CN102703080B - Sulfur oxide high-efficiency infrared up-conversion fluorescent powder and preparation method thereof - Google Patents
Sulfur oxide high-efficiency infrared up-conversion fluorescent powder and preparation method thereof Download PDFInfo
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- CN102703080B CN102703080B CN201210192587.1A CN201210192587A CN102703080B CN 102703080 B CN102703080 B CN 102703080B CN 201210192587 A CN201210192587 A CN 201210192587A CN 102703080 B CN102703080 B CN 102703080B
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Abstract
The invention relates to sulfur oxide high-efficiency infrared up-conversion fluorescent powder and a preparation method thereof. The structural formula of the related fluorescent powder is (Ln1-a-x-y-z,Bia,Ybx,Mny,REz)2O2S, wherein Ln is one or mixture of Y, Gd, La and Lu, RE is one or mixture of Er, Tm and Pr, a is equal to 0-0.07, x is equal to 0-0.20, y is equal to 0.005-0.15, and z is equal to 0.001-0.20. The up-conversion fluorescent powder has high up-conversion luminous intensity under excitation of infrared light (such as 980 nm and 1500 nm).
Description
Technical field
The invention belongs to field of light emitting materials, relate in particular to efficient infrared up-conversion fluorescent powder of a kind of polyion doping oxysulfide and preparation method thereof.
Background technology
Up-conversion luminescent material is that a kind of main application wavelength is long infrared ray excited, sends the material of visible ray.Infrared up-conversion material has very large application potential in national economy and field of solar energy utilization, as infrared detector, biomolecules fluorescent mark, 3-D display, false proof and sun power upconverter part etc.Such up-conversion luminescent material has caused people's extensive concern, and has obtained a series of progress.The higher up-conversion of efficiency mainly contains glass or the monocrystalline of rare earth ion doped halogenide, oxyhalogenide at present, yet the chemical stability of these materials is generally poor, and preparation condition is harsh, has seriously hindered the market application of up-conversion.
Rare-earth oxide sulfate has environmental protection, low toxicity and high chemical stability.And because suitable phonon energy (is about 500cm
-1) and wide energy gap, there is very high photoabsorption and upper efficiency of conversion, be suitable as the substrate material of up-conversion luminescent material.In recent years, the rare earth doped oxysulfide up-conversion luminescent material of trivalent rare earth ions is paid close attention to by people more and more, adds progress and the development of infrared laser technology, and the research of infrared up-conversion luminescence is further developed.For example, the people such as G.A.Kumar, at Materials Letters 2012,68, have reported M on 395-398
2o
2s:Er
3+er in (M=Y, Gd, La) fluorescent material
3+the up-conversion luminescence phenomenon of ion.But the up-conversion phosphor luminous efficiency of trivalent rare earth ions list doping is undesirable, is the problem of solution that people pay close attention to always.Therefore relevant scholar solves by the suitable co-dopant ions (rare earth or transition metal) of selection and the concentration of dopant ion the problem that up-conversion luminescence efficiency is lower, and has obtained certain achievement.For example, the people such as Han Pengde, at < < process engineering journal > > 2011,11, have reported La on 701-706
2o
2s:Er, Yb 980nm excite lower on conversion send ruddiness and green glow; Chinese invention patent CN102321481A provides a kind of three doping oxysulfide Ln
2o
2s:Yb
3+, Tm
3+, RE
3+(Ln=Y, Gd, La; RE=Er
3+, Ho
3+, Eu
3+) upper conversion of white light material and preparation method thereof, this material is under 980nm wavelength laser excites, and RGB light is sent in upper conversion, and then compoundly goes out white light.These materials have higher upper efficiency of conversion under 980nm near infrared light excites, but the upper efficiency of conversion of (as 1310nm, 1550nm etc.) is lower under long-wavelength excitation more.
Summary of the invention
The object of the invention is be greater than the lower problem of the infrared ray excited lower up-conversion luminescence efficiency of 980nm in order to solve existing oxysulfide infrared up-conversion fluorescent powder, and provide a kind of polyion to mix altogether efficient infrared up-conversion fluorescent powder of oxysulfide and preparation method thereof.
The present invention has prepared the efficient infrared up-conversion fluorescent powder of a kind of oxysulfide, it is characterized in that phosphor structure formula is for (Ln
1-a-x-y-z, Bi
a, Yb
x, Mn
y, RE
z)
2o
2s.
Wherein, Ln is a kind of in Y, Gd, La, Lu or their mixing;
RE is a kind of in Er, Tm, Pr etc. or their mixing;
In this up-conversion phosphor, must there is Mn ion to exist, thereby improve the up-conversion luminescence efficiency under up-conversion luminescence efficiency, especially > 980nm excitation.
Described a is between 0～0.07, and when x > 0.07, up-conversion luminescence efficiency significantly reduces;
Described x is between 0～0.20, and when x > 0.20, up-conversion luminescence efficiency significantly reduces;
Described y is between 0.005～0.15, and when y < 0.005, up-conversion luminescence efficiency does not have noticeable change, and when y > 0.15, can not obtain oxysulfide crystal, and up-conversion luminescence efficiency significantly reduces;
Described z is between 0.001～0.20, and outside this scope, up-conversion luminescence efficiency all obviously declines.
When RE must comprise Er, the structural formula of described fluorescent material is (Ln
1-a-x-y-z, Bi
a, Yb
x, Mn
y, Er
z)
2o
2during S, a=0～0.07, x=0.02～0.20, y=0.01～0.15, z=0.01～0.10, exceeds this scope, and Up-conversion Intensity all significantly reduces.
For obtaining the up-conversion phosphor of said structure, its preparation method is: the oxygen acid salt of the rare earth compound of required composition, manganese is mixed with sulphur and fusing assistant, and at high temperature calcining, forms through aftertreatment.
Described rare-earth compound is rare earth oxide, rare earth carbonate and rare-earth oxalate;
The oxygen acid salt of described manganese is manganous nitrate, manganous carbonate and manganous oxalate;
Described fusing assistant is Na
2cO
3, K
2cO
3, Li
2cO
3, NH
4h
2pO
4, NaH
2pO
4in a kind of or their mixing, the mass ratio of rare earth compound: fusing assistant: S is: 1: 0.3～1.5: 2～5, outside this scope, the fluorescent material obtaining all contains dephasign.
It is 1000～1400 ℃ that described high temperature burns till required temperature, firing time 0.5～6 hour, and temperature is low, the time shortly has dephasign to generate, and particle diameter is little, thus luminous intensity significantly declines; , there is burning in excess Temperature, overlong time, particle diameter is too large, and luminous intensity also significantly declines.
This kind of infrared up-conversion luminous material excites and all can send bright visible ray down at infrared light (as 980nm and 1550nm), thereby can be for fields such as 3-D display, false proof, biomolecules fluorescent mark and sun power upconverter parts.The present invention adopts the standby fluorescent material up-conversion of high temperature solid-state sulfuration legal system, has that equipment is simple, cost is low, the cycle is short, stable performance and a up-conversion luminescence efficiency high.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the fluorescent material of embodiment 1;
Fig. 2 is the SEM figure of the fluorescent material of embodiment 1;
Fig. 3 is the fluorescent material of embodiment 1 luminescent spectrum under 980nm laser excitation;
Fig. 4 is the fluorescent material of embodiment 1 luminescent spectrum under 1550nm laser excitation;
Fig. 5 is the fluorescent material of embodiment 2 luminescent spectrum under 980nm laser excitation;
Fig. 6 is the fluorescent material of embodiment 3 luminescent spectrum under 1550nm laser excitation;
Fig. 7 is the fluorescent material of embodiment 4 luminescent spectrum under 1550nm laser excitation;
Embodiment
Below in conjunction with embodiment, the invention will be further described, but should not limit the scope of the invention with this.
Embodiment 1
Preparing structural formula is (Y
0.78yb
0.07mn
0.10er
0.05)
2o
2the fluorescent material of S.Take 3.53g Y
2o
3, 0.55g Yb
2o
3, 0.46g MnCO
3, 0.38g Er
2o
3, 4.92g Na
2cO
3with raw materials such as 3.96g sulphur, ground and mixed is even.By the raw material mixing in carbon reducing atmosphere 1100 ℃ insulation 3 hours.Afterwards sintered product is cleaned, filtered and 100 ℃ of oven dry, obtain required fluorescent material.
Preparing structural formula is (Gd
0.80bi
0.08mn
0.07er
0.05)
2o
2the fluorescent material of S.Take 5.79g Gd
2o
3, 0.75g Bi
2o
3, 0.32g MnCO
3, 0.38g Er
2o
3, 7.24g K
2cO
3with raw materials such as 5.83g sulphur.By the 1050 ℃ of insulations 2.5 hours in carbon reducing atmosphere of the good raw material of ground and mixed.Afterwards sintered product is cleaned, filtered and 100 ℃ of oven dry, obtain required fluorescent material.
Embodiment 3
Preparing structural formula is (La
0.83yb
0.05mn
0.05er
0.05tm
0.02)
2o
2the fluorescent material of S.Take 5.41g La
2o
3, 0.39gYb
2o
3, 0.23g MnCO
3, 0.38g Er
2o
3, 0.15g Tm
2o
3, 6.56g Li
2cO
3with raw materials such as 5.28g sulphur, ground and mixed is even.By the raw material mixing in carbon reducing atmosphere 1150 ℃ insulation 4 hours.Afterwards sintered product is cleaned, filtered and 100 ℃ of oven dry, obtain required fluorescent material.
Embodiment 4
Preparing structural formula is (Y
0.79yb
0.04mn
002er
0.10pr
0.05)
2o
2the fluorescent material of S.Take 3.57g Y
2o
3, 0.32g Yb
2o
3, 0.09g MnCO
3, 0.77g Er
2o
3, 0.33g Pr
2o
3, 5.08g NH
4h
2pO
4with raw materials such as 4.09g sulphur, ground and mixed is even.By the raw material mixing in carbon reducing atmosphere 1100 ℃ insulation 3 hours.Afterwards sintered product is cleaned, filtered and 100 ℃ of oven dry, obtain required fluorescent material.
Reference examples
Preparing structural formula is (Y
0.90yb
0.05er
0.05)
2o
2the fluorescent material of S.Take 4.07g Y
2o
3, 0.39g Yb
2o
3, 0.38gEr
2o
3, 4.85g Na
2cO
3with raw materials such as 3.90g sulphur, ground and mixed is even.By the raw material mixing in carbon reducing atmosphere 1100 ℃ insulation 3 hours.Afterwards sintered product is cleaned, filtered and 100 ℃ of oven dry, obtain required fluorescent material.
Claims (8)
1. the efficient infrared up-conversion fluorescent powder of oxysulfide, is characterized in that phosphor structure formula is for (Ln
1-a-x-y-z, Bi
a, Yb
x, Mn
y, RE
z)
2o
2s, wherein Ln is a kind of in Y, Gd, La, Lu or their mixing, RE is a kind of in Er, Tm, Pr or their mixing, and a=0～0.07, x=0～0.20, y=0.005～0.15, z=0.001～0.20.
2. up-conversion phosphor according to claim 1, when the structural formula of fluorescent material is (Ln
1-a-x-y-z, Bi
a, Yb
x, Mn
y, Er
z)
2o
2during S, a=0～0.07, x=0.02～0.20, y=0.01～0.15, z=0.01～0.10.
3. the preparation method of the efficient infrared up-conversion fluorescent powder of oxysulfide according to claim 1, is characterized in that adopting oxysalt, the Bi of rare-earth compound, manganese
2o
3or Bi (NO
3)
3for raw material, after mixing with sulphur and fusing assistant, high temperature burns till.
4. preparation method according to claim 3, described rare-earth compound is rare earth oxide, rare earth carbonate and rare-earth oxalate.
5. preparation method according to claim 3, the oxysalt of described manganese is manganous nitrate, manganous carbonate and manganous oxalate.
6. preparation method according to claim 3, described fusing assistant is Na
2cO
3, K
2cO
3, Li
2cO
3, NH
4h
2pO
4, NaH
2pO
4in a kind of or their mixing.
7. preparation method according to claim 3, is characterized in that rare earth compound: fusing assistant: the mass ratio of S is: 1: 0.3～1.5: 2～5.
8. preparation method according to claim 3, its firing temperature is 1000～1400 ℃, soaking time is 0.5～6 hour.
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| WO2016203431A1 (en) | 2015-06-18 | 2016-12-22 | Universita' Ca' Foscari | Luminescent bismuth silicates, use and method for producing thereof |
| JP2020158679A (en) * | 2019-03-27 | 2020-10-01 | 株式会社球体研究所 | Fine particle including up-conversion phosphor and manufacturing method therefor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0908503A1 (en) * | 1996-06-21 | 1999-04-14 | Kasei Optonix, Ltd. | Rare earth sulfate phosphor and x-ray detector using the same |
| CN102321481A (en) * | 2011-07-11 | 2012-01-18 | 南京工业大学 | Triple-doped sulfur oxide up-conversion white light material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02276883A (en) * | 1989-04-19 | 1990-11-13 | Hitachi Ltd | Production of fluorescent thin film |
| JP5574755B2 (en) * | 2010-02-26 | 2014-08-20 | 大日本塗料株式会社 | Method for producing inorganic phosphor dispersion, coating composition having inorganic phosphor dispersion, and ink jet ink |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0908503A1 (en) * | 1996-06-21 | 1999-04-14 | Kasei Optonix, Ltd. | Rare earth sulfate phosphor and x-ray detector using the same |
| CN102321481A (en) * | 2011-07-11 | 2012-01-18 | 南京工业大学 | Triple-doped sulfur oxide up-conversion white light material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JP平2-276883A 1990.11.13 |
| JP特开2011-178839A 2011.09.15 |
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