is placed in high temperature
In stove, 420 DEG C of pre-sintering 6h, cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or hydrogen H2Under reducing atmosphere,
Sintered at 1120 DEG C after 18h, natural cooling, appropriate grinding obtains fluorescent material Ba1.9Ca0.1Lu4.99Ce0.02B5O17, its crystal knot
Structure is similar to Example 3, but excites and be weaker than embodiment 3 with emissive porwer.
Embodiment 3
Ba1.8Sr0.2Lu4.65Ce0.05La0.3B5O17Preparation
Stoichiometrically weigh BaCO3：0.3552 gram, H3BO3：0.3092 gram, Lu2O3：0.9252 gram, CeO2：
0.0086 gram, La2O3：0.0489 gram, SrCO3：0.0293 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible
In, capping is placed in high temperature furnace, 450 DEG C of pre-sintering 4h, and cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or
Hydrogen H2Under reducing atmosphere, sintered at 1150 DEG C after 16h, natural cooling, appropriate grinding obtains fluorescent material
Ba1.8Sr0.2Lu4.65Ce0.05La0.3B5O17。
Accompanying drawing 1 is the XRD spectrum of sample manufactured in the present embodiment, it was found from accompanying drawing 1, fluorescent material of the invention with
Ba2Y5B5O17：Ce3+With identical structure.
The curve 1 of accompanying drawing 2 is the excitation spectrum and emission spectrum of the present embodiment sample.It was found from accompanying drawing 2, the fluorescent material swash
It is 200~380nm that hair, which is located at, and excitation spectrum covers very wide ultraviolet/black light region；Launch under near ultraviolet excitation
Peak value is 435nm broadband blue light.
Accompanying drawing 3 is the present embodiment sample and BaMgAl10O17：Eu2+The transmitting light of (standard specimen) under 348nm ultraviolet excitations
Spectrum, the present embodiment sample has wider transmitting band as can be seen from Figure, although the present embodiment electromagnetic radiation peak value is less than
BaMgAl10O17：Eu2+, but emissive porwer (i.e. integral area) is higher than BaMgAl10O17：Eu2+(standard specimen).
Embodiment 4
Ba1.6Sr0.4Lu4.95Ce0.05B5O17Preparation
Stoichiometrically weigh BaCO3：0.3157 gram, H3BO3：0.3092 gram, Lu2O3：0.9849 gram, CeO2：
0.0086 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible, is capped, is placed in high temperature furnace, pre- at 450 DEG C
4h is sintered, cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or hydrogen H2Under reducing atmosphere, sintered at 1150 DEG C
After 16h, natural cooling, appropriate grinding obtains fluorescent material Ba1.6Sr0.4Lu4.95Ce0.05B5O17.Its crystal structure and embodiment 3
It is similar, excite roughly the same compared with Example 3 with emissive porwer.
Embodiment 5
Ba1.0Sr1.0Lu4.95Ce0.05B5O17Preparation
Stoichiometrically weigh BaCO3：0.1973 gram, SrCO3：0.1476 gram, H3BO3：0.3092 gram, Lu2O3：
0.9849 gram, CeO2：0.0086 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible, is capped, is placed in high temperature
In stove, pre-sintering 2h at 550 DEG C, cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or hydrogen H2Reducing atmosphere
Under, sintered at 1190 DEG C after 12h, natural cooling, appropriate grinding obtains fluorescent material Ba1.0Sr1.0Lu4.95Ce0.05B5O17.It is brilliant
Body structure is similar to Example 3, excites roughly the same compared with Example 3 with emissive porwer.
Embodiment 6
Ba2Lu4.95Ce0.05B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.9849 gram, CeO2：
0.0086 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible, is capped, is placed in high temperature furnace, is burnt at 550 DEG C
3h is tied, cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or hydrogen H2Under reducing atmosphere, sintered at 1200 DEG C
After 10h, natural cooling, appropriate grinding obtains fluorescent material Ba2Lu4.95Ce0.05B5O17.Its crystal structure is similar to Example 3,
Excite and slightly weaken compared to embodiment 3 with emissive porwer.
The curve 3 of accompanying drawing 2 is the excitation spectrum and emission spectrum of the present embodiment sample.It was found from accompanying drawing 2, the fluorescent material
Excite positioned at being 200~380nm, excitation spectrum covers very wide ultraviolet/black light region；Issued near ultraviolet excitation
Penetrate the broadband blue light that peak value is 435nm.
Embodiment 7
Ba2Lu4.4Ce0.6B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.8754 gram, CeO2：
0.1033 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible, is capped, is placed in high temperature furnace, 400 DEG C of pre-burnings
8h is tied, cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or hydrogen H2Under reducing atmosphere, sintered at 1250 DEG C
After 4h, natural cooling, appropriate grinding obtains fluorescent material Ba2Lu4.4Ce0.6B5O17.Its crystal structure is similar to Example 3, but
Excite and weakened with emissive porwer compared to embodiment 3.
Embodiment 8
Ba2Lu4.65Ce0.05La0.3B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.9252 gram, CeO2：
0.0086 gram, La2O3：0.0489 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible, is capped, is placed in high temperature
In stove, 400 DEG C of pre-sintering 5h, cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or hydrogen H2Under reducing atmosphere,
Sintered at 1250 DEG C after 5h, natural cooling, appropriate grinding obtains fluorescent material Ba2Lu4.65Ce0.05La0.3B5O17.Its crystal structure
It is similar to Example 3, excite and slightly weaken compared to embodiment 3 with emissive porwer.
The curve 2 of accompanying drawing 2 is the excitation spectrum and emission spectrum of the present embodiment sample.It was found from accompanying drawing 2, the fluorescent material
Excite positioned at being 200~380nm, excitation spectrum covers very wide ultraviolet/black light region；Issued near ultraviolet excitation
Penetrate the broadband blue light that peak value is 435nm.
Embodiment 9
Ba2Lu4.85Ce0.05Gd0.1B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.9650 gram, CeO2：
0.0086 gram, Gd2O3：0.0181 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible, is capped, is placed in high temperature
In stove, pre-sintering 4h at 450 DEG C, cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or hydrogen H2Reducing atmosphere
Under, sintered at 1200 DEG C after 10h, natural cooling, appropriate grinding obtains fluorescent material Ba2Lu4.85Ce0.05Gd0.2B5O17.Its crystal
Structure is similar to Example 3, excites roughly the same compared to embodiment 3 with emissive porwer.
Embodiment 10
Ba2Lu4.9Ce0.05Sc0.05B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.9749 gram, CeO2：
0.0086 gram, Sc2O3：0.0034 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible, is capped, is placed in high temperature
In stove, pre-sintering 3h at 500 DEG C, cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or hydrogen H2Reducing atmosphere
Under, sintered at 1150 DEG C after 16h, natural cooling, appropriate grinding obtains fluorescent material Ba2Lu4.9Ce0.05Sc0.05B5O17.Its crystal
Structure is similar to Example 3, excites roughly the same compared to embodiment 3 with emissive porwer.
Embodiment 11
Ba2Lu4.94Ce0.05Yb0.01B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.9829 gram, CeO2：
0.0086 gram, Yb2O3：0.0020 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible, is capped, is placed in high temperature
In stove, pre-sintering 7h at 500 DEG C, cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or hydrogen H2Reducing atmosphere
Under, sintered at 1200 DEG C after 6h, natural cooling, appropriate grinding obtains fluorescent material Ba2Lu4.94Ce0.05Yb0.01B5O17.Its crystal
Structure is similar to Example 3, excites roughly the same compared with Example 3 with emissive porwer.
Embodiment 12
Ba2Lu4.94Ce0.05Er0.01B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.9829 gram, CeO2：
0.0086 gram, Er2O3：0.0019 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible, is capped, is placed in high temperature
In stove, pre-sintering 5h at 480 DEG C, cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or hydrogen H2Reducing atmosphere
Under, sintered at 1200 DEG C after 6h, natural cooling, appropriate grinding obtains fluorescent material Ba2Lu4.94Ce0.05Er0.01B5O17.Its crystal
Structure is similar to Example 3, excites roughly the same compared with Example 3 with emissive porwer.
Embodiment 13
Ba2Lu4.65Ce0.05La0.1Gd0.2B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.9252 gram, CeO2：
0.0086 gram, La2O3：0.0163 gram, Gd2O3：0.0363 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible
In, capping is placed in high temperature furnace, pre-sintering 5h at 530 DEG C, and cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or
Person's hydrogen H2Under reducing atmosphere, sintered at 1190 DEG C after 20h, natural cooling, appropriate grinding obtains fluorescent material
Ba2Lu4.65Ce0.05La0.1Gd0.2B5O17.Its crystal structure is similar to Example 3, excites with emissive porwer compared with Example 3
It is roughly the same.
Embodiment 14
Ba2Lu4.55Ce0.05La0.2Sc0.2B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.9053 gram, CeO2：
0.0086 gram, La2O3：0.0326 gram, Sc2O3：0.0139 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible
In, capping is placed in high temperature furnace, pre-sintering 8h at 400 DEG C, and cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or
Person's hydrogen H2Under reducing atmosphere, sintered at 1210 DEG C after 7h, natural cooling, appropriate grinding obtains fluorescent material
Ba2Lu4.55Ce0.05La0.2Sc0.2B5O17.Its crystal structure is similar to Example 3, excites with emissive porwer compared to embodiment 3
Slightly strengthen.
Embodiment 15
Ba2Lu4.55Ce0.05La0.3Yb0.1B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.9053 gram, CeO2：
0.0086 gram, La2O3：0.0489 gram, Yb2O3：0.0197 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible
In, capping is placed in high temperature furnace, pre-sintering 3h at 500 DEG C, and cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or
Person's hydrogen H2Under reducing atmosphere, sintered at 1250 DEG C after 8h, natural cooling, appropriate grinding obtains fluorescent material
Ba2Lu4.55Ce0.05La0.3Yb0.1B5O17.Its crystal structure is similar to Example 3, excites with emissive porwer compared with Example 3
It is roughly the same.
Embodiment 16
Ba2Lu4.45Ce0.05Gd0.2Sc0.3B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.8854 gram, CeO2：
0.0086 gram, Gd2O3：0.0363 gram, Sc2O3：0.0207 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible
In, capping is placed in high temperature furnace, pre-sintering 8h at 550 DEG C, and cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or
Person's hydrogen H2Under reducing atmosphere, sintered at 1250 DEG C after 4h, natural cooling, appropriate grinding obtains fluorescent material
Ba2Lu4.45Ce0.05Gd0.2Sc0.3B5O17.Its crystal structure is similar to Example 3, excites with emissive porwer compared to embodiment 3
Slightly strengthen.
Embodiment 17
Ba2Lu4.75Ce0.05Sc0.1Yb0.1B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.9451 gram, CeO2：
0.0086 gram, Sc2O3：0.0069 gram, Yb2O3：0.0197 gram.Ground and mixed is uniform in agate mortar, is put into corundum crucible
In, capping is placed in high temperature furnace, pre-sintering 4h at 470 DEG C, and cooling is taken out, and is ground several minutes.Then, in carbon monoxide CO or
Person's hydrogen H2Under reducing atmosphere, sintered at 1200 DEG C after 8h, natural cooling, appropriate grinding obtains fluorescent material
Ba2Lu4.75Ce0.05Sc0.1Yb0.1B5O17.Its crystal structure is similar to Example 3, excites with emissive porwer compared with Example 3
It is roughly the same.
Embodiment 18
Ba2Lu4.55Ce0.05La0.1Gd0.2Sc0.1B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.9053 gram, CeO2：
0.0086 gram, La2O3：0.0163 gram, Gd2O3：0.0363 gram, Sc2O3：0.0069 gram.Ground and mixed is uniform in agate mortar,
It is put into corundum crucible, is capped, is placed in high temperature furnace, pre-sintering 5h at 460 DEG C, cooling is taken out, grinds several minutes.Then, exist
Carbon monoxide CO or hydrogen H2Under reducing atmosphere, sintered at 1200 DEG C after 8h, natural cooling, appropriate grinding obtains fluorescent material
Ba2Lu4.55Ce0.05La0.1Gd0.2Sc0.1B5O17.Its crystal structure is similar to Example 3, excites with emissive porwer compared to implementation
Example 3 has strengthened.
Embodiment 19
Ba2Lu4.45Ce0.05Gd0.2Sc0.2Yb0.1B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.9053 gram, CeO2：
0.0086 gram, Gd2O3：0.0363 gram, Sc2O3：0.0069 gram, Yb2O3：0.0197 gram.Ground and mixed is uniform in agate mortar,
It is put into corundum crucible, is capped, is placed in high temperature furnace, pre-sintering 4h at 480 DEG C, cooling is taken out, grinds several minutes.Then, exist
Carbon monoxide CO or hydrogen H2Under reducing atmosphere, sintered at 1190 DEG C after 10h, natural cooling, appropriate grinding obtains fluorescence
Powder Ba2Lu4.45Ce0.05Gd0.2Sc0.2Yb0.1B5O17.Its crystal structure is similar to Example 3, excites and emissive porwer and embodiment
3 compared to roughly the same.
Embodiment 20
Ba2Lu2.95Ce0.05La0.5Gd0.5Sc0.5Yb0.5B5O17Preparation
Stoichiometrically weigh BaCO3：0.3947 gram, H3BO3：0.3092 gram, Lu2O3：0.5870 gram, CeO2：
0.0086 gram, La2O3：0.0815 gram, Gd2O3：0.0906 gram, Sc2O3：0.0345 gram, Yb2O3：0.1970 gram.In agate mortar
Middle ground and mixed is uniform, is put into corundum crucible, is capped, is placed in high temperature furnace, pre-sintering 8h at 400 DEG C, and cooling is taken out, grinding
Several minutes.Then, in carbon monoxide CO or hydrogen H2Under reducing atmosphere, sintered at 1180 DEG C after 12h, natural cooling, suitably
Grinding obtains fluorescent material Ba2Lu2.95Ce0.05La0.5Gd0.5Sc0.5Yb0.5B5O17.Its crystal structure is similar to Example 3, excites
It is roughly the same compared with Example 3 with emissive porwer.
Obviously, above-described embodiment may be used also on the basis of the above description just for the sake of clearly explanation example
To make the variation or change of other forms.Therefore, the obvious changes or variations thus amplified out still falls within this hair
Within bright protection domain.
Claims (9)
1. a kind of blue fluorescent powder for white-light LED, it is characterised in that the chemical general formula of the fluorescent material is：Ba2-mAmLu5-x- nLnCexB5O17, in formula, A is one kind in Ca, Sr, and L is Y, La, Gd, Sc, Yb, Er one or more, and x, m, n are mole
Fraction, span is respectively：0<X≤0.6,0≤m≤1,0≤n≤2.
2. a kind of blue fluorescent powder for white-light LED according to claim 1, it is characterised in that described x, m, n value model
Enclose respectively：0.01≤x≤0.6,0<M≤1,0<n≤2.
3. a kind of blue fluorescent powder for white-light LED according to claim 2, it is characterised in that described x, m, n value model
Enclose respectively：0.01≤x≤0.3,0<M≤0.5,0<n≤1.
4. a kind of preparation method of blue fluorescent powder for white-light LED according to claims 1 to 3 any one, its feature
It is, comprises the following steps：
(1) according to chemical formula Ba2-mAmLu5-x-nLnCexB5O17The stoichiometric proportion of middle each element, is weighed containing Ba respectively2+Change
Compound, contain Ca2+Compound, contain Sr2+Compound, contain Lu3+Compound, contain Ce3+Compound, contain Y3+
Compound, contain La3+Compound, contain Gd3+Compound, contain Sc3+Compound, contain Yb3+Compound, contain
There is Er3+Compound and contain B3+Compound, grind and be well mixed, obtain mixture；
(2) by said mixture in 400 DEG C~550 DEG C 2~8h of pre-sintering；Being warming up to sintering temperature under reducing gas atmosphere is
1100 DEG C~1250 DEG C, sintering time is 4~20h, after sintering products therefrom natural cooling, and grinding produces white light LEDs blue
Color fluorescent material.
5. the preparation method of a kind of blue fluorescent powder for white-light LED according to claim 4, it is characterised in that described to go back
Raw-gas is CO or H2。
6. the preparation method of a kind of blue fluorescent powder for white-light LED according to claim 4, it is characterised in that described to contain
There is Ba2+Compound to contain Ba2+One or more in oxide, carbonate, nitrate and the halide of ion；
It is described to contain Ca2+Compound to contain Ca2+Oxide, carbonate, nitrate and halide in one or more；
It is described to contain Sr2+Compound to contain Sr2+Oxide, carbonate, nitrate and halide in one or more；
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 Ce3+Compound to contain Ce3+Oxide, carbonate, nitrate and halide in one or more；
It is described to contain Y3+Compound to contain Y3+Oxide, carbonate, nitrate and halide in one or more；
It is described to contain La3+Compound to contain La3+Oxide, carbonate, nitrate and halide in one or more；
It is described to contain Gd3+Compound to contain Gd3+Oxide, carbonate, nitrate and halide in one or more；
It is described to contain Sc3+Compound to contain Sc3+Oxide, carbonate, nitrate and halide in one or more；
It is described to contain Yb3+Compound to contain Yb3+Oxide, carbonate, nitrate and halide in one or more；
It is described to contain Er3+Compound to contain Er3+Oxide, carbonate, nitrate and halide in one or more.
7. the preparation method of a kind of blue fluorescent powder for white-light LED according to claim 4, it is characterised in that described to contain
There is B3+Compound be H3BO3。
8. the preparation method of a kind of blue fluorescent powder for white-light LED according to claim 4, it is characterised in that described pre-
After sintering, pre-sintered product is first cooled down, grind it is abundant after, then be sintered.
9. a kind of blue fluorescent powder for white-light LED described in claims 1 to 3 any one is in ultraviolet/near ultraviolet LED chip base
Application in white light LEDs.
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| CN108865138A (en) * | 2018-07-19 | 2018-11-23 | 武汉华星光电半导体显示技术有限公司 | A kind of borate fluorescent powder and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544021A (en) * | 2016-10-19 | 2017-03-29 | 中国科学院长春光学精密机械与物理研究所 | Borate fluorescent powder that a kind of cerium, terbium are co-doped with and preparation method thereof |
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2017
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544021A (en) * | 2016-10-19 | 2017-03-29 | 中国科学院长春光学精密机械与物理研究所 | Borate fluorescent powder that a kind of cerium, terbium are co-doped with and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MARTINHERMUS等: "b InitioStructureDeterminationandPhotoluminescentPropertiesofanEfficient,ThermallyStableBluePhosphor,Ba2Y5B5O17:Ce3+", 《CHEM.MATER.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108865138A (en) * | 2018-07-19 | 2018-11-23 | 武汉华星光电半导体显示技术有限公司 | A kind of borate fluorescent powder and preparation method thereof |
| WO2020015247A1 (en) * | 2018-07-19 | 2020-01-23 | 武汉华星光电半导体显示技术有限公司 | Borate fluorescent powder and preparation method therefor |
| US11306247B2 (en) * | 2018-07-19 | 2022-04-19 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Borate fluorescent powder and preparing method thereof |
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