CN105602564B - A kind of enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn and preparation method - Google Patents
A kind of enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn and preparation method Download PDFInfo
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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Abstract
The invention provides a kind of enhanced rare-earth oxide sulfate up-conversion luminescent materials of Zn and preparation method, the chemical formula of the material is (Ln1‑x‑y‑zYbxREyZnz)2O2S, wherein 0.04≤x≤0.2,0.005≤y≤0.02,0.005≤z≤0.02；Ln is one kind in La, Y or Gd, and RE is one kind in Er, Ho, Tm, Pr, Eu or Tb.The material emission intensity is greatly enhanced, and improves 50%~120%.The preparation method of the material, rare-earth oxidation raw material is obtained using the anti-method dripped of precipitating reagent, then gas cure method is used, reaction condition is simple, easily-controllable, this method can be very good to keep the pattern and particle size of rare earth oxide, is presented spherical the rare-earth oxide sulfate up-conversion luminescent material prepared by this method, particle size uniformity more, particle distribution range is narrower, D90=0.2 0.5 μm.
Description
Technical field
The present invention relates to field of fine chemical, sent out in particular to being changed on a kind of enhanced rare-earth oxide sulfates of Zn
Luminescent material and preparation method.
Background technology
In recent years, the raising of near-infrared semiconductor laser diode power output, is provided for up-conversion luminescent material
Pumping source effectively is excited, up-conversion luminescent material is promoted and develops on a large scale, it is vertical in RGB short wavelength laser, three-dimensional
The fields such as body is shown, infrared detection technique, anti-counterfeiting technology, biomolecule fluorescence labeling and solar cell have obtained actual or latent
Application.Host material is the chief component of up-conversion luminescent material, and its physicochemical properties is largely fixed
The overall performance of up-conversion luminescent material.Oxysulfide is because with good heat endurance and chemical stability, energy gap
For 4.6-4.8eV, it is suitable for Doped ions, its maximum phonon can be 520cm-1, it is considered to be up-conversion luminescent material is potential
Host material.
The preparation method of rare-earth oxide sulfate up-conversion luminescent material has a lot, and the major advantage of wherein sulfur melt method is to fit
For industrial mass production, crystal perfection, luminescent properties are better than product prepared by other method.But the reaction temperature of sulfur melt method
Degree is higher, and usual product reaction temperature of good performance is up to 1200 DEG C, and course of reaction is not easily controlled.Sulphur melts simultaneously
The fluxing agent consumption and species of method are not fixed, and there is presently no a clear and definite scope.In addition, the oxide that sulfur melt method is used
The rare earth oxide that raw material is typically directly bought using in the market, without further optimization processing, particle size is uneven, reunites
It is more serious, the physical property of particle of rare-earth oxide sulfate product can be influenceed.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of enhanced rare-earth oxide sulfate up-conversion luminescent materials of Zn, to solve
Turn on the problem of existing rare-earth oxide sulfate up-conversion luminescent material luminous intensity is weak, the enhanced rare-earth oxide sulfates of described Zn
Luminescent material is changed, because Zn doping optimizes the crystal structure of rare-earth oxide sulfate, crystal structure symmetry harmony is reduced
Sub- energy, luminous intensity is greatly enhanced, and improves 50%~120%.
The second object of the present invention is to provide a kind of described enhanced rare-earth oxide sulfate up-conversion luminescent materials of Zn
Preparation method, this method prepares rare-earth oxidation raw material using the anti-method dripped of precipitating reagent, to solve the rare earth of existing purchase
Oxide raw material particle size is uneven, the problem of reunite more serious, and there is prepared rare-earth oxidation raw material particle to be in
The advantages of showing spherical, even particle size, good dispersion, not needing ball milling, can be used directly.Then, using gas cure method
The traditional sulfur melt method of substitution, reaction condition is simple, easily-controllable, and this method can be very good to keep the pattern and particle of rare earth oxide
Size.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn, the chemical formula of the material is (Ln1-x-y- zYbxREyZnz)2O2S, wherein 0.04≤x≤0.2,0.005≤y≤0.02,0.005≤z≤0.02；Wherein Ln is La, Y or Gd
In one kind, RE be Er, Ho, Tm, Pr, Eu or Tb in one kind.
Up-conversion luminescence is light of the sustainable launch wavelength than excitation light wave length in the case where long wavelength light is excited.Upper conversion
Luminous is substantially that a kind of anti-stocks lights, that is, the energy radiated is more than absorbed energy.Up-conversion, which is mainly, to be mixed
The solid chemical compound of miscellaneous rare earth element, using the metastable energy level feature of rare earth element, can absorb the long wave of multiple low energy
Radiation, so as to make infrared light invisible to the human eye become visible ray.The Zn of divalence2+In rare-earth oxide sulfate up-conversion luminescence material
In material, the crystal structure of rare-earth oxide sulfate is optimized, crystal structure symmetry and phonon energy is reduced, this is due to Zn2+
Enter the lattice of rare-earth oxide sulfate in the way of calking, produce distortion of lattice, change the crystalline field of rare-earth oxide sulfate.
A kind of preparation method of the enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn, comprises the following steps：
(1), by chemical formula (Ln1-x-y-zYbxREyZnz)2O2Raw material Ln (NO needed for S is weighed3)3、Yb(NO3)3、RE(NO3)3
With Zn (NO3)2, above-mentioned raw materials are dissolved, nitrate solution is configured to；
(2), the nitrate solution described in step (1) is instilled in precipitant solution, and stirred；After titration terminates, continue
Stirring, and by after titration solution sealing, it is still aging, filtering；
(3) after, the precipitation after being filtered in step (2) is washed with deionized, dried, precipitation is warming up to 600-800
DEG C, then room temperature is down to after being incubated；
(4), the product after room temperature will be down in step (3) to mix with sulphur simple substance, is then heated up in atmosphere of inert gases
Room temperature is down to 800-1000 DEG C, then after being incubated, the enhanced rare-earth oxide sulfate up-conversion luminescent materials of the Zn are obtained.
When x, y and z select different values in optional scope, the nitrate Ln (NO of equimolar number are weighed3)3、Yb
(NO3)3、RE(NO3)3With Zn (NO3)2, precipitant solution is prepared, then precipitant solution is instilled by nitrate solution is counter.Precipitation
The consumption of agent solution, according to the valence state of anion in precipitating reagent and the Ln (NO weighed3)3、Yb(NO3)3、RE(NO3)3And Zn
(NO3)2Molal quantity determined, it is ensured that the molal quantity and Ln (NO of the anion of precipitation are played in precipitating reagent3)3、Yb
(NO3)3、RE(NO3)3With Zn (NO3)2The molal quantity of oxonium ion is trim on chemical valence, to reach charge balance.Now,
Precipitating reagent is excessive, and precipitation reaction reaction is abundant.After the completion of reaction, filtering cleaning precipitation is warming up to 600-800 DEG C and is incubated, has
Help the formation of crystal, it is ensured that the integrated degree of lattice.Then according to the amount of the raw material weighed, appropriate sulphur simple substance is measured, is mixed
Temperature arrives 800-1000 DEG C after conjunction, is incubated to ensure that reaction is abundant.
The method that the present invention is provided, it is simpler than sulfur melt method, conveniently using gas cure method, and reaction condition is easily controlled
System.
It is preferred that, in step (1), during the precipitating reagent is oxalic acid, and the oxalic acid and the up-conversion luminescent material
The mol ratio of all metallic elements is：1：(1-1.5).
Metal ion can form metal oxalate precipitation with oxalic acid.
It is preferred that, in step (2), the time for continuing to stir is 0.5-1.5h, and the still aging time is
10-20 hours.
Stirring and the operation of ageing, it is ensured that reaction is fully carried out.
It is preferred that, in step (3), the number of times being washed with deionized is 3-5 times.
Washing 3-5 times, can wash away unnecessary impurity.
It is preferred that, in step (3), the temperature of the drying is 60-80 DEG C.
It is preferred that, in step (3) and step (4), the heating is using the chamber type electric resistance furnace that is rapidly heated, and heating rate is
3-5 DEG C/min.
Heating rate suffers from vital effect, heating rate mistake to the Crystallization and surface topography of luminescent material
Crystal growth can be caused too fast soon, make crystal morphology not uniform enough；The efficiency and process tested slowly can be dragged slowly by crossing.
It is preferred that, in step (3), the time of the insulation is 2-4 hours；
And/or；
In step (4), the time of the insulation is 3-5 hours.
It is preferred that, in step (4), the inert gas is one kind in nitrogen or argon gas.
Under inert gas atmosphere, raw material and the oxygen reaction in air can be prevented, the purity of luminescent material is influenceed.
It is preferred that, in step (4), the mol ratio of the sulphur simple substance and the product is 5-7.
Compared with prior art, beneficial effects of the present invention are：
(1) the enhanced rare-earth oxide sulfate up-conversion luminescent materials of a kind of Zn that the present invention is provided, because Zn doping is excellent
The crystal structure of rare-earth oxide sulfate is changed, has reduced crystal structure symmetry and phonon energy, luminous intensity is greatly enhanced, and is carried
It is high by 50%~120%.
(2) preparation method for the enhanced rare-earth oxide sulfate up-conversion luminescent materials of a kind of Zn that the present invention is provided, is used
The anti-method dripped of precipitating reagent obtains rare-earth oxidation raw material, prepared rare-earth oxidation raw material have particle present it is spherical,
The uniform in size, good dispersion of grain, the advantages of do not need ball milling, can be used directly.
(3) preparation method for the enhanced rare-earth oxide sulfate up-conversion luminescent materials of a kind of Zn that the present invention is provided, is used
Gas cure method replaces traditional sulfur melt method, and reaction condition is simple, easily-controllable, and this method can be very good to keep rare earth oxide
Pattern and particle size, are presented spherical the rare-earth oxide sulfate up-conversion luminescent material prepared by this method, particle size is equal more
Even, particle distribution range is narrower, D90=0.2-0.5 μm, product does not need ball milling, can be used directly.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described.
Fig. 1 is the product (La prepared by embodiment 20.775Yb0.2Er0.005Zn0.02)2O2S XRD spectrum；
Fig. 2 is the product (La prepared by embodiment 20.775Yb0.2Er0.005Zn0.02)2O2S SEM pictures；
Fig. 3 is the product (La prepared by embodiment 20.775Yb0.2Er0.005Zn0.02)2O2S up-conversion luminescence spectrum；
Fig. 4 is the product (La prepared by embodiment 30.8175Yb0.16Ho0.0075Zn0.015)2O2S up-conversion luminescence spectrum；
Fig. 5 is the product (Y prepared by embodiment 40.8575Yb0.12Tm0.01Zn0.0125)2O2S up-conversion luminescence spectrum；
Fig. 6 is the product (Y prepared by embodiment 50.8775Yb0.1Pr0.0125Zn0.01)2O2S up-conversion luminescence spectrum；
Fig. 7 is the product (Gd prepared by embodiment 60.8975Yb0.08Eu0.015Zn0.0075)2O2S up-conversion luminescence spectrum；
Fig. 8 is the product (Gd prepared by embodiment 70.935Yb0.04Tb0.02Zn0.005)2O2S up-conversion luminescence spectrum.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, be
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
A kind of enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn, its chemical formula is
(La0.8175Yb0.16Ho0.0075Zn0.015)2O2S。
The preparation method of the rare-earth oxide sulfate up-conversion luminescent material, comprises the following steps：
S11, by chemical formula (La0.8175Yb0.16Ho0.0075Zn0.015)2O2S, raw material 20.171g La needed for weighing
(NO3)3·6H2O、4.095g Yb(NO3)3·5H2O、0.187g Ho(NO3)3·5H2O and 0.254g Zn (NO3)2·6H2O,
Above-mentioned raw materials are dissolved, nitrate solution is configured to；According to the amount of raw material, 7.902g oxalic acid is weighed, and be configured to oxalic acid solution；
S12, the nitrate solution described in step S11 instilled in precipitant solution, and stirred；After titration terminates, continue
Stirring, and by after titration solution sealing, it is still aging, filtering；
S13, the precipitation after being filtered in step S12 is washed with deionized, dried, then the precipitation after washing heats up
To 650 DEG C, room temperature is down to after insulation；
S14, the product being down in step S13 after room temperature mixed with sulphur simple substance again, then risen in atmosphere of inert gases
Temperature is down to room temperature to 850 DEG C after insulation, obtain the enhanced rare-earth oxide sulfate up-conversion luminescent material of the 10g Zn.
Embodiment 2
A kind of enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn, its chemical formula is
(La0.775Yb0.2Er0.005Zn0.02)2O2S。
The preparation method of the rare-earth oxide sulfate up-conversion luminescent material, comprises the following steps：
S21, by chemical formula (La0.775Yb0.2Er0.005Zn0.02)2O2S, raw material 19.020g La (NO needed for weighing3)3·
6H2O、5.091g Yb(NO3)3·5H2O、0.126g Er(NO3)3·5H2O and 0.337g Zn (NO3)2·6H2O, by above-mentioned original
Material dissolving, is configured to nitrate solution；According to the amount of raw material, 7.145g oxalic acid is weighed, and be configured to oxalic acid solution；
S22, the nitrate solution described in step S21 instilled in oxalic acid solution, and stirred；After titration terminates, continue to stir
Mix 0.5 hour, and by after titration solution sealing, still aging 10 hours, filtering；
S23, by step S22 filter after precipitation be washed with deionized 3 times, at 60 DEG C dry, then will washing
Precipitation afterwards is warming up to 600 DEG C, insulation is down to room after 2 hours using the chamber type electric resistance furnace that is rapidly heated with 3 DEG C/min of speed
Temperature；
S24, the product being down in step S23 after room temperature mixed with 4.543g sulphur simple substances again, then in nitrogen atmosphere,
Using the chamber type electric resistance furnace that is rapidly heated, 800 DEG C are warming up to 5 DEG C/min of speed, insulation is down to room temperature after 3 hours, obtains
The enhanced rare-earth oxide sulfate up-conversion luminescent materials of the 10g Zn.
Embodiment 3
A kind of enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn, its chemical formula is
(La0.8175Yb0.16Ho0.0075Zn0.015)2O2S。
The preparation method of the rare-earth oxide sulfate up-conversion luminescent material, comprises the following steps：
S31, by chemical formula (La0.8175Yb0.16Ho0.0075Zn0.015)2O2S, raw material 20.171g La needed for weighing
(NO3)3·6H2O、4.095g Yb(NO3)3·5H2O、0.187g Ho(NO3)3·5H2O and 0.254gZn (NO3)2·6H2O, will
Above-mentioned raw materials dissolve, and are configured to nitrate solution；According to the amount of raw material, 7.902g oxalic acid is weighed, and be configured to oxalic acid solution；
S32, the nitrate solution described in step S31 instilled in oxalic acid solution, and stirred；After titration terminates, continue to stir
Mix 1 hour, and by after titration solution sealing, still aging 12 hours, filtering；
S33, by step S32 filter after precipitation be washed with deionized 4 times, at 70 DEG C dry, then will washing
Precipitation afterwards is warming up to 650 DEG C, insulation is down to after 3 hours using the chamber type electric resistance furnace that is rapidly heated with 3.5 DEG C/min of speed
Room temperature；
S34, the product being down in step S33 after room temperature mixed with 5.025g sulphur simple substances again, then in argon atmosphere,
Using the chamber type electric resistance furnace that is rapidly heated, 850 DEG C are warming up to 4.5 DEG C/min of speed, insulation is down to room temperature after 4 hours, obtains
The enhanced rare-earth oxide sulfate up-conversion luminescent materials of the 10g Zn.
Embodiment 4
A kind of enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn, its chemical formula is
(Y0.8575Yb0.12Tm0.01Zn0.0125)2O2S。
The preparation method of the rare-earth oxide sulfate up-conversion luminescent material, comprises the following steps：
S41, by chemical formula (Y0.8575Yb0.12Tm0.01Zn0.0125)2O2S, raw material 24.968g Y (NO needed for weighing3)3·
6H2O、4.097g Yb(NO3)3·5H2O、0.270g Tm(NO3)3With 0.283gZn (NO3)2·6H2O, above-mentioned raw materials are dissolved,
It is configured to nitrate solution；According to the amount of raw material, 11.50g oxalic acid is weighed, and be configured to oxalic acid solution；
S42, the nitrate solution described in step S41 instilled in oxalic acid solution, and stirred；After titration terminates, continue to stir
Mix 1.5 hours, and by after titration solution sealing, still aging 14 hours, filtering；
S43, by step S42 filter after precipitation be washed with deionized 5 times, at 80 DEG C dry, then will washing
Precipitation afterwards is warming up to 700 DEG C, insulation is down to room after 4 hours using the chamber type electric resistance furnace that is rapidly heated with 4 DEG C/min of speed
Temperature；
S44, the product being down in step S43 after room temperature mixed with 7.413g sulphur simple substances again, then in nitrogen atmosphere,
Using the chamber type electric resistance furnace that is rapidly heated, 900 DEG C are warming up to 4 DEG C/min of speed, insulation is down to room temperature after 5 hours, obtains
The enhanced rare-earth oxide sulfate up-conversion luminescent materials of the 10g Zn.
Embodiment 5
A kind of enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn, its chemical formula is
(Y0.8775Yb0.1Pr0.0125Zn0.01)2O2S。
The preparation method of the rare-earth oxide sulfate up-conversion luminescent material, comprises the following steps：
S51, by chemical formula (Y0.8775Yb0.1Pr0.0125Zn0.01)2O2S, raw material 25.899g Y (NO needed for weighing3)3·
6H2O、3.461g Yb(NO3)3·5H2O、0.419g Pr(NO3)3With 0.229g Zn (NO3)2·6H2O, above-mentioned raw materials are molten
Solution, stirs, is configured to nitrate solution；According to the amount of raw material, 12.629g oxalic acid is weighed, and is configured to oxalic acid solution, is stirred
Mix uniform；
S52, the nitrate solution described in step S51 instilled in oxalic acid solution, and stirred；After titration terminates, continue to stir
Mix 0.5 hour, and by after titration solution sealing, still aging 16 hours, filtering；
S53, by step S52 filter after precipitation be washed with deionized 3 times, at 60 DEG C dry, then will washing
Precipitation afterwards is warming up to 700 DEG C, insulation is down to room after 2 hours using the chamber type electric resistance furnace that is rapidly heated with 4 DEG C/min of speed
Temperature；
S54, the product being down in step S53 after room temperature mixed with 7.413g sulphur simple substances again, then in argon atmosphere,
Using the chamber type electric resistance furnace that is rapidly heated, 900 DEG C are warming up to 4 DEG C/min of speed, insulation is down to room temperature after 3 hours, obtains
The enhanced rare-earth oxide sulfate up-conversion luminescent materials of the 10g Zn.
Embodiment 6
A kind of enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn, its chemical formula is
(Gd0.8975Yb0.08Eu0.015Zn0.0075)2O2S。
The preparation method of the rare-earth oxide sulfate up-conversion luminescent material, comprises the following steps：
S61, by chemical formula (Gd0.8975Yb0.08Eu0.015Zn0.0075)2O2S, raw material 21.345g Gd needed for weighing
(NO3)3·6H2O、1.893g Yb(NO3)3·5H2O、0.353g Eu(NO3)3·6H2O and 0.118g Zn (NO3)2·6H2O,
Above-mentioned raw materials are dissolved, stirred, nitrate solution is configured to；According to the amount of raw material, 9.30g oxalic acid is weighed, and be configured to
Oxalic acid solution, stirs；
S62, the nitrate solution described in step S61 instilled in oxalic acid solution, and stirred；After titration terminates, continue to stir
Mix 1 hour, and by after titration solution sealing, still aging 18 hours, filtering；
S63, by step S62 filter after precipitation be washed with deionized 4 times, at 70 DEG C dry, then will washing
Precipitation afterwards is warming up to 750 DEG C, insulation is down to after 3 hours using the chamber type electric resistance furnace that is rapidly heated with 4.5 DEG C/min of speed
Room temperature；
S64, the product being down in step S63 after room temperature mixed with 5.491g sulphur simple substances again, then in nitrogen atmosphere,
Using the chamber type electric resistance furnace that is rapidly heated, 950 DEG C are warming up to 3.5 DEG C/min of speed, insulation is down to room temperature after 4 hours, obtains
The enhanced rare-earth oxide sulfate up-conversion luminescent materials of the 10g Zn.
Embodiment 7
A kind of enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn, its chemical formula is
(Gd0.935Yb0.04Tb0.02Zn0.005)2O2S。
The preparation method of the rare-earth oxide sulfate up-conversion luminescent material, comprises the following steps：
S71, by chemical formula (Gd0.935Yb0.04Tb0.02Zn0.005)2O2S, raw material 22.271g Gd (NO needed for weighing3)3·
6H2O、0.948g Yb(NO3)3·5H2O、0.478g Tb(NO3)3·6H2O and 0.078g Zn (NO3)2·6H2O, by above-mentioned original
Material dissolving, stirs, is configured to nitrate solution；According to the amount of raw material, 9.979g oxalic acid is weighed, and it is molten to be configured to oxalic acid
Liquid, stirs；
S72, the nitrate solution described in step S71 instilled in oxalic acid solution, and stirred；After titration terminates, continue to stir
Mix 1.5 hours, and by after titration solution sealing, still aging 20 hours, filtering；
S73, by step S72 filter after precipitation be washed with deionized 5 times, at 80 DEG C dry, then will washing
Precipitation afterwards is warming up to 800 DEG C, insulation is down to room after 4 hours using the chamber type electric resistance furnace that is rapidly heated with 5 DEG C/min of speed
Temperature；
S74, the product being down in step S73 after room temperature mixed with 5.923g sulphur simple substances again, then in argon atmosphere,
Using the chamber type electric resistance furnace that is rapidly heated, 1000 DEG C are warming up to 3 DEG C/min of speed, insulation is down to room temperature after 5 hours, obtains
The enhanced rare-earth oxide sulfate up-conversion luminescent materials of the 10g Zn.
The enhanced rare-earth oxide sulfate up-conversion luminescent material phase compositions of the Zn of experimental example 1, pattern and grain size analysis
The enhanced rare-earth oxide sulfate up-conversion luminescent materials of Zn provided embodiment 1-7, use X-ray diffractometer
(XRD, D/Max2500) carries out crystal species analysis, and particle size and shape are carried out with SEM (SEM, JEOL-6310)
Looks are analyzed, and particle size statistics, its D are carried out using software90Statistical result is as shown in table 1.
The embodiment 1-7D of table 190Statistical result
It is demonstrated experimentally that the XRD spectrum for the enhanced rare-earth oxide sulfate up-conversion luminescent materials of Zn that the present invention is provided is shown
The position of main diffraction peak is all corresponding with six side's rare-earth oxide sulfates, and the peak without other material phases is present, wherein, figure
1 is the product (La prepared by embodiment 20.775Yb0.2Er0.005Zn0.02)2O2S XRD spectrum；Use SEM
(SEM, JEOL-6310) carries out particle size and morphology analysis, and it is spherical, even particle distribution as a result to show granule-morphology, its
In, Fig. 2 is the product (La prepared by embodiment 20.775Yb0.2Er0.005Zn0.02)2O2S SEM pictures；Using software progress
Particle size is counted, D90=0.20-0.50 μm.
The enhanced rare-earth oxide sulfate up-conversion luminescent material luminescent properties tests of the Zn of experimental example 2
Up-conversion luminescence performance test is carried out with XRF (PL, FL3-221), as a result with the sample phase undoped with Zn
Than the degree that luminous intensity is improved is as shown in table 2.
The embodiment 1-7 luminous intensities of table 2 improve degree
It is demonstrated experimentally that because Zn doping optimizes the crystal structure of rare-earth oxide sulfate, reducing crystal structure symmetrical
Property and phonon energy, luminous intensity are greatly enhanced, and improve 50%~120%.Wherein, Fig. 3-8 is embodiment 2-7 upper conversion
Luminescent spectrum.
In summary, the enhanced rare-earth oxide sulfate up-conversion luminescent materials of a kind of Zn that the present invention is provided, due to Zn's
Doping optimizes the crystal structure of rare-earth oxide sulfate, reduces crystal structure symmetry and phonon energy, luminous intensity is significantly
Enhancing, improves 50%~120%.A kind of system for the enhanced rare-earth oxide sulfate up-conversion luminescent materials of Zn that the present invention is provided
Preparation Method, rare-earth oxidation raw material is obtained using the anti-method dripped of precipitating reagent, and prepared rare-earth oxidation raw material has particle
The advantages of spherical, even particle size, good dispersion is presented, does not need ball milling, can be used directly；The preparation method, using gas
Body vulcanization method replaces traditional sulfur melt method, and reaction condition is simple, easily-controllable, and this method can be very good to keep the shape of rare earth oxide
Looks and particle size, are presented spherical the rare-earth oxide sulfate up-conversion luminescent material prepared by this method more, particle size uniformity,
Particle distribution range is narrower, D90=0.2-0.5 μm, product does not need ball milling, can be used directly.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that without departing substantially from the present invention's
Many other changes and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn, it is characterised in that the chemical formula of the material is
(Ln1-x-y-zYbxREyZnz)2O2S, wherein 0.04≤x≤0.2,0.005≤y≤0.02,0.005≤z≤0.02；Wherein Ln is
One kind in La, Y or Gd, RE is one kind in Er, Ho, Tm, Pr, Eu or Tb.
2. a kind of preparation method of the enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn according to claim 1, its
It is characterised by, comprises the following steps：
(1), by chemical formula (Ln1-x-y-zYbxREyZnz)2O2Raw material Ln (NO needed for S is weighed3)3、Yb(NO3)3、RE(NO3)3And Zn
(NO3)2, above-mentioned raw materials are dissolved, nitrate solution is configured to；
(2), the nitrate solution described in step (1) is instilled in precipitant solution, and stirred；After titration terminates, continue to stir,
And by after titration solution sealing, it is still aging, filtering；
(3) after, the precipitation after filtering in step (2) is washed with deionized, dried, precipitation is warming up to 600-800 DEG C, then
Room temperature is down to after insulation；
(4), the product after room temperature will be down in step (3) to mix with sulphur simple substance, is then warming up in atmosphere of inert gases
800-1000 DEG C, then room temperature is down to after being incubated, obtain the enhanced rare-earth oxide sulfate up-conversion luminescent materials of the Zn.
3. the preparation method of the enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn according to claim 2, its feature
It is, in step (1), the precipitating reagent is oxalic acid, and the oxalic acid and all metals in the up-conversion luminescent material are first
Element mol ratio be：1：(1-1.5).
4. the preparation method of the enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn according to claim 2, its feature
It is, in step (2), the time for continuing to stir is 0.5-1.5 hours, and the still aging time is that 10-20 is small
When.
5. the preparation method of the enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn according to claim 2, its feature
It is, in step (3), the number of times being washed with deionized is 3-5 times.
6. the preparation method of the enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn according to claim 2, its feature
It is, in step (3), the temperature of the drying is 60-80 DEG C.
7. the preparation method of the enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn according to claim 2, its feature
It is, in step (3) and step (4), the heating is using the chamber type electric resistance furnace that is rapidly heated, and heating rate is 3-5 DEG C/minute
Clock.
8. the preparation method of the enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn according to claim 2, its feature
It is, in step (3), the time of the insulation is 2-4 hours；
And/or；
In step (4), the time of the insulation is 3-5 hours.
9. the preparation method of the enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn according to claim 2, its feature
It is, in step (4), the inert gas is one kind in nitrogen or argon gas.
10. the preparation method of the enhanced rare-earth oxide sulfate up-conversion luminescent material of Zn according to claim 2, its feature
It is, in step (4), the mol ratio of the sulphur simple substance and the product is 5-7.
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