CN104650917A - Thulium- holmium- co-doped IIIA-group yttrium fluosilicate up-conversion luminescent materials, and preparing method and applications thereof - Google Patents

Thulium- holmium- co-doped IIIA-group yttrium fluosilicate up-conversion luminescent materials, and preparing method and applications thereof Download PDF

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CN104650917A
CN104650917A CN201310581031.6A CN201310581031A CN104650917A CN 104650917 A CN104650917 A CN 104650917A CN 201310581031 A CN201310581031 A CN 201310581031A CN 104650917 A CN104650917 A CN 104650917A
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codoped
conversion luminescent
races
luminescent material
diu
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周明杰
陈吉星
王平
钟铁涛
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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

Thulium- holmium- co-doped IIIA-group yttrium fluosilicate up-conversion luminescent materials are provided. The general chemical formula of the materials is MeYSiF10:xTm<3+>,yHo<3+>, wherein the x is 0.01-0.08, the y is 0-0.06, and the Me is at least one of gallium, indium and thallium. The excitation wave length of one of the materials is 650 nm, and obtained luminescence peaks at 454 nm and 476 nm are respectively formed by transition radiation from the 1D2 to the 3H4 and transition radiation from the 1G4 to the 3H6 of the Tm<3+>. Blue-light short-wave luminescence from radiation excitation of long waves from infrared to green rays is achieved. A preparing method and applications of the materials are also provided.

Description

Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material, preparation method and application
Technical field
The present invention relates to a kind of Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material, its preparation method and use the Organic Light Emitting Diode of this Diu Huo codoped three races silicofluoric acid yttrium 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 Diu Huo codoped three races silicofluoric acid yttrium 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 Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material of blue light, its preparation method by long-wave radiation and use the Organic Light Emitting Diode of this Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material.
A kind of Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material, its chemical formula is MeYSiF 10: xTm 3+, yHo 3+, wherein, x is 0.01 ~ 0.08, y be 0 ~ 0.06, Me is gallium element, at least one in phosphide element and thallium element.
Described x is 0.04, y is 0.03.
A preparation method for Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material, comprises the following steps:
According to MeYSiF 10: xTm 3+, yHo 3+the stoichiometric ratio of each element takes Me 2o 3, Y 2o 3, SiO, Tm 2o 3and Ho 2o 3powder, wherein, x is 0.01 ~ 0.08, y be 0 ~ 0.06, Me is gallium element, at least one in phosphide element and thallium 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 MeYSiF 10: xTm 3+, yHo 3+diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material.
Described x is 0.04, y is 0.03.
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 Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material in described transparent encapsulated layer, the chemical general formula of described Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material is MeYSiF 10: xTm 3+, yHo 3+, wherein, x is 0.01 ~ 0.08, y be 0 ~ 0.06, Me is gallium element, at least one in phosphide element and thallium element.
Described x is 0.04, y is 0.03.
The preparation method of above-mentioned Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material is comparatively simple, and cost is lower; In the photoluminescence spectra of the Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material of preparation, the excitation wavelength of Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material is 650nm, and corresponding respectively at the glow peak of 454nm and 476nm is Tm 3+ion 1d 2→ 3h 4, 1g 4→ 3h 6transition radiation form glow peak, achieve that to inspire blue light shortwave by the infrared long-wave radiation to green glow luminous; Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material is dispersed with in the transparent encapsulated layer of Organic Light Emitting Diode, the excitation wavelength of Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material is 650nm, and corresponding respectively at the glow peak of 454nm and 476nm is Tm 3+ion 1d 2→ 3h 4, 1g 4→ 3h 6transition 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 Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material prepared by embodiment 1;
Fig. 4 is the XRD spectra of Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material prepared by embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments to Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material, its preparation method and use the Organic Light Emitting Diode of this Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material to illustrate further.
The Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material of one embodiment, its chemical formula is MeYSiF 10: xTm 3+, yHo 3+, wherein, x is 0.01 ~ 0.08, y be 0 ~ 0.06, Me is gallium element, at least one in phosphide element and thallium element.
Preferably, x is 0.04, y is 0.03.
In the photoluminescence spectra of this Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material, the excitation wavelength of Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material is 650nm, when material is subject to the radiation of long wavelength (as 650nm) time, and Tm 3+the energy of this illumination of ionic absorption, now Tm 3+ion by 1d 2→ 3h 4, 1g 4→ 3h 6transition, send the blue light of 454nm and 476nm, achieve that to inspire blue light shortwave by the infrared long-wave radiation to green glow luminous.
The preparation method of above-mentioned Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material, comprises the following steps;
Step S101, according to MeYSiF 10: xTm 3+, yHo 3+the stoichiometric ratio of each element takes Me 2o 3, Y 2o 3, SiO, Tm 2o 3and Ho 2o 3powder, wherein, x is 0.01 ~ 0.08, y be 0 ~ 0.06, Me is gallium element, at least one in phosphide element and thallium element.
Preferably, x is 0.04, y is 0.03.
Being appreciated that in this step also can according to mol ratio 1:1:2:(0.01 ~ 0.08): (0 ~ 0.06) takes Me 2o 3, Y 2o 3, SiO, Tm 2o 3and Ho 2o 3powder.
Preferably, also Me can be taken according to mol ratio 1:1:2:0.03:0.04 in this step 2o 3, Y 2o 3, SiO, Tm 2o 3and Ho 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 Me 3+, Y 3+, Si 4+, Tm 3+and Ho 3+.
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 MeYSiF 10: xTm 3+, yHo 3+diu Huo codoped three races silicofluoric acid yttrium 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 Diu Huo codoped three races silicofluoric acid yttrium 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 Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material of preparation, the excitation wavelength 650nm of Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material, corresponding respectively at the glow peak of 454nm and 476nm is Tm 3+ion 1d 2→ 3h 4, 1g 4→ 3h 6transition 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 200 of an embodiment, this Organic Light Emitting Diode 200 comprises the substrate 1, negative electrode 2, organic luminous layer 3, transparent anode 4 and the transparent encapsulated layer 5 that stack gradually.The chemical formula of silicofluoric acid yttrium up-conversion luminescent material 6, Diu Huo codoped three races of Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material is dispersed with for being MeYSiF in transparent encapsulated layer 5 10: xTm 3+, yHo 3+, wherein, x is 0.01 ~ 0.08, y be 0 ~ 0.06, Me is gallium element, at least one in phosphide element and thallium element.
Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material 6 is dispersed with in the transparent encapsulated layer 5 of Organic Light Emitting Diode 200, the excitation wavelength of Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material is 650nm, and corresponding respectively at the glow peak of 454nm and 476nm is Tm 3+ion 1d 2→ 3h 4, 1g 4→ 3h 6transition 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 Ga 2o 3, Y 2o 3, SiO, Tm 2o 3and Ho 2o 3the mole number of powder is 0.5mmol, 0.5mmol, 1mmol, 0.04mmol and 0.03mmol, 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 GaYSiF 10: 0.04Tm 3+, 0.03Ho 3+up-conversion phosphor.
Refer to Fig. 3, the photoluminescence spectra of the Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material that curve 2 obtains for the present embodiment in Fig. 3.As can be seen from Fig. 3 curve 2, the excitation wavelength of the Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material that embodiment 1 obtains is 650nm, when material is subject to the radiation of long wavelength (as 650nm) time, and now Tm 3+ion 1d 2→ 3h 4, 1g 4→ 3h 6transition, just sends the blue light of 454nm and 476nm, can as blue light emitting material, and curve 1 is the comparative example GaYSiF of holmium element of not adulterating 10: 0.04Tm 3+, contrast the known codoped adding holmium, luminous position does not change, and luminous efficiency significantly improves.
Refer to Fig. 4, in Fig. 4, curve is the XRD curve of Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material prepared by enforcement 1, test comparison standard P DF card, in figure, diffraction peak is depicted as the crystalline phase of three races's silicofluoric acid yttrium, do not occur illustrating that thulium holmium doped element is the lattice entering three races's silicofluoric acid yttrium in the peak that thulium holmium element is relevant.
Embodiment 2
Take Ga 2o 3, Y 2o 3, SiO, Tm 2o 3and Ho 2o 3the mole number of powder is 0.5mmol, 0.5mmol, 1mmol, 0.01mmol and 0.01mmol, 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 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 GaYSiF 10: 0.01Tm 3+, 0.01Ho 3+up-conversion phosphor.
Embodiment 3
Take Ga 2o 3, Y 2o 3, SiO, Tm 2o 3and Ho 2o 3the mole number of powder is 0.5mmol, 0.5mmol, 1mmol, 1mmol and 0.08mmol, 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 GaYSiF 10: 0.08Tm 3+up-conversion phosphor.
Embodiment 4
Take In 2o 3, Y 2o 3, SiO, Tm 2o 3and Ho 2o 3the mole number of powder is 0.5mmol, 0.5mmol, 1mmol, 0.04mmol and 0.03mmol, 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 InYSiF 10: 0.04Tm 3+, 0.03Ho 3+up-conversion phosphor.
Embodiment 5
Take In 2o 3, Y 2o 3, SiO, Tm 2o 3and Ho 2o 3the mole number of powder is 0.5mmol, 0.5mmol, 1mmol, 0.01mmol and 0.01mmol, 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 InYSiF 10: 0.01Tm 3+, 0.01Ho 3+up-conversion phosphor.
Embodiment 6
Take In 2o 3, Y 2o 3, SiO, Tm 2o 3and Ho 2o 3the mole number of powder is 0.5mmol, 0.5mmol, 1mmol, 1mmol and 0.08mmol, 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 InYSiF 10: 0.08Tm 3+up-conversion phosphor.
Embodiment 7
Take Tl 2o 3, Y 2o 3, SiO, Tm 2o 3and Ho 2o 3the mole number of powder is 0.5mmol, 0.5mmol, 1mmol, 0.04mmol and 0.03mmol, 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 TlYSiF 10: 0.04Tm 3+, 0.03Ho 3+up-conversion phosphor.
Embodiment 8
Take Tl 2o 3, Y 2o 3, SiO, Tm 2o 3and Ho 2o 3the mole number of powder is 0.5mmol, 0.5mmol, 1mmol, 0.01mmol and 0.01mmol, 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 TlYSiF 10: 0.01Tm 3+, 0.01Ho 3+up-conversion phosphor.
Embodiment 9
Take Tl 2o 3, Y 2o 3, SiO, Tm 2o 3and Ho 2o 3the mole number of powder is 0.5mmol, 0.5mmol, 1mmol, 0.08mmol, 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 TlYSiF 10: 0.08Tm 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 Zhong Diuhuo codoped three races silicofluoric acid yttrium up-conversion luminescent material, is characterized in that: its chemical formula is MeYSiF 10: xTm 3+, yHo 3+, wherein, x is 0.01 ~ 0.08, y be 0 ~ 0.06, Me is gallium element, at least one in phosphide element and thallium element.
2. Diu Huo codoped three races according to claim 1 silicofluoric acid yttrium up-conversion luminescent material, is characterized in that, described x is 0.04, y is 0.03.
3. the preparation method of a Zhong Diuhuo codoped three races silicofluoric acid yttrium up-conversion luminescent material, is characterized in that, comprise the following steps:
According to MeYSiF 10: xTm 3+, yHo 3+the stoichiometric ratio of each element takes Me 2o 3, Y 2o 3, SiO, Tm 2o 3and Ho 2o 3powder, wherein, x is 0.01 ~ 0.08, y be 0 ~ 0.06, Me is gallium element, at least one in phosphide element and thallium 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 MeYSiF 10: xTm 3+, yHo 3+diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material.
4. the preparation method of Diu Huo codoped three races according to claim 3 silicofluoric acid yttrium up-conversion luminescent material, is characterized in that, described x is 0.04, y is 0.03.
5. the preparation method of Diu Huo codoped three races according to claim 3 silicofluoric acid yttrium up-conversion luminescent material, 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 Diu Huo codoped three races according to claim 5 silicofluoric acid yttrium up-conversion luminescent material, it is characterized in that, described dispersion agent is polyoxyethylene glycol.
7. the preparation method of Diu Huo codoped three races according to claim 3 silicofluoric acid yttrium up-conversion luminescent material, 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 Diu Huo codoped three races according to claim 7 silicofluoric acid yttrium up-conversion luminescent material, 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 Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material in described transparent encapsulated layer, the chemical general formula of described Diu Huo codoped three races silicofluoric acid yttrium up-conversion luminescent material is MeYSiF 10: xTm 3+, yHo 3+, wherein, x is 0.01 ~ 0.08, y be 0 ~ 0.06, Me is gallium element, at least one in phosphide element and thallium element.
10. Organic Light Emitting Diode according to claim 9, is characterized in that, described x is 0.04, y is 0.03.
CN201310581031.6A 2013-11-18 2013-11-18 Thulium- holmium- co-doped IIIA-group yttrium fluosilicate up-conversion luminescent materials, and preparing method and applications thereof Pending CN104650917A (en)

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