CN101020824A - Infrared ray excited up-conversion luminescent material and its prepn - Google Patents
Infrared ray excited up-conversion luminescent material and its prepn Download PDFInfo
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- CN101020824A CN101020824A CN 200710055399 CN200710055399A CN101020824A CN 101020824 A CN101020824 A CN 101020824A CN 200710055399 CN200710055399 CN 200710055399 CN 200710055399 A CN200710055399 A CN 200710055399A CN 101020824 A CN101020824 A CN 101020824A
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Abstract
The present invention is one kind of infrared ray excited up-conversion luminescent material and its preparation process. The luminescent material is complex fluoride in the chemical composition of NaY1-x-yYbxReyF4, where, x is 0.05-0.3, y is 0.001-0.1, and Re is Er or Tm. It is prepared through converting NaF, RE nitrate and RE chloride into corresponding oxide, hydroxide, carbonate, etc; depositing in water solution to generate NaY1-x-yYbxReyF4; treatment at 500-700 deg.c under protecting atmosphere for 1-10 hr and cooling. It has luminescent strength higher than that of commercial BaYF5:Yb material and pure light color, and may be used widely for stereo display, infrared detection, biological tracing and other fields.
Description
Technical field
The present invention relates to a kind of infrared ray excited up-conversion luminescent material and preparation method thereof.
Background technology
Infrared up-conversion luminous material is a kind of material in infrared ray excited down visible emitting, and it is at three stereo displays, infrared acquisition, and bioluminescence spike, all many-sides such as false proof are with a wide range of applications.Employed efficient up-conversion luminescent material mainly is a fluorochemical at present, and it has lower phonon energy, less radiationless transition probability, therefore, the luminous efficiency that available acquisition is higher.In converting luminescent material of fluoride, NaYF
4: Yb, Er be because its luminous efficiency height, good stability and being used widely.At present it mainly be under protection of inert gas, utilize high-temperature solid phase reaction method pass through rare earth fluorine and Sodium Silicofluoride reaction acquisition.Thereby cause environmental pollution because precursor rare earth fluorine complicated process of preparation and Sodium Silicofluoride produce a large amount of tetrafluoro silicon toxic gases in the process of reaction, therefore, improve its preparation method is the direction that people study always.The method of this luminescent material of preparation has multiple at present, as K.W.Kr mer (Chem.Mater.2004,16,1244-1251) propose to utilize rare earth oxide, yellow soda ash, hydrofluoric acid, Hydrogen bromide in the aqueous solution, to form Sodium Fluoride and the rare earth fluorine method of this luminescent material of acquisition in hydrogen fluoride and argon mixture gas then, this method preparation process complexity, hydrogen fluoride gas in the preparation process pollutes environment, is not the preparation method of a practicality therefore.And for example utilize also available this luminescent material of preparation of hydrothermal method, hydrothermal method has the low advantage of synthesis temperature, but because reaction process is under high pressure to carry out, and the luminous efficiency of the luminescent material of preparing is lower, therefore, and this method incompatibility mass production.
Summary of the invention
The purpose of this invention is to provide a kind of infrared ray excited up-conversion luminescent material and preparation method thereof.
The chemical constitution formula of the up-conversion luminescent material that the present invention relates to is:
NaY
1-x-yYb
xRe
yF
4
Wherein, 0.05≤x≤0.3; 0.001≤y≤0.1; Re is Er or Tm.
The preparation method of infrared ray excited up-conversion luminescent material involved in the present invention adopts the fluorine source of Sodium Fluoride as complex fluoride; in the aqueous solution, generate complex fluoride with rare earth ion, thus then under protective atmosphere pyroprocessing obtain the method for efficient up-conversion luminescent material.
A kind of preparation method's of infrared ray excited up-conversion luminescent material step and condition are as follows:
The starting material that adopted are Yttrium trinitrate, ytterbium nitrate, Erbium trinitrate, thulium nitrate or corresponding rare earth chloride or can be converted into the oxide compound, oxyhydroxide, carbonate of corresponding compounds as the rare earth ion source by nitric acid or hydrochloric acid; Sodium Fluoride is as fluorine source and sodium source; Nitric acid, hydrochloric acid;
The corresponding starting material of chemical constitution formula weighing according to up-conversion luminescent material provided by the invention, above-mentioned rare earth compound is dissolved in the container obtains the rare earth ion aqueous solution, Sodium Fluoride is dissolved in another container and obtains sodium fluoride aqueous solution, then rare-earth ion solution is joined gradually and form precipitation in the Fluorinse of continuous stirring, leave standstill after continuing to stir for some time, outwell supernatant liquor, add deionized water again, leave standstill after the stirring, outwell supernatant liquor, filter, get throw out with alcohol flushing, throw out is dried, under protective atmosphere, 500～700 ℃ of calcinations 1～10 hour, cooling is pulverized, washing, oven dry promptly obtains a kind of infrared ray excited up-conversion luminescent material;
Said protective atmosphere is that nitrogen, argon gas, hydrogen, tetrafluoro silicon gas and hydrogen fluoride gas are at least a.
The preparation method of a kind of infrared ray excited up-conversion luminescent material provided by the invention, avoid using hydrofluoric acid in the preparation process, thus the harm of having avoided hydrofluoric acid that human body and environment are caused, and whole process of preparation is simple to operate, safety, it is available to be widely used for actual production; A kind of infrared ray excited up-conversion luminescent material that is obtained has high luminous intensity under 980nm excites, with commercial luminescent material BaYF
5: Yb, the luminous intensity of Er is 100, it is 120 that its up-conversion luminescence intensity is about; Its glow color is pure; Its available three stereo displays, infrared acquisition of being widely used in, bioluminescence spike and all many-sides such as false proof.
Description of drawings
Fig. 1 is the X-ray diffraction spectrum of luminescent material
Fig. 2 is the last switching emission spectrum of a kind of infrared ray excited up-conversion luminescent material of 980nm under exciting; 1 is the prepared up-conversion luminescent material of embodiment 1, and 2 is commercial BaYF
5: Yb, Er luminescent material.
Embodiment
Embodiment 1
Take by weighing 15.3 gram YCl
36H
2O, 0.443 gram ErCl
36H
2O, 3.72 gram YbCl
35H
2O puts into the container of 500ml, adds the 300ml secondary deionized water, stirs they are dissolved fully, forms rare-earth ion solution.Take by weighing 11.6g NaF, put into the container of another 800ml, add the stirring of 300ml secondary deionized water water and make its dissolving.Then rare-earth ion solution is joined gradually and form precipitation in the Fluorinse of continuous stirring, continue to stir after 1 hour and leave standstill, outwell supernatant liquor, add deionized water again, leave standstill after the stirring, outwell supernatant liquor, filter, get throw out with alcohol flushing.The throw out oven dry under argon shield, in 500 ℃ of calcinations 10 hours, is taken out it behind the naturally cooling, pulverizes, and washing, oven dry obtains a kind of infrared ray excited up-conversion luminescent material.The up-conversion luminescence intensity of the luminescent material that is obtained is 120.(commercial luminescent material BaYF
5: Yb, its intensity of Er is 100, following examples are all with this commercialization luminescent material BaYF
5: Yb, the Er luminous intensity is 100).
Embodiment 2
Take by weighing 16.3 gram Y (NO
3)
36H
2O, 0.443 gram Er (NO
3)
35H
2O, 3.82 gram Yb (NO
3)
33H
2O puts into the container of 500ml, adds the 300ml secondary deionized water, stirs they are dissolved fully, forms rare-earth ion solution.Take by weighing 10.6g NaF, put into the container of another 800ml, add the stirring of 300ml water and make its dissolving.Then rare-earth ion solution is joined gradually and form precipitation in the Fluorinse of continuous stirring, continue to leave standstill after 2 times of stirring, outwell supernatant liquor, add deionized water again, leave standstill after the stirring, outwell supernatant liquor, filter, get throw out with alcohol flushing.Throw out oven dry, its put into stove under nitrogen protection in 600 ℃ of calcinations 3 hours, take out behind the naturally cooling, pulverize, washing, oven dry obtains a kind of infrared ray excited up-conversion luminescent material.The up-conversion luminescence intensity that is obtained is 120.
Embodiment 3
Take by weighing 16.3 gram Y (NO
3)
36H
2O, 0.443 gram Er (NO
3)
35H
2O, 3.82 gram Yb (NO
3)
33H
2O puts into the container of 500ml, adds the 300ml secondary deionized water, stirs they are dissolved fully, forms rare-earth ion solution.Take by weighing 12.6g NaF, put into the container of another 800ml, add the stirring of 300ml water and make its dissolving.Then rare-earth ion solution is joined gradually and form precipitation in the Fluorinse of continuous stirring, continue to leave standstill after 3 times of stirring, outwell supernatant liquor, add deionized water again, leave standstill after the stirring, outwell supernatant liquor, filter, get throw out with alcohol flushing.Throw out oven dry, its put into stove under nitrogen and hydrogen gas mixture protection in 650 ℃ of calcinations 2 hours, take out behind the naturally cooling, pulverize, washing, oven dry obtains a kind of infrared ray excited up-conversion luminescent material.The up-conversion luminescence intensity of the luminescent material that is obtained is 122.
Embodiment 4
Take by weighing 7.026 gram Y
2O
3, 0.406 gram Er
2O
3, 3.237 gram Yb
2O
3Put into the container of 500ml, add the 100ml secondary deionized water, stir into and stick with paste dress, enter a certain amount of concentrated nitric acid (65%) stirring then gradually they are dissolved fully, add the 200ml deionized water again and form rare-earth ion solution.Take by weighing 18g NaF, put into the container of another 800ml, add the stirring of 400ml water and make its dissolving.Then rare-earth ion solution is joined gradually and form precipitation in the Fluorinse of continuous stirring, continue to stir after 4 hours and leave standstill, outwell supernatant liquor, add deionized water again, leave standstill after the stirring, outwell supernatant liquor, filter, get throw out with alcohol flushing.Throw out baking, its put into stove under the protection of nitrogen and hydrogen fluoride gas in 700 ℃ of calcinations 1 hour, take out behind the naturally cooling, pulverize, washing, oven dry obtains a kind of infrared ray excited up-conversion luminescent material.The up-conversion luminescence intensity of the luminescent material that is obtained is 121.
Embodiment 5
Take by weighing 7.026 gram Y
2O
3, 0.406 gram Er
2O
3, 3.237 gram Yb
2O
3Put into the container of 500ml, add the 100ml secondary deionized water, stir into and stick with paste dress, enter a certain amount of concentrated hydrochloric acid (36%) stirring then gradually they are dissolved fully, add the 200ml deionized water again and form rare-earth ion solution.Take by weighing 18g NaF, put into the container of another 800ml, add the stirring of 400ml water and make its dissolving.Then rare-earth ion solution is joined gradually and form precipitation in the Fluorinse of continuous stirring, stirs and leave standstill after 2 hours, outwell supernatant liquor, add deionized water again, leave standstill after the stirring, outwell supernatant liquor, filtration gets throw out with alcohol flushing.The throw out oven dry is put into stove to it under the protection of nitrogen and silicon tetrafluoride mixed gas, in 600 ℃ of calcinations 4 hours, takes out behind the naturally cooling, pulverize, and washing, oven dry promptly gets a kind of infrared ray excited up-conversion luminescent material.The luminescent material up-conversion luminescence intensity that is obtained is 119.
Embodiment 6
Take by weighing 15.3 gram Y (NO
3)
36H
2O, 0.083 gram Tm (NO
3)
36H
2O, 3.02 gram Yb (NO
3)
33H
2O puts into the container of 500ml, adds the 300ml secondary deionized water, stirs they are dissolved fully, forms rare-earth ion solution.Take by weighing 13.6g NaF, put into the container of another 800ml, add the stirring of 300ml water and make its dissolving.Then rare-earth ion solution is joined gradually and form precipitation in the Fluorinse of continuous stirring, leave standstill after stirring 4 hour time, outwell supernatant liquor, add deionized water again, leave standstill after the stirring, outwell supernatant liquor, filtration gets throw out with alcohol flushing.The throw out oven dry is put into stove to it under argon shield, and in 600 ℃ of calcinations 5 hours, naturally cooling was pulverized, washing, and oven dry obtains a kind of infrared ray excited up-conversion luminescent material.The up-conversion luminescence intensity of the luminescent material that is obtained is 110.
Claims (2)
1, a kind of infrared ray excited up-conversion luminescent material is characterized in that, the chemical formula of described luminescent material is:
NaY
1-x-yYb
xRe
yF
4
Wherein, 0.05≤x≤0.3; 0.001≤y≤0.1; Re is Er or Tm.
2, the preparation method of a kind of infrared ray excited up-conversion luminescent material as claimed in claim 1 is characterized in that step and condition are as follows:
The starting material that adopted are: Yttrium trinitrate, ytterbium nitrate, Erbium trinitrate, thulium nitrate or corresponding rare earth chloride or the oxide compound, oxyhydroxide, carbonate etc. that can be converted into corresponding compounds by nitric acid or hydrochloric acid are as the rare earth ion source; Sodium Fluoride is as fluorine source and sodium source; Secondary deionized water; Nitric acid, hydrochloric acid;
The corresponding starting material of chemical constitution formula weighing according to up-conversion luminescent material provided by the invention, above-mentioned rare earth compound is dissolved in the container obtains rare-earth ion solution, Sodium Fluoride is dissolved in another container, rare-earth ion solution is joined gradually to form precipitation in the Fluorinse of continuous stirring then, leaves standstill after stirring for some time, outwell supernatant liquor, add deionized water again, leave standstill after the stirring, outwell supernatant liquor, filter, get throw out with alcohol flushing, throw out is 120 ℃ of oven dry, under protective atmosphere, 500～700 ℃ of calcinations 1～10 hour, cooling is pulverized, washing, oven dry obtains a kind of infrared ray excited up-conversion luminescent material;
Said protective atmosphere is that nitrogen, argon gas, hydrogen, tetrafluoro silicon gas and hydrogen fluoride gas are at least a.
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| CN101020824A true CN101020824A (en) | 2007-08-22 |
| CN100519697C CN100519697C (en) | 2009-07-29 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982522A (en) * | 2010-10-20 | 2011-03-02 | 中国科学院长春应用化学研究所 | Infrared up-conversion luminescent material and preparation method thereof |
| CN102337135A (en) * | 2011-07-19 | 2012-02-01 | 上海华明高纳稀土新材料有限公司 | Blue-light infrared up-conversion luminescent material and preparation method thereof |
| CN102382653A (en) * | 2011-08-31 | 2012-03-21 | 上海华明高纳稀土新材料有限公司 | Blue-light infrared up-converting rare-earth luminescent material and its preparation method |
| CN102559186A (en) * | 2010-12-23 | 2012-07-11 | 上海华明高技术（集团）有限公司 | Infrared up-conversion fluorescent powder and preparation method thereof |
| CN102798720A (en) * | 2012-08-09 | 2012-11-28 | 河南省农业科学院 | Immune chromatography test paper for quantitative determination of clenbuterol based on up-conversion fluorescent nanoparticle label and preparation method thereof |
| WO2021134812A1 (en) * | 2019-12-31 | 2021-07-08 | 天津市中环天佳电子有限公司 | Bronze red printer toner employing rare earth spectroscopy tracing |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1536050A (en) * | 2003-04-11 | 2004-10-13 | 姚瑞刚 | Preparation method of infrared anti-false luminous material and its application |
| CN1298808C (en) * | 2004-10-26 | 2007-02-07 | 清华大学 | Method for burning synthesis of ytterbium and erbium -codoped conversion luminescent material on sodium yttrium fluoride |
-
2007
- 2007-03-12 CN CNB2007100553993A patent/CN100519697C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982522A (en) * | 2010-10-20 | 2011-03-02 | 中国科学院长春应用化学研究所 | Infrared up-conversion luminescent material and preparation method thereof |
| CN101982522B (en) * | 2010-10-20 | 2013-04-10 | 中国科学院长春应用化学研究所 | Infrared up-conversion luminescent material and preparation method thereof |
| CN102559186A (en) * | 2010-12-23 | 2012-07-11 | 上海华明高技术（集团）有限公司 | Infrared up-conversion fluorescent powder and preparation method thereof |
| CN102559186B (en) * | 2010-12-23 | 2014-07-30 | 上海华明高技术（集团）有限公司 | Infrared up-conversion fluorescent powder and preparation method thereof |
| CN102337135A (en) * | 2011-07-19 | 2012-02-01 | 上海华明高纳稀土新材料有限公司 | Blue-light infrared up-conversion luminescent material and preparation method thereof |
| CN102382653A (en) * | 2011-08-31 | 2012-03-21 | 上海华明高纳稀土新材料有限公司 | Blue-light infrared up-converting rare-earth luminescent material and its preparation method |
| CN102798720A (en) * | 2012-08-09 | 2012-11-28 | 河南省农业科学院 | Immune chromatography test paper for quantitative determination of clenbuterol based on up-conversion fluorescent nanoparticle label and preparation method thereof |
| CN102798720B (en) * | 2012-08-09 | 2015-01-21 | 河南省农业科学院 | Immune chromatography test paper for quantitative determination of clenbuterol based on up-conversion fluorescent nanoparticle label and preparation method thereof |
| WO2021134812A1 (en) * | 2019-12-31 | 2021-07-08 | 天津市中环天佳电子有限公司 | Bronze red printer toner employing rare earth spectroscopy tracing |
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|---|---|
| CN100519697C (en) | 2009-07-29 |
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