CN104342153A - Dysprosium and ytterbium co-doped alkali yttrium fluoride glass up-conversion luminescent material, and preparation method and application thereof - Google Patents
Dysprosium and ytterbium co-doped alkali yttrium fluoride glass up-conversion luminescent material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a dysprosium and ytterbium co-doped alkali yttrium fluoride glass up-conversion luminescent material with a chemical formula of RYF4:xDy<3+>,yYb<3+>, wherein x is 0.01-0.06, y is 0.01-0.04, and R is at least one selected from lithium element, sodium elemental, potassium element, rubidium element and caesium element. The dysprosium and ytterbium co-doped alkali yttrium fluoride glass up-conversion luminescent material excitation wavelength is 796nm; and a 482nm light emission peak is corresponding to light emission peak formed by Dy<3+> ion <4>F9/2 to <6>F15/2 transition radiation, such that blue-light short-wave luminescence excited by long-wave radiation of infrared to green light is realized. The invention also provides a preparation method and an application of the dysprosium and ytterbium co-doped alkali yttrium fluoride glass up-conversion luminescent material.
Description
Technical field
The present invention relates to a kind of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material, its preparation method and use the Organic Light Emitting Diode of this dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material.
Background technology
Organic Light Emitting Diode (OLED) because unit construction is simple, the characteristic such as cheap, the luminous of production cost, reaction times is short, flexible, and obtain a very wide range of application.But because the OLED blue light material obtaining stability and high efficiency is at present more difficult, significantly limit the development of white light OLED device and light source industry.
Upconverting fluorescent material can launch visible ray under long wave (as infrared) radiation excitation, even UV-light, is with a wide range of applications in the field such as optical fiber communication technology, fibre amplifier, 3 D stereo display, biomolecules fluorescence labelling, infrared detective.But, can by infrared, the long-wave radiations such as red-green glow inspire the dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material of blue emission, have not yet to see report.
Summary of the invention
Based on this, being necessary to provide a kind of can inspire the dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material of blue light, its preparation method by long-wave radiation and use the Organic Light Emitting Diode of this dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material.
A kind of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material, its chemical formula is RYF
4: xDy
3+, yYb
3+, wherein, x is 0.01 ~ 0.06, y be 0.01 ~ 0.04, R is elemental lithium, sodium element, potassium element, at least one in rubidium element and cesium element.
Described x is 0.03, y is 0.02.
A preparation method for dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material, comprises the following steps:
According to RYF
4: xDy
3+, yYb
3+the stoichiometric ratio of each element takes R
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3powder, wherein, x is 0.01 ~ 0.06, y be 0.01 ~ 0.04, R is elemental lithium, sodium element, potassium element, at least one in rubidium element and cesium element;
The powder taken is dissolved in hydrofluoric acid to be mixed with the cationic concentration of concentration metal be the solution of 0.5mol/L ~ 3mol/L;
Pass into carrier gas the silica tube generation presoma that temperature is 100 DEG C ~ 220 DEG C after described solution mist is changed into mist, wherein, the diameter of silica tube is 30mm ~ 150mm, and length is 0.5m ~ 3m, and the flow of carrier gas is 1L/min ~ 15L/min;
Being calcined at 600 DEG C ~ 1300 DEG C by described presoma and within 2 hours ~ 5 hours, obtaining chemical formula is RYF
4: xDy
3+, yYb
3+dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material.
Described x is 0.03, y is 0.02.
The powder taken is dissolved in hydrogen fluoride the step being mixed with solution also comprise: in described solution, add dispersion agent, the concentration of described dispersion agent is 0.005mol/L ~ 0.05mol/L.
Described dispersion agent is polyoxyethylene glycol.
The step described solution mist being changed into mist is, carrier gas and described solution are passed into together in spraying gun and make described solution mist change into mist, described carrier gas is rare gas element or reducing gas.
The flow of described carrier gas is 5L/min ~ 8L/min.
A kind of Organic Light Emitting Diode, comprise the substrate, negative electrode, organic luminous layer, anode and the transparent encapsulated layer that stack gradually, doped with dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material in described transparent encapsulated layer, the chemical general formula of described dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material is RYF
4: xDy
3+, yYb
3+, wherein, x is 0.01 ~ 0.06, y be 0.01 ~ 0.04, R is elemental lithium, sodium element, potassium element, at least one in rubidium element and cesium element.
Described x is 0.03, y is 0.02.
The preparation method of above-mentioned dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material is comparatively simple, and cost is lower; In the photoluminescence spectra of the dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material of preparation, the excitation wavelength of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material is 796nm, and corresponding respectively at the glow peak of 482nm is Dy
3+ion
4f
9/2→
6f
15/2transition radiation form glow peak, achieve that to inspire blue light shortwave by the infrared long-wave radiation to green glow luminous; Be dispersed with dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material in the transparent encapsulated layer of Organic Light Emitting Diode, the excitation wavelength of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material is 796nm, and corresponding respectively at the glow peak of 482nm is Dy
3+ion
4f
9/2→
6f
15/2transition radiation form glow peak, excited can be launched blue light by red-green glow, blue light mixes with red-green glow and afterwards forms the Organic Light Emitting Diode emitted white light.
Accompanying drawing explanation
Fig. 1 is the structural representation of the spray pyrolysis equipment of an embodiment;
Fig. 2 is the structural representation of the Organic Light Emitting Diode of an embodiment;
Fig. 3 is the photoluminescence spectrogram of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material prepared by embodiment 1;
Fig. 4 is the XRD spectra of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material prepared by embodiment 1;
Fig. 5 is the spectrogram doped with the Organic Light Emitting Diode of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material formation in the transparent encapsulated layer of embodiment 1 preparation.
Embodiment
Below in conjunction with the drawings and specific embodiments to dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material, its preparation method and use the Organic Light Emitting Diode of this dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material to illustrate further.
The dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material of one embodiment, its chemical formula is RYF
4: xDy
3+, yYb
3+, wherein, x is 0.01 ~ 0.06, y be 0.01 ~ 0.04, R is elemental lithium, sodium element, potassium element, at least one in rubidium element and cesium element.
Preferably, x is 0.03, y is 0.02.
In the photoluminescence spectra of this dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material, the excitation wavelength of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material is 796nm, when material is subject to the radiation of long wavelength (as 796nm) time, and Dy
3+the energy of this illumination of ionic absorption, now Dy
3+ion by
4f
9/2→
6f
15/2transition, send the blue light of 482nm, achieve that to inspire blue light shortwave by the infrared long-wave radiation to green glow luminous.
The preparation method of above-mentioned dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material, comprises the following steps;
Step S101, according to RYF
4: xDy
3+, yYb
3+the stoichiometric ratio of each element takes R
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3powder, wherein, x is 0.01 ~ 0.06, y be 0.01 ~ 0.04, R is elemental lithium, sodium element, potassium element, at least one in rubidium element and cesium element.
Preferably, x is 0.03, y is 0.02.
Being appreciated that in this step also can according to mol ratio 1:(0.9 ~ 0.98): (0.01 ~ 0.06): (0.01 ~ 0.04) takes R
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3powder.
Preferably, also R can be taken according to mol ratio 1:0.95:0.03:0.02 in this step
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3powder.
Step S102, the powder taken is dissolved in hydrofluoric acid the concentration being mixed with metallic cation is the solution of 0.5mol/L ~ 3mol/L.
Metallic cation in solution is R
+, Y
3+, Dy
3+, Yb
3+, R
+for lithium ion, sodium ion, potassium ion, at least one in rubidium ion and cesium ion.
Preferably, the powder taken is dissolved in hydrofluoric acid the step being mixed with solution and also comprises: in solution, add dispersion agent, the concentration of dispersion agent is 0.005mol/L ~ 0.05mol/L.In present embodiment, dispersion agent is polyoxyethylene glycol.
Refer to Fig. 1, the spray pyrolysis equipment 100 shown in Fig. 1 comprises container for storing liquid 10, gas-holder 20, spraying gun 30, silica tube 40 and collector 50.
In present embodiment, solution prepared by step S102 deposits in container for storing liquid 10.
S103, solution mist is changed into mist after to pass into temperature with carrier gas be that the silica tube 40 of 100 DEG C ~ 220 DEG C generates presoma, wherein the diameter of silica tube 40 is 30mm ~ 150mm, and length is 0.5m ~ 3m, and the flow of carrier gas is 1L/min ~ 15L/min.
Preferably, the diameter of silica tube is 95mm, and length is 1.4m.
In present embodiment, use spraying gun 30 by solution atomization, spraying gun 30 is compression atomizing device.Concrete, the solution stored in the carrier gas stored in gas-holder 20 and container for storing liquid 10 is together passed into spraying gun 30 and makes solution mist change into mist.Carrier gas is rare gas element or reducing gas, as: at least one in nitrogen, argon gas and hydrogen, the flow of carrier gas is 5L/min ~ 8L/min.
Silica tube 40 outer wall is wrapped resistance wire 42.
Pass into from one end of silica tube 40 after solution mist changes into mist, in silica tube 40, generate presoma, presoma is trickle powder, and pulverous presoma sprays with the other end of carrier gas from silica tube.Further, presoma flows out rear use collector 50 from silica tube 40 and collects.In present embodiment, collector 50 is the acidproof filtration funnel of micropore.
S104, presoma calcined at 600 DEG C ~ 1300 DEG C within 2 hours ~ 5 hours, to obtain chemical formula be RYF
4: xDy
3+, yYb
3+dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material.
Preferably, presoma is placed in the calcination 3 hours at 800 DEG C of temperature programmed control stove.
The preparation method of above-mentioned dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material is spray pyrolysis, raw material mixes under solution state, uniform component distribution can be ensured, and technological process is simple, component loss is few, accurately can control stoichiometric ratio, especially be applicable to preparing polycomponent composite powder; Micro mist is by the aerial droplet drying that suspends, and particle is generally the spherical of rule, and few reunion, without the need to follow-up washing grinding, and the high purity of guarantee product, high reactivity; Whole process completed rapidly in short several seconds, and therefore drop has little time solute segregation occurs in reaction process, ensures the homogeneity of component distribution further; Reaction process is simple, and namely a step obtains finished product, and without filtration, washing, dry, crushing process, simple to operation, production process is continuous, and production capacity is large, and production efficiency is high, is very beneficial for large suitability for industrialized production; In the photoluminescence spectra of the dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material of preparation, the excitation wavelength 796nm of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material, corresponding respectively at the glow peak of 482nm is Dy
3+ion
4f
9/2→
6f
15/2transition radiation form glow peak, excited can be launched blue light by red-green glow, achieve that to inspire blue light shortwave by the infrared long-wave radiation to green glow luminous.
Refer to Fig. 2, the Organic Light Emitting Diode 100 of an embodiment, this Organic Light Emitting Diode 100 comprises the substrate 1, negative electrode 2, organic luminous layer 3, transparent anode 4 and the transparent encapsulated layer 5 that stack gradually.Be dispersed with dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material 6 in transparent encapsulated layer 5, the chemical formula of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material is RYF
4: xDy
3+, yYb
3+, wherein, x is 0.01 ~ 0.06, y be 0.01 ~ 0.04, R is elemental lithium, sodium element, potassium element, at least one in rubidium element and cesium element.
Dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material 6 is dispersed with in the transparent encapsulated layer 5 of Organic Light Emitting Diode 100, the excitation wavelength of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material is 796nm, and corresponding respectively at the glow peak of 482nm is Dy
3+ion
4f
9/2→
6f
15/2transition radiation form glow peak, excited can be launched blue light by red-green glow, blue light mixes with red-green glow and afterwards forms the Organic Light Emitting Diode emitted white light.
Be specific embodiment below.
Embodiment 1
Take Li
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3the mol ratio of powder is 1:0.95:0.03:0.02, is dissolved in the solution that hydrofluoric acid is mixed with 1.5mol/L, and adds the polyoxyethylene glycol additive of 0.01mol/L.Then solution is put into atomisation unit, backward atomisation unit pass into the argon gas of 5L/min.Solution presoma enters with argon carrier the silica tube generation presoma that temperature is 180 DEG C, and wherein the diameter of silica tube is 95mm, and length is 1.4m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.Collect the presoma of fluorescent material, be placed in temperature programmed control stove calcining 3 hours, calcining temperature 1100 DEG C, obtains LiYF
4: 0.03Dy
3+, 0.02Yb
3+up-conversion phosphor.
Refer to Fig. 3, the photoluminescence spectra of the dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material that curve 1 obtains for the present embodiment in Fig. 3.As seen from Figure 3, the excitation wavelength of the dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material that embodiment 1 obtains is 796nm, when material is subject to the radiation of long wavelength (as 796nm) time, and now Dy
3+ion
4f
9/2→
6f
15/2transition, just sends the blue light of 482nm, can as blue light emitting material.
Refer to Fig. 4, in Fig. 4, curve is the XRD curve of dysprosium ytterbium codoped alkali yttrium converting luminescent material of fluoride prepared by enforcement 1, test comparison standard P DF card, the diffraction peak in figure is the peak crystallization of alkali yttrium fluorochemical, does not occur the diffraction peak of doped element and other impurity; Illustrate that the product that this preparation method obtains has good crystalline quality.
Glass substrate 1 adopt vacuum plating techniques of deposition thickness be the metallic aluminium (Al) of 120nm, as the negative electrode 2 of device, then on negative electrode 2, deposit a layer thickness is that two (2-phenylquinoline) (methyl ethyl diketones) of 50nm close the organic luminous layer 3 of iridium (III) (Ir (2-phq) 2 (acac)) as device, on organic luminous layer 3, deposit a layer thickness is again 100nm, square resistance is that the tin indium oxide (ITO) of 10 ~ 20 Ω/mouth is as transparent anode 4, finally the transparent encapsulated layer 5 of SiO as device that a layer thickness is 300nm is set on transparent anode 4, dysprosium ytterbium codoped alkali yttrium fluorochemical up-conversion phosphor obtained in embodiment 1 is dispersed with in described transparent encapsulated layer 5, as indicated with 6, therefore, the concrete structure of this organic electroluminescence device can be expressed as substrate/Al (120nm)/Ir (2-phq) 2 (acac) (50nm)/ITO (100nm)/SiO (300nm), wherein, slash "/" represents laminate structure, when this organic electroluminescence device uses, the part ruddiness excitated fluorescent powder 6 of luminescent layer 3 sends blue light, and this blue light sends white light after mixing with remaining ruddiness in luminescent layer 3.
Refer to Fig. 5, Fig. 5 curve 1 is the spectrogram forming the Organic Light Emitting Diode emitted white light in transparent encapsulated layer doped with neodymium ytterbium codoped alkali yttrium fluoride salt glass up-conversion luminescent material material, and curve 2 is not doped with the contrast of neodymium ytterbium codoped alkali yttrium fluoride salt glass up-conversion luminescent material material in transparent encapsulated layer.Can find out in figure, fluorescent material by the red light of long wave, can inspire the blue light of shortwave, blendes together white light.
Embodiment 2
Take Li
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3mol ratio be 1:0.98:0.01:0.01, be dissolved in hydrofluoric acid the solution being mixed with 3mol/L, and add the polyoxyethylene glycol additive of 0.05mol/L.Then solution is put into atomisation unit, backward atomisation unit pass into the argon gas of 15L/min.Solution presoma enters with argon carrier the silica tube generation presoma that temperature is 220 DEG C, and wherein the diameter of silica tube is 150mm, and length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.Collect the presoma of fluorescent material, be placed in temperature programmed control stove calcining 5 hours, calcining temperature 1300 DEG C, obtains LiYF
4: 0.01Dy
3+, 0.01Yb
3+up-conversion phosphor.
Embodiment 3
Take Li
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3the mol ratio of powder is 1:0.9:0.06:0.04, is dissolved in hydrofluoric acid the solution being mixed with 0.5mol/L, and adds the polyoxyethylene glycol additive of 0.005mol/L.Then solution is put into atomisation unit, backward atomisation unit pass into the argon gas of 1L/min.Solution presoma enters with argon carrier silica tube generation presoma, wherein the diameter 30mm of silica tube that temperature is 150 DEG C, and length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.Collect the presoma of fluorescent material, be placed in temperature programmed control stove calcining 2 hours, calcining temperature 600 DEG C, obtains LiYF
4: 0.06Dy
3+, 0.04Yb
3+up-conversion phosphor.
Embodiment 4
Take Na
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3the mol ratio of powder is 1:0.95:0.03:0.02, is dissolved in hydrofluoric acid the solution being mixed with 1.5mol/L, and adds the polyoxyethylene glycol additive of 0.01mol/L.Then solution is put into atomisation unit, backward atomisation unit pass into the argon gas of 5L/min.Solution presoma enters with argon carrier silica tube generation presoma, wherein the diameter 30mm of silica tube that temperature is 180 DEG C, and length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.Collect the presoma of fluorescent material, be placed in temperature programmed control stove calcining 3 hours, calcining temperature 1100 DEG C, obtains NaYF
4: 0.03Dy
3+, 0.02Yb
3+up-conversion phosphor.
Embodiment 5
Take Na
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3the mol ratio of powder is 1:0.95:0.03:0.02, is dissolved in hydrofluoric acid the solution being mixed with 3mol/L, and adds the polyoxyethylene glycol additive of 0.05mol/L.Then solution is put into atomisation unit, backward atomisation unit pass into the argon gas of 15L/min.Solution presoma enters with argon carrier silica tube generation presoma, wherein the diameter 30mm of silica tube that temperature is 220 DEG C, and length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.Collect the presoma of fluorescent material, be placed in temperature programmed control stove calcining 5 hours, calcining temperature 1300 DEG C, obtains NaYF
4: 0.01Dy
3+, 0.01Yb
3+up-conversion phosphor.
Embodiment 6
Take Na
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3the mol ratio of powder is 1:0.9:0.06:0.04, is dissolved in hydrofluoric acid the solution being mixed with 0.5mol/L, and adds the polyoxyethylene glycol additive of 0.005mol/L.Then solution is put into atomisation unit, backward atomisation unit pass into the argon gas of 1L/min.Solution presoma enters with argon carrier silica tube generation presoma, wherein the diameter 30mm of silica tube that temperature is 150 DEG C, and length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.Collect the presoma of fluorescent material, be placed in temperature programmed control stove calcining 2 hours, calcining temperature 600 DEG C, obtains NaYF
4: 0.06Dy
3+, 0.04Yb
3+up-conversion phosphor.
Embodiment 7
Take K
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3the mol ratio of powder is 1:0.95:0.03:0.02, is dissolved in hydrofluoric acid the solution being mixed with 1.5mol/L, and adds the polyoxyethylene glycol additive of 0.01mol/L.Then solution is put into atomisation unit, backward atomisation unit pass into the argon gas of 5L/min.Solution presoma enters with argon carrier silica tube generation presoma, wherein the diameter 30mm of silica tube that temperature is 180 DEG C, and length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.Collect the presoma of fluorescent material, be placed in temperature programmed control stove calcining 3 hours, calcining temperature 1100 DEG C, obtains KYF
4: 0.03Dy
3+, 0.02Yb
3+up-conversion phosphor.
Embodiment 8
Take K
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3the mol ratio of powder is 1:0.95:0.03:0.02, is dissolved in hydrofluoric acid the solution being mixed with 3mol/L, and adds the polyoxyethylene glycol additive of 0.05mol/L.Then solution is put into atomisation unit, backward atomisation unit pass into the argon gas of 15L/min.Solution presoma enters with argon carrier silica tube generation presoma, wherein the diameter 30mm of silica tube that temperature is 220 DEG C, and length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.Collect the presoma of fluorescent material, be placed in temperature programmed control stove calcining 5 hours, calcining temperature 1300 DEG C, obtains KYF
4: 0.01Dy
3+, 0.01Yb
3+up-conversion phosphor.
Embodiment 9
Take K
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3the mol ratio of powder is 1:0.9:0.06:0.04, is dissolved in hydrofluoric acid the solution being mixed with 0.5mol/L, and adds the polyoxyethylene glycol additive of 0.005mol/L.Then solution is put into atomisation unit, backward atomisation unit pass into the argon gas of 1L/min.Solution presoma enters with argon carrier silica tube generation presoma, wherein the diameter 30mm of silica tube that temperature is 150 DEG C, and length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.Collect the presoma of fluorescent material, be placed in temperature programmed control stove calcining 2 hours, calcining temperature 600 DEG C, obtains KYF
4: 0.06Dy
3+, 0.04Yb
3+up-conversion phosphor.
Embodiment 10
Take Rb
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3the mol ratio of powder is 1:0.95:0.03:0.02, is dissolved in hydrofluoric acid the solution being mixed with 1.5mol/L, and adds the polyoxyethylene glycol additive of 0.01mol/L.Then solution is put into atomisation unit, backward atomisation unit pass into the argon gas of 5L/min.Solution presoma enters with argon carrier silica tube generation presoma, wherein the diameter 30mm of silica tube that temperature is 180 DEG C, and length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.Collect the presoma of fluorescent material, be placed in temperature programmed control stove calcining 3 hours, calcining temperature 1100 DEG C, obtains RbYF
4: 0.03Dy
3+, 0.02Yb
3+up-conversion phosphor.
Embodiment 11
Take Rb
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3the mol ratio of powder is 1:0.95:0.03:0.02, is dissolved in hydrofluoric acid the solution being mixed with 3mol/L, and adds the polyoxyethylene glycol additive of 0.05mol/L.Then solution is put into atomisation unit, backward atomisation unit pass into the argon gas of 15L/min.Solution presoma enters with argon carrier silica tube generation presoma, wherein the diameter 30mm of silica tube that temperature is 220 DEG C, and length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.Collect the presoma of fluorescent material, be placed in temperature programmed control stove calcining 5 hours, calcining temperature 1300 DEG C, obtains RbYF
4: 0.01Dy
3+, 0.01Yb
3+up-conversion phosphor.
Embodiment 12
Take Rb
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3the mol ratio of powder is 1:0.9:0.06:0.04, is dissolved in hydrofluoric acid the solution being mixed with 0.5mol/L, and adds the polyoxyethylene glycol additive of 0.005mol/L.Then solution is put into atomisation unit, backward atomisation unit pass into the argon gas of 1L/min.Solution presoma enters with argon carrier silica tube generation presoma, wherein the diameter 30mm of silica tube that temperature is 150 DEG C, and length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.Collect the presoma of fluorescent material, be placed in temperature programmed control stove calcining 2 hours, calcining temperature 600 DEG C, obtains RbYF
4: 0.06Dy
3+, 0.04Yb
3+up-conversion phosphor.
Embodiment 13
Take Cs
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3the mol ratio of powder is 1:0.95:0.03:0.02, is dissolved in hydrofluoric acid the solution being mixed with 1.5mol/L, and adds the polyoxyethylene glycol additive of 0.01mol/L.Then solution is put into atomisation unit, backward atomisation unit pass into the argon gas of 5L/min.Solution presoma enters with argon carrier silica tube generation presoma, wherein the diameter 30mm of silica tube that temperature is 180 DEG C, and length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.Collect the presoma of fluorescent material, be placed in temperature programmed control stove calcining 3 hours, calcining temperature 1100 DEG C, obtains CsYF
4: 0.03Dy
3+, 0.02Yb
3+up-conversion phosphor.
Embodiment 14
Take Cs
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3the mol ratio of powder is 1:0.95:0.03:0.02, is dissolved in hydrofluoric acid the solution being mixed with 3mol/L, and adds the polyoxyethylene glycol additive of 0.05mol/L.Then solution is put into atomisation unit, backward atomisation unit pass into the argon gas of 15L/min.Solution presoma enters with argon carrier silica tube generation presoma, wherein the diameter 30mm of silica tube that temperature is 220 DEG C, and length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.Collect the presoma of fluorescent material, be placed in temperature programmed control stove calcining 5 hours, calcining temperature 1300 DEG C, obtains CsYF
4: 0.01Dy
3+, 0.01Yb
3+up-conversion phosphor.
Embodiment 15
Take Cs
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3the mol ratio of powder is 1:0.9:0.06:0.04, is dissolved in hydrofluoric acid the solution being mixed with 0.5mol/L, and adds the polyoxyethylene glycol additive of 0.005mol/L.Then solution is put into atomisation unit, backward atomisation unit pass into the argon gas of 1L/min.Solution presoma enters with argon carrier silica tube generation presoma, wherein the diameter 30mm of silica tube that temperature is 150 DEG C, and length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.Collect the presoma of fluorescent material, be placed in temperature programmed control stove calcining 2 hours, calcining temperature 600 DEG C, obtains CsYF
4: 0.06Dy
3+, 0.04Yb
3+up-conversion phosphor.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material, is characterized in that: its chemical formula is RYF
4: xDy
3+, yYb
3+, wherein, x is 0.01 ~ 0.06, y be 0.01 ~ 0.04, R is elemental lithium, sodium element, potassium element, at least one in rubidium element and cesium element.
2. dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material according to claim 1, it is characterized in that, described x is 0.03, y is 0.02.
3. a preparation method for dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material, is characterized in that, comprise the following steps:
According to RYF
4: xDy
3+, yYb
3+the stoichiometric ratio of each element takes R
2cO
3, Y
2o
3, Dy
2o
3and Yb
2o
3powder, wherein, x is 0.01 ~ 0.06, y be 0.01 ~ 0.04, R is elemental lithium, sodium element, potassium element, at least one in rubidium element and cesium element;
The powder taken being dissolved in hydrofluoric acid the concentration being mixed with metallic cation is the solution of 0.5mol/L ~ 3mol/L;
Pass into carrier gas the silica tube generation presoma that temperature is 100 DEG C ~ 220 DEG C after described solution mist is changed into mist, wherein, the diameter of silica tube is 30mm ~ 150mm, and length is 0.5m ~ 3m, and the flow of carrier gas is 1L/min ~ 15L/min;
Described presoma is calcined at 600 DEG C ~ 1300 DEG C and within 2 hours ~ 5 hours, obtains chemical formula RYF
4: xDy
3+, yYb
3+dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material.
4. the preparation method of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material according to claim 3, it is characterized in that, described x is 0.03, y is 0.02.
5. the preparation method of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material according to claim 3, it is characterized in that, the powder taken is dissolved in hydrofluoric acid the step being mixed with solution also comprise: in described solution, add dispersion agent, the concentration of described dispersion agent is 0.005mol/L ~ 0.05mol/L.
6. the preparation method of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material according to claim 5, it is characterized in that, described dispersion agent is polyoxyethylene glycol.
7. the preparation method of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material according to claim 3, it is characterized in that, the step described solution mist being changed into mist is, carrier gas and described solution being passed into together in spraying gun makes described solution mist change into mist, and described carrier gas is rare gas element or reducing gas.
8. the preparation method of dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material according to claim 7, it is characterized in that, the flow of described carrier gas is 5L/min ~ 8L/min.
9. an Organic Light Emitting Diode, comprise the substrate, negative electrode, organic luminous layer, anode and the transparent encapsulated layer that stack gradually, it is characterized in that, doped with dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material in described transparent encapsulated layer, the chemical general formula of described dysprosium ytterbium codoped alkali yttrium fluoride glass up-conversion luminescent material is RYF
4: xDy
3+, yYb
3+, wherein, x is 0.01 ~ 0.06, y be 0.01 ~ 0.04, R is elemental lithium, sodium element, potassium element, at least one in rubidium element and cesium element.
10. Organic Light Emitting Diode according to claim 9, is characterized in that, described x is 0.03, y is 0.02.
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Application publication date: 20150211 |