CN103275706A - Blue up-conversion luminescent material and preparation method thereof - Google Patents
Blue up-conversion luminescent material and preparation method thereof Download PDFInfo
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- CN103275706A CN103275706A CN201310213040XA CN201310213040A CN103275706A CN 103275706 A CN103275706 A CN 103275706A CN 201310213040X A CN201310213040X A CN 201310213040XA CN 201310213040 A CN201310213040 A CN 201310213040A CN 103275706 A CN103275706 A CN 103275706A
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Abstract
The invention discloses a blue up-conversion luminescent material and a preparation method thereof. The adopted technical scheme is as follows: the blue up-conversion luminescent material has a chemical reaction formula with an initial component formula: nRF-(1-x-y-z-n)ZnF2-xSrF2-yYbF3-zTmF3, wherein R is Li or Na; n, x, y and z stand for the mole ratios of all initial components, 0.001<=n<=0.03, 0.5<=x<=0.7, 0.1<=y<=0.25, and 0.001<=z<=0.004; and a high-temperature solid state sintering method is combined in the preparation method. The defects of rigorous preparation process conditions, long production processes, higher production cost, longer production period and the like in the development process of the traditional up-conversion luminescent material are overcome; and the blue up-conversion luminescent material is suitable for the search and application of small visible and ultraviolet band all-solid lasers and particularly suitable for the search and application in the fields such as three-dimensional display, infrared detection, bioluminescence disappearance, anti-counterfeiting and the like.
Description
Technical field
The present invention relates to the luminescent material technical field, relate in particular to infrared up-conversion luminous material of a kind of blue light-emitting and preparation method thereof.
Background technology
In the existing up-conversion luminescent material research, the research of three primary colors fluorescent powder has caused extensive concern both domestic and external, and in different substrate materials, the different rare earth ion that mixes can be realized the red, green, blue up-conversion luminescence of rare earth ion, wherein especially with Yb
3+/ Er
3+Green up-conversion luminescence research at most, the research of blue up-conversion luminescence is then less relatively: announced a kind of blue up-conversion luminous material NaYF as [Chinese patent publication number CN101476151]
4: Yb
3+/ Tm
3+And preparation method thereof, take by weighing set amount solid rare earth nitrate Y (NO3) 36H2O at first in proportion, it is Yb ion or La ion that Yb (NO3) 36H2O, Tm (NO3) 36H2O make its rare earth ion mol ratio: the Yb ion: the Tm ion equals (70～90): (0～29): (0.001～15); Add tetrafluoroborate class ionic liquid 1-ethyl-3-methyl imidazolium tetrafluoroborate then, 1-butyl-3-methyl imidazolium tetrafluoroborate or 1-octyl group-3-methyl imidazolium tetrafluoroborate, 100～150 ℃ of following violent stirring to remove the crystal water in the rare earth nitrate and to make rare earth nitrate be dissolved in the ionic liquid fully, wait doubly to the NaCl solid of total rare earth (TRE) ion molar weight adding in the mixed ionic liquid that obtains, continue to stir, the NaCl solid is dissolved in this mixed ionic liquid fully, again the mixing solutions of gained is put into the teflon-lined autoclave, it is interior after reacting by heating is finished under 180～220 ℃ of temperature to insert baking oven, naturally cool to room temperature, throw out with the reactant centrifugation carries out supersound washing with ethanol and deionized water at last, 50～80 ℃ of vacuum-dryings, obtain nano level NaYF
4: Yb
3+/ Tm
3+, there is the processing condition harshness in this blue up-conversion luminous material and preparation method thereof, production process is tediously long, production cost higher etc. defective.Another [Chinese patent application 201110201553.x] also announced a kind of blue colour conversion material and preparation method thereof, it is the rare earth source with rare earth oxide, oxyhydroxide, carbonate or nitrate, with ammonium bifluoride or Neutral ammonium fluoride as the fluorine source, stirring reaction obtains throw out in the aqueous solution, then with NaF, NH
4F and Na
2CO
3Or NaHCO
3Mixture in one or more mechanically mixing obtain precursor, at last precursor roasting in retort furnace is obtained having NaY
1-x-yYb
xTm
yF
4The blue light up-conversion luminescent material that the atomic ratio of expression is formed; It is loaded down with trivial details equally that this preparation method relates to process, and the production cycle is also longer.
Summary of the invention
At above-mentioned situation; the object of the present invention is to provide a kind of blue up-conversion luminous material and preparation method thereof; it had both had the chemical purity height, luminous mass is good; have again that preparation technology is simple, production operation is easy; also having the products production cost reduces; capital contribution is few, can realize industrialization, mass-producing, commercialization, and economical and practical, be convenient to penetration and promotion.
To achieve these goals, a kind of blue up-conversion luminous material, initial composition composition formula is:
nRF-(1-x-y-z-n)ZnF
2-xSrF
2-yYbF
3-zTmF
3
Wherein
N, x, y, z are the molar ratio of each initial composition composition, and 0.001≤n≤0.03,0.5≤x≤0.7,0.1≤y≤0.25,0.001≤z≤0.004;
RF is that LiF(fluoridizes Lithium) or the NaF(Sodium Fluoride);
With the following steps preparations blue 465nm infrared up-conversion luminous material under infrared 980nm laser pumping light source:
(1) by initial composition composition formula mol ratio, takes by weighing ZnF respectively
2(zinc fluoride), SrF
2(strontium fluoride), YbF
3(fluoridizing ytterbium), TmF
3(fluoridizing thulium), LiF(fluoridize Lithium) or the NaF(Sodium Fluoride), evenly mix the back and ground 1～2 hour;
(2) under protective atmosphere, described mixture is placed on calcination in the retort furnace;
(3) behind the naturally cooling, grind and obtain the blue infrared up-conversion luminescence powdered material of target.
In order to improve over-all properties of the present invention, implementation structure, effect optimization, its further step is:
Milling time is 1.6 hours.
Calcination temperature is 700 ℃～900 ℃.
Calcination time is 50～70 minutes.
Protective atmosphere is the fluorine gas atmosphere.
A kind of blue up-conversion luminous material and preparation method thereof, it adopts its initial composition composition formula is nRF-(1-x-y-z-n) ZnF
2-xSrF
2-yYbF
3-zTmF
3Chemical equation, and be Li or Na with R; N, x, y, z are the molar ratio of each initial composition composition, and 0.001≤n≤0.03,0.5≤x≤0.7,0.1≤y≤0.25,0.001≤z≤0.004 and the technical scheme that combines with the high temperature solid-phase sintering method; It has overcome in the development of existing up-conversion luminescent material defective such as have the preparation process condition harshness, production process is tediously long, production cost is higher, the production cycle is long.
The beneficial effect that the present invention produces compared to existing technology:
It is nRF-(1-x-y-z-n) ZnF that (I) the present invention adopts its initial composition composition formula
2-xSrF
2-yYbF
3-zTmF
3Chemical equation and the technical scheme that the high temperature solid-phase sintering method combines, the luminescent material stable performance that makes, the blue 465nm up-conversion luminescence under infrared 980nm laser pumping light source and tool high brightness, high color purity characteristics;
It is nRF-(1-x-y-z-n) ZnF that (II) the present invention adopts its initial composition composition formula
2-xSrF
2-yYbF
3-zTmF
3Chemical equation and the technical scheme that the high temperature solid-phase sintering method combines, realized that manufacturing process is simple, production operation is simple and easy, production energy consumption is than low, capital contribution is few, development cost is low;
It is nRF-(1-x-y-z-n) ZnF that (III) the present invention adopts its initial composition composition formula
2-xSrF
2-yYbF
3-zTmF
3The optimization technology that combines with the high temperature solid-phase sintering method of chemical equation, for solid basis has been established in industrialization, mass-producing, the commercialization of implementing product;
It is nRF-(1-x-y-z-n) ZnF that (IV) the present invention adopts its initial composition composition formula
2-xSrF
2-yYbF
3-zTmF
3The optimization technology that combines with the high temperature solid-phase sintering method of chemical equation, numerous areas has been established good prospects for application in order to implement that 3 D stereo shows and false proof etc.;
(V) the present invention adopts with ZnF
2And SrF
2Be base matrix, the simple process in conjunction with only needing mixed grinding and calcining to get final product greatly reduces product cost, and it is synthetic convenient, special suitable batch production possesses the implementation condition of penetration and promotion and broadened application, and its trade benefit and market distant view can be expected.
The present invention is fit to development and the application of small-sized visible and ultraviolet band all solid laser; Be particularly suitable for development and application in field such as 3 D stereo demonstration, infrared acquisition, bioluminescence be missing, false proof.
Below in conjunction with drawings and Examples the present invention is described in further detail.
Description of drawings
The emmission spectrum figure of luminescent material under 980nm is infrared ray excited that Fig. 1 provides for the embodiment of the invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing technical solution of the present invention is further described.
Embodiment 1
By initial composition composition formula 0.001LiF-0.398ZnF
2-0.5SrF
2-0.1YbF
3-0.001TmF
3In stoichiometry (mole) ratio of each element, take by weighing zinc fluoride ZnF respectively
2: 1.6420 grams, strontium fluoride SrF
2: 2.5059 grams, fluoridize ytterbium YbF
3: 0.9178 gram, fluoridize thulium TmF
3: 0.009 gram and lithium fluoride LiF:0.001 gram, evenly to mix the back and grind, milling time is 1.0 hours;
Mixture after grinding is placed on ammonium bifluoride provides calcination in the retort furnace of fluorine gas atmosphere, and sintering temperature is 900 ℃, and sintering time is 50 minutes; Powered-down takes out sample when waiting it to be chilled to room temperature then;
Take out behind the sample that grind into powder namely gets described up-conversion luminescent material in agate mortar; Inversion spectrum is as shown in Figure 1 on 980nm excites down for it.
Embodiment 2
By initial composition composition formula 0.005LiF-0.393ZnF
2-0.5SrF
2-0.1YbF
3-0.002TmF
3In stoichiometry (mole) ratio of each element, take by weighing zinc fluoride ZnF respectively
2: 1.6231 grams, strontium fluoride SrF
2: 2.5085 grams, fluoridize ytterbium YbF
3: 0.9187 gram, fluoridize thulium TmF
3: 0.018 gram and lithium fluoride LiF:0.0052 gram, evenly to mix the back and grind, milling time is 1.3 hours;
Mixture after grinding is placed on ammonium bifluoride provides calcination in the retort furnace of fluorine gas atmosphere, and sintering temperature is 850 ℃, and sintering time is 55 minutes; Powered-down takes out sample when waiting it to be chilled to room temperature then;
Take out behind the sample that grind into powder namely gets described up-conversion luminescent material in agate mortar.
Embodiment 3
By initial composition composition formula 0.01LiF-0.288ZnF
2-0.55SrF
2-0.15YbF
3-0.002TmF
3In stoichiometry (mole) ratio of each element, take by weighing zinc fluoride ZnF respectively
2: 1.1333 grams, strontium fluoride SrF
2: 2.6291 grams, fluoridize ytterbium YbF
3: 1.3131 grams, fluoridize thulium TmF
3: 0.0172 gram and lithium fluoride LiF:0.0099 gram, evenly to mix the back and grind, milling time is 1.5 hours;
Mixture after grinding is placed on ammonium bifluoride provides calcination in the retort furnace of fluorine gas atmosphere, and sintering temperature is 850 ℃, and sintering time is 55 minutes; Powered-down takes out sample when waiting it to be chilled to room temperature then;
Take out behind the sample that grind into powder namely gets described up-conversion luminescent material in agate mortar.
Embodiment 4
By initial composition composition formula 0.02LiF-0.228ZnF
2-0.55SrF
2-0.2YbF
3-0.002TmF
3In stoichiometry (mole) ratio of each element, take by weighing zinc fluoride ZnF respectively
2: 0.8656 gram, strontium fluoride SrF
2: 2.5366 grams, fluoridize ytterbium YbF
3: 1.6891 grams, fluoridize thulium TmF
3: 0.0166 gram and lithium fluoride LiF:0.019 gram, evenly to mix the back and grind, milling time is 1.6 hours;
Mixture after grinding is placed on ammonium bifluoride provides calcination in the retort furnace of fluorine gas atmosphere, and sintering temperature is 800 ℃, and sintering time is 60 minutes; Powered-down takes out sample when waiting it to be chilled to room temperature then;
Take out behind the sample that grind into powder namely gets described up-conversion luminescent material in agate mortar.
Embodiment 5
By initial composition composition formula 0.01NaF-0.238ZnF
2-0.6SrF
2-0.15YbF
3-0.002TmF
3In stoichiometry (mole) ratio of each element, take by weighing zinc fluoride ZnF respectively
2: 0.9276 gram, strontium fluoride SrF
2: 2.8407 grams, fluoridize ytterbium YbF
3: 1.3005 grams, fluoridize thulium TmF
3: 0.017 gram and Sodium Fluoride NaF:0.0158 gram, evenly to mix the back and grind, milling time is 1.6 hours;
Mixture after grinding is placed on ammonium bifluoride provides calcination in the retort furnace of fluorine gas atmosphere, and sintering temperature is 800 ℃, and sintering time is 60 minutes; Powered-down takes out sample when waiting it to be chilled to room temperature then;
Take out behind the sample that grind into powder namely gets described up-conversion luminescent material in agate mortar.
Embodiment 6
By initial composition composition formula 0.015NaF-0.182ZnF
2-0.6SrF
2-0.2YbF
3-0.003TmF
3In stoichiometry (mole) ratio of each element, take by weighing zinc fluoride ZnF respectively
2: 0.6822 gram, strontium fluoride SrF
2: 2.7321 grams, fluoridize ytterbium YbF
3: 1.6677 grams, fluoridize thulium TmF
3: 0.0246 gram and Sodium Fluoride NaF:0.0228 gram, evenly to mix the back and grind, milling time is 1.6 hours;
Mixture after grinding is placed on ammonium bifluoride provides calcination in the retort furnace of fluorine gas atmosphere, and sintering temperature is 750 ℃, and sintering time is 60 minutes; Powered-down takes out sample when waiting it to be chilled to room temperature then;
Take out behind the sample that grind into powder namely gets described up-conversion luminescent material in agate mortar.
Embodiment 7
By initial composition composition formula 0.02NaF-0.127ZnF
2-0.65SrF
2-0.2YbF
3-0.003TmF
3In stoichiometry (mole) ratio of each element, take by weighing zinc fluoride ZnF respectively
2: 0.4729 gram, strontium fluoride SrF
2: 2.9406 grams, fluoridize ytterbium YbF
3: 1.6569 grams, fluoridize thulium TmF
3: 0.0244 gram and Sodium Fluoride NaF:0.0302 gram, evenly to mix the back and grind, milling time is 1.8 hours;
Mixture after grinding is placed on ammonium bifluoride provides calcination in the retort furnace of fluorine gas atmosphere, and sintering temperature is 750 ℃, and sintering time is 65 minutes; Powered-down takes out sample when waiting it to be chilled to room temperature then;
Take out behind the sample that grind into powder namely gets described up-conversion luminescent material in agate mortar.
Embodiment 8
By initial composition composition formula 0.025NaF-0.021ZnF
2-0.7SrF
2-0.25YbF
3-0.004TmF
3In stoichiometry (mole) ratio of each element, take by weighing zinc fluoride ZnF respectively
2: 0.0748 gram, strontium fluoride SrF
2: 3.0276 grams, fluoridize ytterbium YbF
3: 1.9801 grams, fluoridize thulium TmF
3: 0.0311 gram and Sodium Fluoride NaF:0.0361 gram, evenly to mix the back and grind, milling time is 2.0 hours;
Mixture after grinding is placed on ammonium bifluoride provides calcination in the retort furnace of fluorine gas atmosphere, and sintering temperature is 700 ℃, and sintering time is 70 minutes; Powered-down takes out sample when waiting it to be chilled to room temperature then;
Take out behind the sample that grind into powder namely gets described up-conversion luminescent material in agate mortar.
Above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (5)
1. blue up-conversion luminous material, initial composition composition formula is:
nRF-(1-x-y-z-n)ZnF
2-xSrF
2-yYbF
3-zTmF
3
Wherein
N, x, y, z are the molar ratio of each initial composition composition, and 0.001≤n≤0.03,0.5≤x≤0.7,0.1≤y≤0.25,0.001≤z≤0.004;
RF is LiF or NaF;
With the following steps preparations blue 465nm infrared up-conversion luminous material under infrared 980nm laser pumping light source:
(1) by initial composition composition formula mol ratio, takes by weighing ZnF respectively
2, SrF
2, YbF
3, TmF
3, LiF or NaF, evenly mix the back and ground 1～2 hour;
(2) under protective atmosphere, described mixture is placed on calcination in the retort furnace;
(3) behind the naturally cooling, grind and obtain the blue infrared up-conversion luminescence powdered material of target.
2. a kind of blue up-conversion luminous material according to claim 1 is characterized in that described milling time is 1.6 hours.
3. a kind of blue up-conversion luminous material according to claim 1 is characterized in that described calcination temperature is 700 ℃～900 ℃.
4. a kind of blue up-conversion luminous material according to claim 1 is characterized in that described calcination time is 50～70 minutes.
5. according to claim 1 described a kind of blue up-conversion luminous material, it is characterized in that described protective atmosphere is the fluorine gas atmosphere.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974251A (en) * | 2017-11-30 | 2018-05-01 | 华南理工大学 | A kind of up-converting phosphor material and preparation method and application |
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| JPH04328191A (en) * | 1991-04-30 | 1992-11-17 | Central Glass Co Ltd | Infrared-visible light converting fluorescent substance comprising fluoride glass |
| US5846684A (en) * | 1994-01-25 | 1998-12-08 | Eastman Kodak Company | Device for converting invisible and visible radiation to visible light and/or UV radiation |
| US6654161B2 (en) * | 1998-11-25 | 2003-11-25 | University Of Central Florida | Dispersed crystallite up-conversion displays |
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| CN102826850A (en) * | 2012-08-20 | 2012-12-19 | 长春理工大学 | Barium fluoride up-conversion transparent ceramic and preparation method thereof |
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2013
- 2013-05-31 CN CN201310213040.XA patent/CN103275706B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04328191A (en) * | 1991-04-30 | 1992-11-17 | Central Glass Co Ltd | Infrared-visible light converting fluorescent substance comprising fluoride glass |
| US5846684A (en) * | 1994-01-25 | 1998-12-08 | Eastman Kodak Company | Device for converting invisible and visible radiation to visible light and/or UV radiation |
| US6654161B2 (en) * | 1998-11-25 | 2003-11-25 | University Of Central Florida | Dispersed crystallite up-conversion displays |
| CN1676679A (en) * | 2005-01-20 | 2005-10-05 | 中国科学院上海光学精密机械研究所 | Up-conversion laser crystal Er3+,Yb3+,Na+:CaF2 |
| CN102826850A (en) * | 2012-08-20 | 2012-12-19 | 长春理工大学 | Barium fluoride up-conversion transparent ceramic and preparation method thereof |
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| NING-NING DONG ET AL.: "NIR-to-NIR Two-Photon Excited CaF2:Tm3+,Yb3+ Nanoparticles: Multifunctional Nanoprobes for Highly Penetrating Fluorescence Bio-Imaging", 《ACS NANO》, vol. 5, no. 11, 29 September 2011 (2011-09-29) * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974251A (en) * | 2017-11-30 | 2018-05-01 | 华南理工大学 | A kind of up-converting phosphor material and preparation method and application |
| WO2019105488A1 (en) * | 2017-11-30 | 2019-06-06 | 华南理工大学 | Upconversion phosphorescent material, and preparation method therefor and application thereof |
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