CN103059844B - Sulfide upconversion luminous fluorescent powder, preparation method and application thereof - Google Patents

Sulfide upconversion luminous fluorescent powder, preparation method and application thereof Download PDF

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CN103059844B
CN103059844B CN201110318800.4A CN201110318800A CN103059844B CN 103059844 B CN103059844 B CN 103059844B CN 201110318800 A CN201110318800 A CN 201110318800A CN 103059844 B CN103059844 B CN 103059844B
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sulfide
fluorescent material
preparation
powder
conversion luminescence
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CN103059844A (en
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周明杰
王平
陈吉星
张振华
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention belongs to the field of fluorescent powder, and discloses a sulfide upconversion luminous fluorescent powder, and a preparation method and application thereof. The fluorescent powder has a structure of AGeS2-bGa2S3:cTm<3+>; Tm<3+> is a doping ion; and a, b and c are molar coefficients, and satisfy the following relations: 0.52<=a<=0.7, 0.28<=b<=0.45, 0.005<=c<=0.03, and a+b+c=1. The sulfide upconversion luminous fluorescent powder prepared by the invention can realize blue short-wavelength light emitting through excitation by long-wave radiation from infrared to green ray. Therefore, the fluorescent powder can make up for the lack of blue material in current display and luminous material.

Description

Fluorescent material of sulfide up-conversion luminescence and its preparation method and application
Technical field
The present invention relates to a kind of fluorescent material, relate in particular to fluorescent material of a kind of sulfide up-conversion luminescence and its preparation method and application.
Background technology
The full name Organic Light Emitting Diode of OLED, Organic Light Emitting Diode.It has a lot of advantages, and its unit construction is simple, and production cost is cheap, and self luminous characteristic adds that the reaction times of OLED is short, more has flexible characteristic, makes its range of application extremely wide.But owing to obtaining at present, the OLED blue light material of stability and high efficiency is more difficult, has limited greatly the development of white light OLED device and light source industry.
Upconverting fluorescent material can be launched visible ray under long wave (as infrared) radiation excitation, even UV-light, is with a wide range of applications in fields such as optical fiber communication technology, fibre amplifier, 3 D stereo demonstration, biomolecules fluorescence labelling, infrared detectives.But be prepared into fluorescent material and be applied to the field of OLED, still rarely seen report.
Summary of the invention
One of object of the present invention is to provide a kind of fluorescent material that can be inspired by long wavelength radiations such as infrared, red-green glows the sulfide up-conversion luminescence of blue emission.
A fluorescent material for sulfide up-conversion luminescence, its structural formula is aGeS 2-bGa 2s 3: cTm 3+; Wherein, Tm 3+for dopant ion, a, b, c are mole coefficient, 0.52≤a≤0.7,0.28≤b≤0.45,0.005≤c≤0.03, and a+b+c=1; Preferably, a=0.6, b=0.38, c=0.02.
The preparation method who another object of the present invention is to the fluorescent material that above-mentioned sulfide up-conversion luminescence is provided, comprises the steps:
Step S1, according to molecular fraction, take powder: GeS 2, 52%～70%; Ga 2s 3, 28%～45%; Tm 2s 3, 0.5%～3%;
Step S2, the powder that step S1 is taken mix, grind 20～60 minutes, obtain powder presoma;
Step S3, the powder presoma of step S2 is calcined 0.5～5 hour at 800～1000 DEG C, be cooled to subsequently 100～300 DEG C, and be cooled to room temperature be incubated 0.5～3 hour at this temperature after, obtain block product;
Step S4, the block product in step S3 is ground, obtain the fluorescent material of described sulfide up-conversion luminescence; The structural formula of this fluorescent material is aGeS 2-bGa 2s 3: cTm 3+; Wherein, Tm 3+for dopant ion, a, b, c are mole coefficient, 0.52≤a≤0.7,0.28≤b≤0.45,0.005≤c≤0.03, and a+b+c=1.
In the preparation method of the fluorescent material of above-mentioned sulfide up-conversion luminescence:
Preferably, a=0.6, b=0.38, c=0.02;
In step S2, the milling time of described powder is 40 minutes;
In step S3, the calcining temperature of described calcination process is 950 DEG C, and calcination time is 3 hours; After calcination process finishes, the temperature of described insulating process is 200 DEG C, and soaking time is 2 hours.
The application of the fluorescent material that another object of the present invention is to provide above-mentioned sulfide up-conversion luminescence in Organic Light Emitting Diode is mainly the luminescent layer material as Organic Light Emitting Diode.These fluorescent material are being, after the Organic Light Emitting Diode of carrying out monochrome (as ruddiness) is made, fluorescent material to be mixed in packaged material and to be coated in Organic Light Emitting Diode outside, are subject to exciting of ruddiness, give off blue light.
The fluorescent material of sulfide up-conversion luminescence prepared by the present invention, can realize that to inspire blue light shortwave by the infrared long-wave radiation to green glow luminous.Therefore, this fluorescent material can make up the deficiency of blue light material in current demonstration and luminescent material.
In addition, the preparation method of the fluorescent material of sulfide up-conversion luminescence provided by the invention is simple, is with low costly applicable to production, and reaction process, without three industrial wastes, belongs to environmental protection, less energy-consumption, high benefit industry.
Brief description of the drawings
Fig. 1 is preparation technology's schema of the fluorescent material of sulfide up-conversion luminescence of the present invention;
Fig. 2 is the electroluminescent spectrum figure of the fluorescent material of the sulfide up-conversion luminescence that makes of embodiment 1;
Fig. 3 is the structural representation of Organic Light Emitting Diode in the present embodiment.
Embodiment
The fluorescent material of a kind of sulfide up-conversion luminescence provided by the invention, its structural formula is aGeS 2-bGa 2s 3: cTm 3+; Wherein, Tm 3+for dopant ion, aGeS 2-bGa 2s 3system be that one can allow Tm 3+realize the matrix of transform light energy, a, b, c are mole coefficient, 0.52≤a≤0.7,0.28≤b≤0.45,0.005≤c≤0.03, and a+b+c=1; Preferably, a=0.6, b=0.38, c=0.02.
The fluorescent material of sulfide up-conversion luminescence prepared by the present invention, can realize that to inspire blue light shortwave by the infrared long-wave radiation to green glow luminous.Therefore, this fluorescent material can make up the deficiency of blue light material in current demonstration and luminescent material.
The preparation method of the fluorescent material of above-mentioned sulfide up-conversion luminescence, as shown in Figure 1, comprises the steps:
Step S1, according to molecular fraction, take powder: GeS 2, 52%～70%; Ga 2s 3, 28%～45%; Tm 2s 3, 0.5%～3%;
Step S2, the powder that step S1 is taken mix, grind 20～60 minutes, obtain powder presoma;
Step S3, the powder presoma of step S2 is calcined 0.5～5 hour at 800～1000 DEG C, be cooled to subsequently 100～300 DEG C, and be cooled to room temperature be incubated 0.5～3 hour at this temperature after, obtain block product;
Step S4, the block product in step S3 is ground, obtain the fluorescent material of described sulfide up-conversion luminescence; The structural formula of this fluorescent material is aGeS 2-bGa 2s 3: cTm 3+; Wherein, Tm 3+for dopant ion, a, b, c are mole coefficient, 0.52≤a≤0.7,0.28≤b≤0.45,0.005≤c≤0.03, and a+b+c=1.
In the preparation method of the fluorescent material of above-mentioned sulfide up-conversion luminescence:
Preferably, a=0.6, b=0.38, c=0.02;
In step S2, the milling time of described powder is 40 minutes;
In step S3, the calcining temperature of described calcination process is 950 DEG C, and calcination time is 3 hours; After calcination process finishes, the temperature of described insulating process is 200 DEG C, and soaking time is 2 hours.
The application of the fluorescent material of above-mentioned sulfide up-conversion luminescence in Organic Light Emitting Diode is mainly the luminescent layer material as Organic Light Emitting Diode.These fluorescent material are being, after the Organic Light Emitting Diode of carrying out monochrome (as ruddiness) is made, fluorescent material to be mixed in packaged material and to be coated in Organic Light Emitting Diode outside, are subject to exciting of ruddiness, give off blue light.
The preparation method of the fluorescent material of sulfide up-conversion luminescence provided by the invention is simple, is with low costly applicable to production, and reaction process, without three industrial wastes, belongs to environmental protection, less energy-consumption, high benefit industry.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
1, selecting purity is 99.99% powder: GeS 2, Ga 2s 3and Tm 2s 3powder, its molecular fraction is respectively 60%, 38% and 2%;
2, above-mentioned powder is placed in to corundum mortar, grinds and it was evenly mixed in 40 minutes, obtain powder presoma;
3, powder presoma is placed in to retort furnace, calcination 3 hours at 900 DEG C, is then cooled to 200 DEG C of insulations 2 hours, then naturally cools to room temperature taking-up block product,
4, block product is ground, pulverized, obtaining structural formula is 0.6GeS 2-0.38Ga 2s 3: 0.02Tm 3+up-conversion phosphor.
Fig. 2 is the electroluminescent spectrum figure of the fluorescent material of the sulfide up-conversion luminescence that makes of embodiment 1; As shown in Figure 2, excitation wavelength is 796nm; That the glow peak of the 475nm obtaining is corresponding is Tm 3+ion 1g 4→ 3h 6transition radiation luminous.
Embodiment 2
1, selecting purity is 99.99% powder: GeS 2, Ga 2s 3and Tm 2s 3powder, its molecular fraction is respectively 52%, 45% and 3%;
2, above-mentioned powder is placed in to corundum mortar and grinds and it was evenly mixed in 20 minutes, obtain powder presoma;
3, powder presoma is placed in to retort furnace, calcination 5 hours at 800 DEG C, is then cooled to 300 DEG C of insulations 0.5 hour, then naturally cools to room temperature taking-up block product;
4, block product is ground, pulverized, obtaining structural formula is 0.52GeS 2-0.45Ga 2s 3: 0.03Tm 3+up-conversion phosphor.
Embodiment 3
1, selecting purity is 99.99% powder: GeS 2, Ga 2s 3and Tm 2s 3powder, its molecular fraction is respectively 70%, 29.5% and 0.5%;
2, above-mentioned powder is placed in to corundum mortar and grinds and it was evenly mixed in 60 minutes, obtain powder presoma;
3, powder presoma is placed in to retort furnace, calcination 0.5 hour at 1000 DEG C, is then cooled to 100 DEG C of insulations 3 hours, then naturally cools to room temperature taking-up block product;
4, block product is ground, pulverized, obtaining structural formula is 0.7GeS 2-0.295Ga 2s 3: 0.005Tm 3+up-conversion phosphor.
Embodiment 4
The present embodiment 4 is Organic Light Emitting Diode, refers to Fig. 3, and the structure of this Organic Light Emitting Diode is substrate 1, negative electrode 2, organic luminous layer 3, transparent anode 4 and the transparent encapsulated layer 5 stacking gradually; Wherein, in transparent encapsulated layer 5, be dispersed with the fluorescent material 6 making in embodiment 1.
When this Organic Light Emitting Diode uses, the part ruddiness excitated fluorescent powder 6 of organic luminous layer 3 sends blue light, and this blue light inspires white light after mixing with remaining ruddiness in luminescent layer 3.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.

Claims (5)

1. a preparation method for the fluorescent material of sulfide up-conversion luminescence, is characterized in that, comprises the steps:
Step S1, according to molecular fraction, take powder: GeS 2, 52%～70%; Ga 2s 3, 28%～45%; Tm 2s 3, 0.5%～3%;
Step S2, the powder that step S1 is taken mix, grind 20～60 minutes, obtain powder presoma;
Step S3, the powder presoma of step S2 is calcined 0.5～5 hour at 800～1000 DEG C, be cooled to subsequently 100～300 DEG C, and be cooled to room temperature be incubated 0.5～3 hour at this temperature after, obtain block product;
Step S4, the block product in step S3 is ground, obtain the fluorescent material of described sulfide up-conversion luminescence; The structural formula of this fluorescent material is aGeS 2-bGa 2s 3: cTm 3+; Wherein, Tm 3+for dopant ion, a, b, c are mole coefficient, 0.52≤a≤0.7,0.28≤b≤0.45,0.005≤c≤0.03, and a+b+c=1.
2. the preparation method of the fluorescent material of sulfide up-conversion luminescence according to claim 1, is characterized in that, a=0.6, b=0.38, c=0.02.
3. the preparation method of the fluorescent material of sulfide up-conversion luminescence according to claim 1, is characterized in that, in step S2, the milling time of described powder is 40 minutes.
4. the preparation method of the fluorescent material of sulfide up-conversion luminescence according to claim 1, is characterized in that, in step S3, the calcining temperature of described calcination process is 950 DEG C, and calcination time is 3 hours.
5. the preparation method of the fluorescent material of sulfide up-conversion luminescence according to claim 1, is characterized in that, in step S3, after calcination process finishes, the temperature of described insulating process is 200 DEG C, and soaking time is 2 hours.
CN201110318800.4A 2011-10-19 2011-10-19 Sulfide upconversion luminous fluorescent powder, preparation method and application thereof Active CN103059844B (en)

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CN103540320B (en) * 2013-11-01 2014-12-10 哈尔滨工业大学 Method for preparing up-conversion red light-emitting indium sulfide

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