CN104099096A - Holmium-doped alkali columbate up-conversion luminescent material and preparation method thereof, and organic light-emitting diode - Google Patents
Holmium-doped alkali columbate up-conversion luminescent material and preparation method thereof, and organic light-emitting diode Download PDFInfo
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Abstract
The invention provides a holmium-doped alkali columbate up-conversion luminescent material. The general chemical formula of the luminescent material is MeNbO3: xHo3+, wherein x is in a range of 0.01 to 0.06, and Me is one selected from the group consisting of lithium, sodium, potassium, rubidium and caesium. In the photoluminescence spectrum of the holmium-doped alkali columbate up-conversion luminescent material, the excitation wavelength of the holmium-doped alkali columbate up-conversion luminescent material is 640 nm, and a luminescence peak at 490 nm is formed by transition radiation of Ho3+ ions from 5F3 to 5I8. The invention further provides a preparation method for the holmium-doped alkali columbate up-conversion luminescent material and an organic light-emitting diode using the holmium-doped alkali columbate up-conversion luminescent material.
Description
Technical field
The present invention relates to a kind of holmium alkali-doped niobate up-conversion luminescent material, preparation method and Organic Light Emitting Diode.
Background technology
Organic Light Emitting Diode (OLED) because unit construction is simple, the characteristic such as cheap, the luminous of production cost, reaction times be short, flexible, apply widely and obtained the utmost point.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, can be by infrared, the long-wave radiations such as red-green glow inspire the holmium alkali-doped niobate 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 be inspired holmium alkali-doped niobate up-conversion luminescent material, the preparation method of blue light and be used the Organic Light Emitting Diode of this holmium alkali-doped niobate up-conversion luminescent material by long-wave radiation.
A kind of holmium alkali-doped niobate up-conversion luminescent material, has following chemical formula MeNbO
3: xHo
3+, wherein, x is that 0.01～0.06, Me is the one in lithium, sodium, potassium, rubidium and cesium element.
In an embodiment, x is 0.03 therein.
A preparation method for holmium alkali-doped niobate up-conversion luminescent material, comprises the following steps:
According to MeNbO
3: xHo
3+the stoichiometric ratio of each element takes Me
2o, Nb
2o
5and Ho
2o
3powder, wherein, x is that 0.01～0.06, Me is the one in lithium, sodium, potassium, rubidium and cesium element;
The powder taking is dissolved in and in nitric acid, is mixed with the solution that the concentration of metallic cation is 0.5mol/L～3mol/L;
Described solution mist is changed into after mist to pass into temperature with carrier gas be that the silica tube of 500 DEG C～1400 DEG C generates presoma, 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, obtained chemical formula MeNbO
3: xHo
3+holmium alkali-doped niobate up-conversion luminescent material.
In an embodiment, described x is 0.03 therein.
Therein in an embodiment, describedly the powder taking is dissolved in to the step that is mixed with solution in nitric acid also comprises: in described solution, add dispersion agent, the quality of described dispersion agent is 0.1g～2g.
Therein in an embodiment, the step that described solution mist is changed into mist is, carrier gas and described solution are passed into together in spraying gun and makes described solution mist change into mist, and described carrier gas is rare gas element or reducing gas.
In an embodiment, described dispersion agent is oxalic acid, ethanol, trolamine, water soluble starch or polyoxyethylene glycol therein.
In an embodiment, the flow of described carrier gas is 5L/min～8L/min therein.
A kind of Organic Light Emitting Diode, comprise the substrate, negative electrode, organic luminous layer, anode and the encapsulated layer that stack gradually, in described encapsulated layer, doped with holmium alkali-doped niobate up-conversion luminescent material, the chemical general formula of this holmium alkali-doped niobate up-conversion luminescent material is MeNbO
3: xHo
3+, wherein, x is that 0.01～0.06, Me is the one in lithium, sodium, potassium, rubidium and cesium element.
Hydrothermal method mild condition, the synthesis temperature of above-mentioned holmium alkali-doped niobate up-conversion luminescent material are low more easy to control, and granularity and the pattern of product are controlled, the powder complete crystallization of preparation, good dispersity, cost is lower, produces comparatively environmental protection in simultaneous reactions process without the three wastes; In the photoluminescence spectra of holmium alkali-doped niobate up-conversion luminescent material of preparation, the excitation wavelength of holmium alkali-doped niobate up-conversion luminescent material is 640nm, and corresponding respectively at the glow peak of 490nm is Ho
3+ion
5f
3→
5i
8transition radiation form glow peak, can be used as blue light emitting material.
Brief description of the drawings
Fig. 1 is the structural representation of the Organic Light Emitting Diode of an embodiment;
Fig. 2 is the structural representation of the spray pyrolysis equipment of an embodiment;
Fig. 3 is the photoluminescence spectrogram of the holmium alkali-doped niobate up-conversion luminescent material prepared of embodiment 1;
Fig. 4 is the XRD spectra of the holmium alkali-doped niobate up-conversion luminescent material prepared of embodiment 1;
Fig. 5 is the spectrogram doped with the Organic Light Emitting Diode of holmium alkali-doped niobate up-conversion luminescent material in the transparent encapsulated layer prepared of embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, holmium alkali-doped niobate up-conversion luminescent material and preparation method thereof is further illustrated.
The holmium alkali-doped niobate up-conversion luminescent material of one embodiment, has following chemical general formula MeNbO
3: xHo
3+, wherein, x is that 0.01～0.06, Me is the one in lithium, sodium, potassium, rubidium and cesium element.
Preferably, x is 0.03.
In the photoluminescence spectra of this holmium alkali-doped niobate up-conversion luminescent material, the excitation wavelength of holmium alkali-doped niobate up-conversion luminescent material is 640nm, in the time that material is subject to long wavelength's (as 640nm) radiation, the glow peak of 490nm is corresponding is respectively Ho
3+ion
5f
3→
5i
8, can be used as blue light emitting material.
The preparation method of above-mentioned holmium alkali-doped niobate up-conversion luminescent material, comprises the following steps;
Step S101, according to MeNbO
3: xHo
3+the stoichiometric ratio of each element takes Me
2o, Nb
2o
5and Ho
2o
3powder, wherein, x is that 0.01～0.06, Me is lithium, sodium, potassium, rubidium or caesium.
Preferably, x is 0.03.
Being appreciated that in this step also can be according to mol ratio 1:(0.94～0.99): (0.01～0.06) takes Me
2o, Nb
2o
5and Ho
2o
3powder.
Preferably, in this step, also can take Me according to mol ratio 1:0.97:0.03
2o, Nb
2o
5and Ho
2o
3powder.
Step S102, the powder taking is dissolved in and in nitric acid, is mixed with the solution that the concentration of metallic cation is 0.5mol/L～3mol/L.
Metallic cation in solution is Me
+, Nb
5+, Ho
3+, wherein, Me
+for the one in lithium ion, sodium ion, potassium ion, rubidium ion and cesium ion.
Preferably, the powder taking being dissolved in to the step that is mixed with solution in nitric acid also comprises: in solution, add dispersion agent, the quality of dispersion agent is 0.1g～2g.
Preferred dispersion agent can comprise oxalic acid, ethanol, trolamine, water soluble starch or polyoxyethylene glycol.
In present embodiment, dispersion agent is polyoxyethylene glycol.
Refer to Fig. 2, the spray pyrolysis equipment 100 shown in Fig. 2 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 is deposited in container for storing liquid 10.
S103, solution mist is changed into after mist to pass into temperature with carrier gas be that the silica tube 40 of 500 DEG C～1400 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 of the carrier gas of gas-holder 20 interior storages and container for storing liquid 10 interior storages is together passed into spraying gun 30 and make 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 walls are being wound around resistance wire 42.
Solution mist passes into from one end of silica tube 40 after changing into mist, and at the interior generation presoma of silica tube 40, presoma is trickle powder, and pulverous presoma is the other end ejection from silica tube with carrier gas.Further, presoma uses collector 50 to collect after silica tube 40 flows out.In present embodiment, collector 50 is the acidproof filtration funnel of micropore.
S104, presoma is calcined at 600 DEG C～1300 DEG C within 2 hours～5 hours, to obtain chemical formula be MeNbO
3: xHo
3+holmium alkali-doped niobate 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 holmium alkali-doped niobate up-conversion luminescent material is spray pyrolysis, and raw material mixes under solution state, can ensure uniform component distribution, and technological process is simple, component loss is few, can accurately control stoichiometric ratio, is especially applicable to preparing polycomponent composite powder; Micro mist is by being suspended in airborne droplet drying, and particle is generally the spherical of rule, and few reunion, grinds without follow-up washing, ensures the high purity of product, high reactivity; Whole process completed rapidly in short several seconds, and therefore drop has little time to occur solute segregation in reaction process, further ensured the homogeneity that component distributes; Reaction process is simple, and 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 holmium alkali-doped niobate up-conversion luminescent material of preparation, the excitation wavelength of holmium alkali-doped niobate up-conversion luminescent material is 640nm, and corresponding respectively at the glow peak of 490nm is Ho
3+ion
5f
3→
5i
8transition radiation form glow peak, realized that to inspire blue light shortwave by the infrared long-wave radiation to green glow luminous.
Refer to Fig. 1, 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 encapsulated layer 5 that stack gradually.In encapsulated layer 5, be dispersed with holmium alkali-doped niobate up-conversion luminescent material 6, the chemical general formula of holmium alkali-doped niobate up-conversion luminescent material is MeNbO
3: xHo
3+, wherein, x is that 0.01～0.06, Me is the one in lithium, sodium, potassium, rubidium and cesium element.
In the encapsulated layer 5 of Organic Light Emitting Diode 100, be dispersed with holmium alkali-doped niobate up-conversion luminescent material 6, the excitation wavelength of holmium alkali-doped niobate up-conversion luminescent material is 640nm, and corresponding respectively at the glow peak of 490nm is Ho
3+ion
5f
3→
5i
8transition radiation form glow peak, excite and can launch blue light by red-green glow, blue light mixes the Organic Light Emitting Diode that afterwards formation emits white light with red-green glow.
Be specific embodiment below.
Embodiment 1
Take Li
2o, Nb
2o
5and Ho
2o
3the mole number of powder is respectively 1mmol, 0.97mmol, and 0.03mmol, is dissolved in the solution that is mixed with 1.5mol/L in nitric acid, and adds the polyoxyethylene glycol additive of 1.2g.Then solution is put into atomisation unit, pass into afterwards the argon gas of 5L/min to atomisation unit.Solution presoma with argon carrier enter temperature be 1200 DEG C silica tube generate presoma, wherein the diameter of silica tube is 95mm, length is 1.4m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.The presoma of collecting fluorescent material, is placed in temperature programmed control stove and calcines 3 hours, and 1100 DEG C of calcining temperatures, obtain LiNbO
3: 0.03Ho
3+up-conversion phosphor.
The substrate 1 stacking gradually use soda-lime glass, negative electrode 2 use metal A g layer, organic luminous layer 3 use Ir (piq) 2 (acac) Chinese name two (1-phenyl-isoquinoline 99.9) (methyl ethyl diketones) close iridium (III), transparent anode 4 uses tin indium oxide ITO, and transparent encapsulated layer 5 tetrafluoroethylene.In transparent encapsulated layer 5, be dispersed with holmium alkali-doped niobate up-conversion luminescent material 6, the chemical formula of holmium alkali-doped niobate up-conversion luminescent material is LiNbO
3: 0.03Ho
3+.
Refer to Fig. 3, Figure 3 shows that the holmium alkali-doped niobate up-conversion luminescent material chemical general formula that this enforcement obtains is LiNbO
3: 0.03Ho
3+photoluminescence spectra figure.As seen from Figure 3, the excitation wavelength of the holmium alkali-doped niobate up-conversion luminescent material that the present embodiment obtains is 640nm, in 490nm wavelength zone by Ho
3+ion
5f
3→
5i
8transition radiation form glow peak, this holmium alkali-doped niobate up-conversion luminescent material can be used as blue light emitting material.
Refer to Fig. 4, in Fig. 4, curve is the XRD curve of implementing the holmium alkali-doped niobate up-conversion luminescent material of 1 preparation, test comparison standard P DF card.Contrast PDF card, can find out that all diffraction peaks are all the crystallization phasess of corresponding alkali niobic acid, and does not have doped element and other dephasign to occur, illustrates that the product that this preparation method obtains has good crystalline quality.
Fig. 5 is the spectrogram that has the Organic Light Emitting Diode that holmium alkali-doped niobate up-conversion luminescent material forms in the transparent encapsulated layer prepared of embodiment 1, and curve 2 is not for adding the contrast of fluorescent material.In figure, can find out, fluorescent material can, by the red light of long wave, inspire the blue light of shortwave, blendes together white light.
Embodiment 2
Take Li
2o, Nb
2o
5and Ho
2o
3the mole number of powder is respectively 1mmol, 0.99mmol, and 0.01mmol, is dissolved in the solution that is mixed with 0.5mol/L in nitric acid, and adds the polyoxyethylene glycol additive of 2g.Then solution is put into atomisation unit, pass into afterwards the argon gas of 1L/min to atomisation unit.Solution presoma with argon carrier enter temperature be 500 DEG C silica tube generate presoma, wherein the diameter of silica tube is 150mm, length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.The presoma of collecting fluorescent material, is placed in temperature programmed control stove and calcines 5 hours, and 1300 DEG C of calcining temperatures, obtain LiNbO
3: 0.01Ho
3+up-conversion phosphor.
Embodiment 3
Take Li
2o, Nb
2o
5and Ho
2o
3the mole number of powder is respectively 1mmol, 0.94mmol, and 0.06mmol, is dissolved in the solution that is mixed with 3mol/L in nitric acid, and adds the polyoxyethylene glycol additive of 0.2g.Then solution is put into atomisation unit, pass into afterwards the argon gas of 15L/min to atomisation unit.Solution presoma with argon carrier enter temperature be 1400 DEG C silica tube generate presoma, wherein the diameter of silica tube is 30mm, length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.The presoma of collecting fluorescent material, is placed in temperature programmed control stove and calcines 2 hours, and 600 DEG C of calcining temperatures, obtain LiNbO
3: 0.06Ho
3+up-conversion phosphor.
Embodiment 4
Take Na
2o, Nb
2o
5and Ho
2o
3the mole number of powder is respectively 1mmol, 0.97mmol, and 0.03mmol, is dissolved in the solution that is mixed with 1.5mol/L in nitric acid, and adds the polyoxyethylene glycol additive of 1.2g.Then solution is put into atomisation unit, pass into afterwards the argon gas of 5L/min to atomisation unit.Solution presoma with argon carrier enter temperature be 1200 DEG C silica tube generate presoma, wherein the diameter of silica tube is 95mm, length is 1.4m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.The presoma of collecting fluorescent material, is placed in temperature programmed control stove and calcines 3 hours, and 1100 DEG C of calcining temperatures, obtain NaNbO
3: 0.03Ho
3+up-conversion phosphor.
Embodiment 5
Take Na
2o, Nb
2o
5and Ho
2o
3the mole number of powder is respectively 1mmol, 0.99mmol, and 0.01mmol, is dissolved in the solution that is mixed with 0.5mol/L in nitric acid, and adds the polyoxyethylene glycol additive of 2g.Then solution is put into atomisation unit, pass into afterwards the argon gas of 1L/min to atomisation unit.Solution presoma with argon carrier enter temperature be 500 DEG C silica tube generate presoma, wherein the diameter of silica tube is 150mm, length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.The presoma of collecting fluorescent material, is placed in temperature programmed control stove and calcines 5 hours, and 1300 DEG C of calcining temperatures, obtain NaNbO
3: 0.01Ho
3+up-conversion phosphor.
Embodiment 6
Take Na
2o, Nb
2o
5and Ho
2o
3the mole number of powder is respectively 1mmol, 0.94mmol, and 0.06mmol, is dissolved in the solution that is mixed with 3mol/L in nitric acid, and adds the polyoxyethylene glycol additive of 0.2g.Then solution is put into atomisation unit, pass into afterwards the argon gas of 15L/min to atomisation unit.Solution presoma with argon carrier enter temperature be 1400 DEG C silica tube generate presoma, wherein the diameter of silica tube is 30mm, length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.The presoma of collecting fluorescent material, is placed in temperature programmed control stove and calcines 2 hours, and 600 DEG C of calcining temperatures, obtain NaNbO
3: 0.06Ho
3+up-conversion phosphor.
Embodiment 7
Take K
2o, Nb
2o
5and Ho
2o
3the mole number of powder is respectively 1mmol, 0.97mmol, and 0.03mmol, is dissolved in the solution that is mixed with 1.5mol/L in nitric acid, and adds the polyoxyethylene glycol additive of 1.2g.Then solution is put into atomisation unit, pass into afterwards the argon gas of 5L/min to atomisation unit.Solution presoma with argon carrier enter temperature be 1200 DEG C silica tube generate presoma, wherein the diameter of silica tube is 95mm, length is 1.4m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.The presoma of collecting fluorescent material, is placed in temperature programmed control stove and calcines 3 hours, and 1100 DEG C of calcining temperatures, obtain KNbO
3: 0.03Ho
3+up-conversion phosphor.
Embodiment 8
Take K
2o, Nb
2o
5and Ho
2o
3the mole number of powder is respectively 1mmol, 0.99mmol, and 0.01mmol, is dissolved in the solution that is mixed with 0.5mol/L in nitric acid, and adds the polyoxyethylene glycol additive of 2g.Then solution is put into atomisation unit, pass into afterwards the argon gas of 1L/min to atomisation unit.Solution presoma with argon carrier enter temperature be 500 DEG C silica tube generate presoma, wherein the diameter of silica tube is 150mm, length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.The presoma of collecting fluorescent material, is placed in temperature programmed control stove and calcines 5 hours, and 1300 DEG C of calcining temperatures, obtain KNbO
3: 0.01Ho
3+up-conversion phosphor.
Embodiment 9
Take K
2o, Nb
2o
5and Ho
2o
3the mole number of powder is respectively 1mmol, 0.94mmol, and 0.06mmol, is dissolved in the solution that is mixed with 3mol/L in nitric acid, and adds the polyoxyethylene glycol additive of 0.2g.Then solution is put into atomisation unit, pass into afterwards the argon gas of 15L/min to atomisation unit.Solution presoma with argon carrier enter temperature be 1400 DEG C silica tube generate presoma, wherein the diameter of silica tube is 30mm, length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.The presoma of collecting fluorescent material, is placed in temperature programmed control stove and calcines 2 hours, and 600 DEG C of calcining temperatures, obtain KNbO
3: 0.06Ho
3+up-conversion phosphor.
Embodiment 10
Take Rb
2o, Nb
2o
5and Ho
2o
3the mole number of powder is respectively 1mmol, 0.97mmol, and 0.03mmol, is dissolved in the solution that is mixed with 1.5mol/L in nitric acid, and adds the polyoxyethylene glycol additive of 1.2g.Then solution is put into atomisation unit, pass into afterwards the argon gas of 5L/min to atomisation unit.Solution presoma with argon carrier enter temperature be 1200 DEG C silica tube generate presoma, wherein the diameter of silica tube is 95mm, length is 1.4m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.The presoma of collecting fluorescent material, is placed in temperature programmed control stove and calcines 3 hours, and 1100 DEG C of calcining temperatures, obtain RbNbO
3: 0.03Ho
3+up-conversion phosphor.
Embodiment 11
Take Rb
2o, Nb
2o
5and Ho
2o
3the mole number of powder is respectively 1mmol, 0.99mmol, and 0.01mmol, is dissolved in the solution that is mixed with 0.5mol/L in nitric acid, and adds the polyoxyethylene glycol additive of 2g.Then solution is put into atomisation unit, pass into afterwards the argon gas of 1L/min to atomisation unit.Solution presoma with argon carrier enter temperature be 500 DEG C silica tube generate presoma, wherein the diameter of silica tube is 150mm, length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.The presoma of collecting fluorescent material, is placed in temperature programmed control stove and calcines 5 hours, and 1300 DEG C of calcining temperatures, obtain RbNbO
3: 0.01Ho
3+up-conversion phosphor.
Embodiment 12
Take Rb
2o, Nb
2o
5and Ho
2o
3the mole number of powder is respectively 1mmol, 0.94mmol, and 0.06mmol, is dissolved in the solution that is mixed with 3mol/L in nitric acid, and adds the polyoxyethylene glycol additive of 0.2g.Then solution is put into atomisation unit, pass into afterwards the argon gas of 15L/min to atomisation unit.Solution presoma with argon carrier enter temperature be 1400 DEG C silica tube generate presoma, wherein the diameter of silica tube is 30mm, length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.The presoma of collecting fluorescent material, is placed in temperature programmed control stove and calcines 2 hours, and 600 DEG C of calcining temperatures, obtain RbNbO
3: 0.06Ho
3+up-conversion phosphor.
Embodiment 13
Take Cs
2o, Nb
2o
5and Ho
2o
3the mole number of powder is respectively 1mmol, 0.97mmol, and 0.03mmol, is dissolved in the solution that is mixed with 1.5mol/L in nitric acid, and adds the polyoxyethylene glycol additive of 1.2g.Then solution is put into atomisation unit, pass into afterwards the argon gas of 5L/min to atomisation unit.Solution presoma with argon carrier enter temperature be 1200 DEG C silica tube generate presoma, wherein the diameter of silica tube is 95mm, length is 1.4m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.The presoma of collecting fluorescent material, is placed in temperature programmed control stove and calcines 3 hours, and 1100 DEG C of calcining temperatures, obtain CsNbO
3: 0.03Ho
3+up-conversion phosphor.
Embodiment 14
Take Cs
2o, Nb
2o
5and Ho
2o
3the mole number of powder is respectively 1mmol, 0.99mmol, and 0.01mmol, is dissolved in the solution that is mixed with 0.5mol/L in nitric acid, and adds the polyoxyethylene glycol additive of 2g.Then solution is put into atomisation unit, pass into afterwards the argon gas of 1L/min to atomisation unit.Solution presoma with argon carrier enter temperature be 500 DEG C silica tube generate presoma, wherein the diameter of silica tube is 150mm, length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.The presoma of collecting fluorescent material, is placed in temperature programmed control stove and calcines 5 hours, and 1300 DEG C of calcining temperatures, obtain CsNbO
3: 0.01Ho
3+up-conversion phosphor.
Embodiment 15
Take Cs
2o, Nb
2o
5and Ho
2o
3the mole number of powder is respectively 1mmol, 0.94mmol, and 0.06mmol, is dissolved in the solution that is mixed with 3mol/L in nitric acid, and adds the polyoxyethylene glycol additive of 0.2g.Then solution is put into atomisation unit, pass into afterwards the argon gas of 15L/min to atomisation unit.Solution presoma with argon carrier enter temperature be 1400 DEG C silica tube generate presoma, wherein the diameter of silica tube is 30mm, length is 3m.Then fluorescent material enters condenser with air-flow, finally collected by the acidproof filtration funnel of micropore.The presoma of collecting fluorescent material, is placed in temperature programmed control stove and calcines 2 hours, and 600 DEG C of calcining temperatures, obtain CsNbO
3: 0.06Ho
3+up-conversion phosphor.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore 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 holmium alkali-doped niobate up-conversion luminescent material, is characterized in that: have following chemical general formula MeNbO
3: xHo
3+, wherein, x is that 0.01～0.06, Me is the one in lithium, sodium, potassium, rubidium and cesium element.
2. holmium alkali-doped niobate up-conversion luminescent material according to claim 1, is characterized in that, described x is 0.03.
3. a preparation method for holmium alkali-doped niobate up-conversion luminescent material, is characterized in that, comprises the following steps:
According to MeNbO
3: xHo
3+the stoichiometric ratio of each element takes Me
2o, Nb
2o
5and Ho
2o
3powder, wherein, x is that 0.01～0.06, Me is the one in lithium, sodium, potassium, rubidium and cesium element;
The powder taking is dissolved in and in nitric acid, is mixed with the solution that the concentration of metallic cation is 0.5mol/L～3mol/L;
Described solution mist is changed into after mist to pass into temperature with carrier gas be that the silica tube of 500 DEG C～1400 DEG C generates presoma, 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, obtained chemical formula MeNbO
3: xHo
3+holmium alkali-doped niobate up-conversion luminescent material.
4. the preparation method of holmium alkali-doped niobate up-conversion luminescent material according to claim 3, is characterized in that, described x is 0.03.
5. the preparation method of holmium alkali-doped niobate up-conversion luminescent material according to claim 3, it is characterized in that, describedly the powder taking is dissolved in to the step that is mixed with solution in nitric acid also comprises: in described solution, add dispersion agent, the quality of described dispersion agent is 0.1g～2g.
6. the preparation method of holmium alkali-doped niobate up-conversion luminescent material according to claim 3, is characterized in that, described dispersion agent is oxalic acid, ethanol, trolamine, water soluble starch or polyoxyethylene glycol.
7. the preparation method of holmium alkali-doped niobate up-conversion luminescent material according to claim 3, it is characterized in that, the step that described solution mist is changed into mist is, carrier gas and described solution are passed into together in spraying gun and makes described solution mist change into mist, and described carrier gas is rare gas element or reducing gas.
8. the preparation method of holmium alkali-doped niobate up-conversion luminescent material according to claim 3, 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, in described transparent encapsulated layer, doped with holmium alkali-doped niobate up-conversion luminescent material, the chemical general formula of described holmium alkali-doped niobate up-conversion luminescent material is MeNbO
3: xHo
3+, wherein, x is that 0.01～0.06, Me is the one in lithium, sodium, potassium, rubidium and cesium element.
10. Organic Light Emitting Diode according to claim 9, is characterized in that, described x is 0.03.
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