CN100358972C - Up-converting fluorescent material and preparation method thereof - Google Patents
Up-converting fluorescent material and preparation method thereof Download PDFInfo
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- CN100358972C CN100358972C CNB2005100239634A CN200510023963A CN100358972C CN 100358972 C CN100358972 C CN 100358972C CN B2005100239634 A CNB2005100239634 A CN B2005100239634A CN 200510023963 A CN200510023963 A CN 200510023963A CN 100358972 C CN100358972 C CN 100358972C
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Abstract
The present invention relates to an up-conversion fluorescent material and a preparation method thereof. Rare earth lutetium oxide is selected as a base material, trivalent ytterbium is selected as sensitizing ions, and one of trivalent holmium, thulium, erbium, praseodymium, samarium and dysprosium is codoped. Ammonia water and ammonium bicarbonate or mixed solution of the ammonia water and the ammonium bicarbonate are used as precipitating agents, and the rare earth ion doped up-conversion fluorescence material of lutetium oxide base is prepared by adopting coprecipitation technology. Molar fraction percent of the composition of the up-conversion fluorescent material of Lu<3+> to Yb<3+> to other rare earth ions is (99.7 to 800): (0.2 to 10): (0.1 to 10). The up-conversion fluorescence material prepared by the two methods provided by the present invention has uniform particle size distribution, the particle size is below 1 mu m, and obvious visual light with different colors can be observed when the up-conversion fluorescence material is excitated by infrared light whose wavelength is within 935 to 980 nm. The present invention has the advantages of simple preparation technology process, convenient synthesis, stable performance and excellent up-conversion luminescence property.
Description
Technical field
The present invention relates to a kind of upconverting fluorescent material and preparation technology thereof, relating to a kind of or rather is matrix with the lutecium oxide, be upconverting fluorescent material of a kind of composition among sensitized ions codoped trivalent Ho, Tm, Er, Pr, Sm or the Dy and preparation method thereof with the trivalent ytterbium, belong to structure and function integration material field.
Background technology
Upconverting fluorescent material is a kind of at the infrared ray excited luminescent material that can send visible light down, can be used for preparing photodiode, solid substrate visible laser, highly sensitive biomolecules fluorescence labeling material etc.People have carried out extensive studies to this since finding to go up conversion phenomena in 1964, but mostly in monocrystalline or glass system.Because the required condition harshness of single crystal growing, the chemical stability of glass and bad mechanical strength, and pottery has good stability, can manufacture, low cost and other advantages, therefore recently the research of upconverting fluorescent material has caused extensive concern in ceramic systems, for example people such as J.A.Capobianco in 2002 at Chem.Mater, 14, reported Y on the 2915-2921
2O
3: Ho
3+The up-conversion luminescence phenomenon, people such as Paras N.Prasad have reported ZrO 2002 at J.Phys.Chem.B 106 on the 1909-1912
2Doping Er
3+Nanocrystalline up-conversion luminescence.Relevant with the lutecium oxide be matrix upconverting fluorescent material report seldom, onlyly comprise that people such as J.A.Capobianco are at J.Phys.Chem.B 2002,106,5622-5628 and Optical Materials 2002,19,259-268 has reported the up-conversion luminescence phenomenon with the erbium ion list doping lutecium oxide of combustion method preparation, and other rare earth ion doped lutecia based up-conversions do not appear in the newspapers as yet.This material has superior physicals (as high-melting-point, stable mutually, thermal expansion is low etc.), low phonon energy (about 600cm
-1), up-conversion luminescence is good, and preparation process is simple, and is synthetic convenient, steady performance.
Summary of the invention
The objective of the invention is to propose a kind of upconverting fluorescent material; Another object of the present invention provides a kind of preparation method of described upconverting fluorescent material.Upconverting fluorescent material of the present invention is that selection rare-earth oxidation lutetium is a matrix, with the trivalent ytterbium is a kind of in sensitized ions codoped trivalent holmium, thulium, erbium, praseodymium, samarium or the dysprosium ion, mixing solutions with ammoniacal liquor, bicarbonate of ammonia or ammoniacal liquor and bicarbonate of ammonia is made precipitation agent, adopts coprecipitation technology to prepare rare earth ion doped lutecia based material.
For achieving the above object, the technical solution used in the present invention is: a kind of upconverting fluorescent material, it is to be matrix with the lutecium oxide, with the trivalent ytterbium ion is sensitized ions, be doped with in ytterbium, holmium, thulium, erbium, praseodymium, samarium or the dysprosium a kind ofly, the molar percentage of its rare earth ion is a lutetium ion: ytterbium ion: other rare earth ion=99.7-80: 0.2-10: 0.1-10.
It is 99.99% lutecium oxide, ytterbium oxide, Holmium trioxide, Erbium trioxide, trioxide, Praseodymium trioxide, Samarium trioxide, dysprosium oxide with analytically pure nitric acid dissolve or corresponding nitrate that raw material used in the present invention is selected purity for use, precipitation agent is the mixing solutions of analytically pure ammoniacal liquor, bicarbonate of ammonia or ammoniacal liquor and bicarbonate of ammonia, and the volume ratio of ammoniacal liquor and bicarbonate of ammonia is 0.5～5 in the mixing solutions.
The preparation method of above-mentioned upconverting fluorescent material, by stoichiometry above-mentioned required rare earth nitrate is mixed at ambient temperature, be mixed with the solution that concentration is 0.1-0.4mol/l with deionized water, with ammoniacal liquor, bicarbonate of ammonia or both mixing solutionss dilution 1-10 are doubly, the employing coprecipitation technology slowly adds this solution in the quantitative above-mentioned rare earth nitrate solution or above-mentioned rare earth nitrate solution is slowly added the ammoniacal liquor of dilution, in bicarbonate of ammonia or both mixing solutionss, fully stirring mixes it, the final pH value is controlled at 7-10, the gained suspension filtered is got white precipitate, and water and ethanol wash the back respectively and obtained precursor powder in dry 15-30 hour in 60-80 ℃ of environment; Precursor powder fully ground be put in the retort furnace after sieving,, promptly get required upconverting fluorescent material in 700-1100 ℃ of calcining 2-8 hour down.
The upconverting fluorescent material of the present invention's preparation is rare earth ion doped lutecia based material, prepared material particle size is evenly distributed, particle size is below 1 μ m, at the infrared ray excited visible light that promptly can be observed tangible different colours down of wavelength 935～980nm.Preparation process is simple, and is synthetic convenient, stable performance, and up-conversion luminescence is good.
Description of drawings
Fig. 1 is the transmission electron microscope of the prepared lutecia based upconverting fluorescent material of the embodiment of the invention 1, and particle diameter is 35nm
Fig. 2 is the up-conversion fluorescence spectrogram of lutecium oxide nanometer upconverting fluorescent material of ytterbium, the holmium codoped of the embodiment of the invention 1 preparation
Fig. 3 is the up-conversion fluorescence spectrogram of lutecium oxide nanometer upconverting fluorescent material of ytterbium, the thulium codoped of the embodiment of the invention 4 preparation
Fig. 4 is the ytterbium of the embodiment of the invention 5 preparation, the up-conversion fluorescence spectrogram of erbium-codoped lutecium oxide nanometer upconverting fluorescent material.
Embodiment
Embodiment 1
Under the room temperature, is lutetium ion with lutecium nitrate, ytterbium nitrate and holmium nitrate solution by the mol ratio of rare earth ion: ytterbium ion: holmium ion=99.6: 0.2: 0.2 is made into the solution that concentration is 0.4mol/l, and ammoniacal liquor and bicarbonate of ammonia mixed also and dilutes one times in 1: 2 by volume.The mixing solutions of ammoniacal liquor and bicarbonate of ammonia is joined in the rare earth nitrate solution of stirring, fully stir to make and mix, when this pH value of solution value is 8, stop to add precipitation agent (mixing solutions of ammoniacal liquor and bicarbonate of ammonia), continue to stir after one hour, the gained suspension filtered is got white precipitate.Obtained precursor powder in 30 hours in 60 ℃ of baking oven inner dryings after water and the washing with alcohol.The gained precursor powder fully ground be put in the retort furnace after sieving, 800 ℃ of calcinings 8 hours down.The gained up-conversion luminescent material excites down at 975nm, sends green glow and ruddiness.
Embodiment 2
Under the room temperature, be lutetium ion with lutecium nitrate, ytterbium nitrate and holmium nitrate solution by the mol ratio of rare earth ion: ytterbium ion: holmium ion=94: 5: 1 is made into the solution that concentration is 0.2mol/l, and ammoniacal liquor and bicarbonate of ammonia mixed also and dilutes three times in 2: 1 by volume.The mixing solutions of ammoniacal liquor and bicarbonate of ammonia is joined in the rare earth nitrate solution of stirring, fully stir to make and mix, when this pH value of solution value is 8, stop to add precipitation agent (mixing solutions of ammoniacal liquor and bicarbonate of ammonia), continue to stir after one hour, the gained suspension filtered is got white precipitate.Obtained precursor powder in 20 hours in 75 ℃ of baking oven inner dryings after water and the washing with alcohol.The gained precursor powder fully ground be put in the retort furnace after sieving, 1000 ℃ of calcinings 4 hours down.The gained up-conversion luminescent material excites down at 975nm, sends green glow and ruddiness.
Embodiment 3
Under the room temperature, be lutetium ion with lutecium nitrate, ytterbium nitrate and holmium nitrate solution by the mol ratio of rare earth ion: ytterbium ion: holmium ion=80: 10: 10 is made into the solution that concentration is 0.1mol/l, and ammoniacal liquor and bicarbonate of ammonia mixed also and dilutes five times in 5: 1 by volume.The mixing solutions of ammoniacal liquor and bicarbonate of ammonia is joined in the rare earth nitrate solution of stirring, fully stir to make and mix, when this pH value of solution value is 9, stop to add precipitation agent (mixing solutions of ammoniacal liquor and bicarbonate of ammonia), continue to stir after one hour, the gained suspension filtered is got white precipitate.Obtained precursor powder in 15 hours in 80 ℃ of baking oven inner dryings after water and the washing with alcohol.The gained precursor powder fully ground be put in the retort furnace after sieving, 1100 ℃ of calcinings 2 hours down.The gained up-conversion luminescent material excites down at 975nm, sends green glow and ruddiness.
Embodiment 4
Under the room temperature, be lutetium ion with lutecium nitrate, ytterbium nitrate and thulium nitrate by the mol ratio of rare earth ion: ytterbium ion: thulium ion=solution was made into the solution that concentration is 0.1mol/l in 98.8: 1: 0.2,10 times of ammoniacal liquor dilutions.The ammonia soln that ammoniacal liquor after the dilution is added above-mentioned rare earth nitrate solution and dilution when stirring, fully stir to make and mix, when this pH value of solution value is 10, stop to add ammoniacal liquor, continue to stir after one hour, the gained suspension filtered is got white precipitate.Obtained precursor powder in 30 hours in 80 ℃ of baking oven inner dryings after water and the washing with alcohol.The gained precursor powder fully ground be put in the retort furnace after sieving, 1100 ℃ of calcinings 2 hours down.The gained up-conversion luminescent material excites down at 940nm, sends blue light and ruddiness.
Embodiment 5
Under the room temperature, be lutetium ion with lutecium nitrate, ytterbium nitrate and Erbium trinitrate by the mol ratio of rare earth ion: ytterbium ion: erbium ion=solution was made into the solution that concentration is 0.1mol/l in 85: 10: 5,5 times of bicarbonate of ammonia dilutions.The ammonium bicarbonate soln that the ammonium bicarbonate soln for preparing is added above-mentioned rare earth nitrate solution and dilution when stirring, fully stir to make and mix, when this pH value of solution value is 7, stop to add bicarbonate of ammonia, continue to stir after one hour, the gained suspension filtered is got white precipitate.Obtained precursor powder in 15 hours in 80 ℃ of baking oven inner dryings after water and the washing with alcohol.The gained precursor powder fully ground be put in the retort furnace after sieving, 800 ℃ of calcinings 4 hours down.The gained up-conversion luminescent material excites down at 975nm, sends green glow and ruddiness.
Claims (4)
1, a kind of preparation method of upconverting fluorescent material is characterized in that technological process is:
(1) at ambient temperature, be lutetium ion by stoichiometric ratio with the molar percentage of rare earth ion:
Ytterbium ion: other rare earth ion=99.7-80: 0.2-10: the 0.1-10 mixed, being made into concentration with deionized water is 0.1-0.4mol/1 solution; Other rare earth ion is for mixing trivalent Ho, Tm, Er, Pr, Sm or Dy altogether;
(2) doubly with ammoniacal liquor, bicarbonate of ammonia or both mixing solutionss dilution 1-10, adopt coprecipitation technology solution to be joined in the solution of step (1) gained or the solution of step (1) gained is progressively joined in this solution, evenly stir, the pH value is controlled at the 7-10 scope, filter white precipitate;
(3) water and ethanol wash the back respectively and obtained precursor powder in 60-80 ℃ of dry 15-30 hour;
(4) precursor powder is made upconverting fluorescent material in 700-1100 ℃ of calcining after grinding is sieved.
2, the described upconverting fluorescent material preparation method of claim 1, it is characterized in that calcining soaking time is 2-8 hour.
3, by the described upconverting fluorescent material preparation method of claim 1, it is characterized in that used Doped Rare Earth ion is corresponding oxide compound or nitrate, its purity is 99.99%; Oxide compound is then made corresponding nitrate with analytically pure salpeter solution.
4, by the described upconverting fluorescent material preparation method of claim 1, it is characterized in that both volume ratios are 0.5-5 in ammoniacal liquor and the bicarbonate of ammonia mixing solutions.
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| CN100358972C true CN100358972C (en) | 2008-01-02 |
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| CN103059853B (en) * | 2011-10-19 | 2014-11-05 | 海洋王照明科技股份有限公司 | Titanate phosphors for up-conversion luminescence, and preparation method and application thereof |
| CN102533267A (en) * | 2011-12-22 | 2012-07-04 | 昆明理工大学 | Three-dimensional ordered macroporous up-conversion luminescent ceramic material with Lu2O3 as substrate and preparation method thereof |
| CN102618284B (en) * | 2012-03-15 | 2014-10-01 | 吉林大学 | Bioluminescent nanoparticle with 800-nanometer strong near infrared up-conversion emission characteristic and application thereof |
| CN104178156A (en) * | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Holmium-doped tungstate up-conversion luminescent material, preparation method and organic light-emitting diode |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5213712A (en) * | 1992-02-10 | 1993-05-25 | General Electric Company | Lanthanum lutetium oxide phosphor with cerium luminescence |
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2005
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5213712A (en) * | 1992-02-10 | 1993-05-25 | General Electric Company | Lanthanum lutetium oxide phosphor with cerium luminescence |
Non-Patent Citations (4)
| Title |
|---|
| NIR to Visible Upconversion in Nanocrystalline and BulkLu2O3:Er3+. Fiorenzo Vetrone et.The Journal of Physical Chemistry,Vol.106 No.22. 2002 * |
| 上传换激光和上传换发光材料的研究进展. 徐东勇等.人工晶体学报，第30卷第2期. 2001 * |
| 上传换荧光材料生物芯片技术中的应用. 鲍俊萍等.上传换荧光材料在生物芯片技术中的应用，第17期. 2003 * |
| 水热合成稀土氟化物材料KZNF3:ER,YB的上传换发光特性. 裴晓将等.中国稀土学报，第21增刊期. 2003 * |
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