CN106867531A - A kind of strontium phosphate potassium fluorescent material of Color tunable - Google Patents
A kind of strontium phosphate potassium fluorescent material of Color tunable Download PDFInfo
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- CN106867531A CN106867531A CN201710033769.7A CN201710033769A CN106867531A CN 106867531 A CN106867531 A CN 106867531A CN 201710033769 A CN201710033769 A CN 201710033769A CN 106867531 A CN106867531 A CN 106867531A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7795—Phosphates
- C09K11/7796—Phosphates with alkaline earth metals
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Abstract
Strontium phosphate potassium fluorescent material of emitting red light Color tunable and preparation method thereof is arrived with a kind of rare earth ion doped green, it is characterised in that its chemical composition is KSr the present invention relates to a kind of white light LEDs(1‑x‑y)PO4:Eux,Tby, 0.001≤x≤0.2；0.001≤y≤0.5.Fluorescent material is synthesized using high-temperature solid phase reaction method, and the fluorescent material that crystal property is good, chemical constituents analysis are uniform, luminous efficiency is high can be prepared under relatively low heat treatment temperature, and the preparation of powder has process is simple, process control, low cost and other advantages.
Description
Technical field
Strontium phosphate potassium fluorescent material the present invention relates to a kind of green to emitting red light Color tunable and preparation method thereof, especially
It is to be related to a kind of trivalent europium ion（Eu3+）And terbium ion（Tb3+）Codope strontium phosphate potassium（KSrPO4）Fluorescent material and its preparation side
Method.
Background technology
Semiconductor light-emitting-diode illuminating device is the class product for most having development potentiality when front lit and display field, its
Conventional illumination device can not only be replaced, the numerous areas such as large display screen, car light are may be also used in.White light LEDs are in recent years
By the developing direction that national governments pay close attention to and support, this is that it has section because white light LEDs and incandescent lamp and fluorescent lamp are contrasted
The advantage such as energy environmental protection, luminous efficiency is high, colour rendering is good, long lifespan, the high, fast response time of brightness.At present, white light LEDs is main
Working mechanism is to launch blue light using GdInN substrates, and the blue light excites Y3Al5O12:Ce3+Fluorescent material, makes powder launch gold-tinted,
White light is obtained by the effect colour mixture of lens, the color of this light source lacks controllability.In order to meet the requirement of various applications,
Need to enable light source to change luminescent spectrum or colour temperature, the method for the treatment of uses the fluorescence of various matrix simultaneously in being included in light fixture
Powder, it is also possible to use matrix of the same race difference activator and its fluorescent material of ratio.
Rare earth ion doped phosphate material is the luminescent material of a class excellent performance.As matrix, phosphate compounds
With physicochemical properties stabilization, low cost of material, process is simple, the low advantage of synthesis temperature, have with lighting field luminous
There is good application value.Strontium phosphate potassium（KSrPO4）With orthorhombic crystal structure, space group Pnma, by [PO4] tetrahedron composition
Crystal network, network space is by K+Ion and Sr2+Ion is filled, and ligancy is respectively 10 and 9, and heat endurance is good.At present,
Develop Eu2+（424 nm）、Tb3+（542 nm）、Sm3+（596 nm）Strontium phosphate potassium Deng doping is the fluorescent material of matrix, the body
The new material of system awaits developing and improving performance.
Trivalent europium ion（Eu3+）And terbium ion（Tb3+）There is feux rouges and green emission respectively, be much practical fluorescence
The activator of powder.Both activator are solidly soluted into same matrix, while producing light transmitting, can simply be obtained
Red, green light fluorescent powder.By changing two kinds of consumptions of activator, the regulation from green glow to feux rouges can be realized.
The content of the invention
The luminescent spectrum of the fluorescent material used present invention aim to address white light LEDs lacks the problem of modulability, carries
For one kind with trivalent europium ion（Eu3+）And terbium ion（Tb3+）It is the centre of luminescence, strontium phosphate potassium（KSrPO4）It is new glimmering for matrix
Light powder and preparation method thereof.
High-temperature solid phase reaction method of the invention prepares KSr(1-x-y)PO4:Eux,TbyThe method of fluorescent material, wherein x=0.001
~0.2, y=0.001~0.5.Comprise the following steps：
（1）Raw material with potassium carbonate, potassium oxalate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate etc. as Element Potassium；With strontium carbonate as elements strontium
Raw material；Raw material with diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate etc. as element phosphor；With europium oxide
It is the raw material of element europium；Take terbium oxide as the raw material of element terbium, according to the order for calculating, weighing, mixing, required raw material is mixed
Thing is sufficiently mixed.
（2）By step（1）Well mixed raw mixture is contained in crucible, then is sent into Muffle furnace, 500~800
Pre-burning 2~10 hours at DEG C.
（3）Powder after pre-burning is poured into mortar, carries out secondary ground and mixed.
（4）The powder of secondary grinding is poured into crucible, in the calcining of kiln high temperature, 800~1200 DEG C of calcining heat is forged
0.5~10 hour burning time, calcination atmosphere is air atmosphere or oxidizing atmosphere.
Described furnace type includes：Muffle furnace, tube-type atmosphere furnace etc..Prioritizing selection tube-type atmosphere furnace is used as high-temperature calcination
Equipment.
Described oxidizing atmosphere includes：High purity oxygen gas gas.
Step（4）Powder after high-temperature calcination needs to be ground to eliminate aggregate.Ginding process can select agate
Mortar treatment, ball mill dry grinding, ball mill wet grinding by hand.
The slurry of described wet ball grinding needs dried process, to exclude liquid phase ingredient, obtains fluorescent material dry powder.
Powder after grinding needs to be sieved, and obtains the powder of the particle diameter distribution needed for being adapted to LED lamp.
Beneficial effects of the present invention：The fluorescent material is presented green emission to red emission under ultraviolet excitation, right respectively
Answer trivalent europium ion（Eu3+）And terbium ion（Tb3+）5d → 4f optical transitions.The light-emitting phosphor excellent performance, spectrum regulation
Scope is from trivalent terbium ion（Tb3+）The nm of main emission peak 544 to europium ion（Eu3+）The nm of main emission peak 620 between, scope
Greatly, the need for going for various applications.The fluorescent powder thermal stability and chemical stability are good, preparation process is simple, cost
It is low, it is adapted to industrialized production.
Brief description of the drawings
Fig. 1 is the KSr of the gained of the embodiment of the present invention 1(1-x-y)PO4:Eux,TbyThe excitation spectrum of red fluorescence powder；
Fig. 2 is the KSr of the gained of the embodiment of the present invention 1(1-x-y)PO4:Eux,TbyThe emission spectrum of red fluorescence powder；
Fig. 3 is the KSr of the gained of the embodiment of the present invention 2(1-x-y)PO4:Eux,TbyThe excitation spectrum of green emitting phosphor；
Fig. 4 is the KSr of the gained of the embodiment of the present invention 2(1-x-y)PO4:Eux,TbyThe emission spectrum of green emitting phosphor.
Fig. 5 is the KSr of the gained of the embodiment of the present invention 3(1-x-y)PO4:Eux,TbyThe excitation spectrum of yellow fluorescent powder；
Fig. 6 is the KSr of the gained of the embodiment of the present invention 3(1-x-y)PO4:Eux,TbyThe emission spectrum of yellow fluorescent powder；
Fig. 7 is the KSr of the gained of the embodiment of the present invention 3(1-x-y)PO4:Eux,TbyThe XRD spectrum of yellow fluorescent powder；
Fig. 8 is the KSr of the gained of the embodiment of the present invention 3(1-x-y)PO4:Eux,TbyThe electron scanning micrograph of yellow fluorescent powder.
Specific embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
The codope europium of the burst of ultraviolel and the strontium phosphate potassium red fluorescence powder of terbium, the expression formula of the red fluorescence powder is
KSr(1-x-y)PO4:Eux,Tby, wherein x represents 0.015 mole value, and y represents 0.0025 mole value.The burst of ultraviolel is total to
The excitation spectrum and emission spectrum of the strontium phosphate potassium red fluorescence powder of europium doped and terbium are as illustrated in fig. 1 and 2.
The red fluorescence powder is by K2CO3、SrCO3、(NH4)2HPO4、Eu2O3And Tb4O7Raw material is according to mol ratio 0.5:
0.9825:1:0.0075:0.000625 is made.The material powder that will be weighed ground and mixed in mortar, mixed powder is moved into
Muffle furnace is put into crucible and with crucible, 500~800 DEG C are warmed up to, calcined 0.5~10 hour, naturally cool to room temperature.Take out
The powder of pre-burning, the ground and mixed in mortar, corundum crucible is poured into by powder again, is together placed on the centre bit of tube-type atmosphere furnace
Put, be to slowly warm up to 900~1200 DEG C, be first passed through nitrogen 20 minutes, then the oxygen in drain be passed through oxygen, calcining 2 again
~10 hours, room temperature is naturally cooling to, takes out the powder after calcining, ground and sieving obtains product red fluorescence powder.
Embodiment 2
The codope europium of the burst of ultraviolel and the strontium phosphate potassium green emitting phosphor of terbium, the expression formula of the green emitting phosphor is
KSr(1-x-y)PO4:Eux,Tby, wherein x represents 0.0075 mole value, and y represents 0.005 mole value.The burst of ultraviolel is total to
The excitation spectrum and emission spectrum of the strontium phosphate potassium green emitting phosphor of europium doped and terbium are as shown in Figure 3 and Figure 4.
The green emitting phosphor is by K2CO3、SrCO3、NH4H2PO4、Eu2O3And Tb4O7Raw material is according to mol ratio 0.5:0.9875:
1:0.00375:0.00125 is made.The material powder that will be weighed ground and mixed in mortar, by mixed powder move into crucible in simultaneously
Muffle furnace is put into crucible, 600~700 DEG C are warmed up to, calcined 2~8 hours, naturally cool to room temperature.The powder of pre-burning is taken out,
The ground and mixed in planetary ball mill, with absolute ethyl alcohol as dispersion liquid.Slurry after ball milling is with beaker in electric heating forced air drying
In 40~100 DEG C of dryings 4~24 hours in machine, to exclude the liquid phase in powder.Dried powder is poured into corundum crucible, one
With the center for being placed on Muffle furnace, 900~1200 DEG C are to slowly warm up to, calcined 2~10 hours, be naturally cooling to room temperature, taken
The powder gone out after calcining, ground and sieving obtains product green emitting phosphor.
Embodiment 3
The codope europium of the burst of ultraviolel and the strontium phosphate potassium yellow fluorescent powder of terbium, the expression formula of the greenish yellow fluorescent powder is
KSr(1-x-y)PO4:Eux,Tby, wherein x represents 0.01 mole value, and y represents 0.0025 mole value.The burst of ultraviolel is co-doped with
The excitation spectrum and emission spectrum of the strontium phosphate potassium yellow fluorescent powder of miscellaneous europium and terbium are as shown in Figure 5 and Figure 6.The XRD spectrum of powder
With electron scanning micrograph as shown in Figure 7 and Figure 8.
The yellow fluorescent powder is by K2HPO4、SrCO3、(NH4)2HPO4、Eu2O3And Tb4O7Raw material is according to mol ratio 0.5:
0.9875:0.5:0.005:0.000625 is made.The material powder that will be weighed ground and mixed in mortar, mixed powder is moved into
It is put into Muffle furnace in crucible and with crucible, is warmed up to 600~700 DEG C, calcined 2~8 hours, naturally cools to room temperature.Take out
The powder of pre-burning, the ground and mixed in planetary ball mill, with deionized water as dispersion liquid.Slurry after ball milling is with beaker in electricity
In 90~120 DEG C of dryings 4~24 hours in hot blast drying machine, to exclude the moisture in powder.Dried powder is poured into
Corundum crucible, is together placed on the center of Muffle furnace, is to slowly warm up to 900~1200 DEG C, calcines 2~10 hours, drops naturally
Warm to room temperature, take out the powder after calcining, ground and sieving obtains product yellow fluorescent powder.
Claims (5)
1. a kind of green arrives the strontium phosphate potassium fluorescent material of emitting red light Color tunable, it is characterised in that consisting of KSr(1-x-y)
PO4:Eux,Tby。
2. one kind prepares white light LEDs KSr as claimed in claim 1(1-x-y)PO4:Eux,TbyThe preparation method of fluorescent material,
It is comprised the following steps that：The salt of potassium, phosphorus, and strontium carbonate and europium oxide, terbium oxide are weighed according to amount of calculation, by its uniform mixing
Pre-burning is to 500~800 DEG C afterwards.Again by the secondary mixing of powder after pre-burning, high-temperature calcination is to 800~1200 DEG C, and it is appropriate to be passed through
Gas, is incubated 0.5~10 hour.Powder after cooling eliminates aggregate by grinding.Eventually pass sieve and obtain suitable particle diameter
The powder of distribution.
3. the preparation method of luminescent powder according to claim 2, it is characterized in that the compound of potassium used is potassium carbonate, grass
Sour potassium, potassium dihydrogen phosphate, dipotassium hydrogen phosphate etc..
4. the preparation method of luminescent powder according to claim 2, it is characterized in that the compound of phosphorus used is phosphoric acid hydrogen two
Ammonium, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate etc..
5. the preparation method of luminescent powder according to claim 2, it is characterized in that calcination atmosphere used can be air or
Oxidizing atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710033769.7A CN106867531A (en) | 2017-01-18 | 2017-01-18 | A kind of strontium phosphate potassium fluorescent material of Color tunable |
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| CN201710033769.7A CN106867531A (en) | 2017-01-18 | 2017-01-18 | A kind of strontium phosphate potassium fluorescent material of Color tunable |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114854410A (en) * | 2022-05-20 | 2022-08-05 | 五邑大学 | Phosphate fluorescent powder with adjustable light emitting color and preparation method and application thereof |
-
2017
- 2017-01-18 CN CN201710033769.7A patent/CN106867531A/en active Pending
Non-Patent Citations (7)
| Title |
|---|
| LE-QI YA ET AL.: "Energy transfer, tunable emission and optical thermometry in Tb3+/Eu3+ co-doped transparent NaCaPO4 glass ceramics", 《CERAMICS INTERNATIONAL》 * |
| TINGMING JIANG ET AL.: "Realization of tunable emission via efficient Tb3+-Eu3+ energy transferin K3Gd(PO4)2 for UV-excited white light-emitting-diodes", 《OPTICAL MATERIALS》 * |
| XINGUO ZHANG ET AL.: "Energy transfer and multicolor tunable emission in single-phase Tb3+, Eu3+ co-doped Sr3La(PO4)3 phosphors", 《CERAMICS INTERNATIONAL》 * |
| XINGUO ZHANG ET AL.: "Luminescence and energy transfer of a color tunable phosphor Tb3+, Eu3+ co-doped KCaY(PO4)2", 《MATERIALS LETTERS》 * |
| ZHIJUAN LIANG ET AL.: "Optical propertiesandenergytransferofNaCaPO4:Tb+,Eu3+ phosphors", 《CERAMICS INTERNATIONAL》 * |
| 张凤: "Eu3+、Tb3+激活的几种含氧酸盐基发光材料的制备及其发光特性研究", 《中国博士学位论文全文数据库基础科学辑》 * |
| 洪广言 等: "《稀土发光材料》", 31 May 2016, 冶金工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114854410A (en) * | 2022-05-20 | 2022-08-05 | 五邑大学 | Phosphate fluorescent powder with adjustable light emitting color and preparation method and application thereof |
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Application publication date: 20170620 |