CN101225304B - Multi-band fluorescent infrared up-conversion material based on sensitizer substrate - Google Patents

Multi-band fluorescent infrared up-conversion material based on sensitizer substrate Download PDF

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CN101225304B
CN101225304B CN2007101926498A CN200710192649A CN101225304B CN 101225304 B CN101225304 B CN 101225304B CN 2007101926498 A CN2007101926498 A CN 2007101926498A CN 200710192649 A CN200710192649 A CN 200710192649A CN 101225304 B CN101225304 B CN 101225304B
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ybf3
tube furnace
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CN101225304A (en
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肖思国
王祥夫
丁建文
阳效良
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Liuyang Huifeng Printing Technology Co., Ltd.
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Xiangtan University
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Abstract

The invention relates to a multiwave fluorescence infrared transition material based on a sensibilizer substrate, which is characterized in that: the sensibilizer and substrate are YbF3, and at leastone ion among Ho<3+>, Er<3+>, Tm<3+> and Pr<3+> is mixed in YbF3, and after coprecipitation and solid phase reaction, the YbF3 with at least one ion among Ho<3+>, Er<3+>, Tm<3+> and Pr<3+> doped is prepared, and under the excitation of near infrared lights of 930 to 990nm, multiwave transition fluorescence output is realized; the preparation steps are that: (1) the Ho<3+>, Er<3+>, Tm<3+> and Pr<3+> are mixed in YbF3 as an activation centre, and the nitrate or chloride solutions of Ho, Er, Tm, Pr and Yb are mixed according to the molal weights of the doped ions with a proportion of 0.0005 > X <0.09, and then a NH4F or NH4HF2 solution is used as a sedimentation reagent, and a precursor powder is prepared by coprecipitation method; (2) the precursor powder is calcined for one to three hoursat the protection condition of HF gas provided by the decomposition of NH4F or NH4HF2 at 600 to 750 degree centigrade to obtain the product. The multiwave fluorescence infrared transition material based on the sensibilizer substrate has the advantages of conquering the drawback that YbF3 is only used as a sensitized material on tradition because of the technical proposal that YbF3 is used as a substrate as well as a sensibilizer, and being used in display, infrared detection, anti-counterfeit, biomarker and other fields.

Description

A kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix
Technical field
The present invention relates to a kind of multiband fluorescence infrared up-conversion material, particularly a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix.
Background technology
Up-conversion is a kind of material that long wavelength light is converted to short-wavelength light output.Particularly up-conversion is extended to and a kind of infrared light is changed into effective material of visible light, and reached practical level.At present, can realize the output of the light of colors such as red, green, blue, purple by infrared upward conversion regime, existing patent of invention comprises red colour conversion material (CN01138926.5), blue colour conversion material (CN01138927.3), green colour conversion material (CN01138928.1) etc.
For a certain up-conversion, common composition comprises matrix, luminescence center and sensitizing agent.Matrix generally is the monobasic of broad stopband or polynary fluorochemical, oxide compound or oxyfluoride crystal, glass, as LaF 3, YF 3, Y 2O 3, LiYF 4, BaY 2F 8Crystal and ZrF 4-BaF 2-LaF 3-NaF, SiO 2-PbF 2Glass etc.Luminescence center is then by Ho 3+, Er 3+, Tm 3+, Pr 3+Plasma constitutes.
In the preparation of infrared up-conversion material, adopt Yb usually 3+Ion is as sensitizing agent, and this is because Yb 3+The stronger uptake factor that ion has in 930-1000nm broad wavelength region, and its level structure is also simple relatively, Yb 3+Can realize sensitization to other rare-earth luminescent center effectively behind the ionic absorption energy, thereby realize the effectively luminous of other rare-earth luminescent center.In report in the past, Yb 3+Ion is introduced in other matrix as sensitized ions usually, to realize the increase of conversion intensity.But weak point is, because of Yb 3+Ion is introduced separately into as sensitized ions usually, and its content is often introduced lower, is no more than 50% (mol) at most, too high Yb 3+Ion is considered to usually to cause the backward energy transmission in the past and makes the up-conversion fluorescence cancellation.In fact, this along with Yb 3+Ionic concn increases and causes the fact of the cancellation of up-conversion fluorescence to be proved, and is considered to a reliable rule for a long time.But, this rule is at doping Yb 3+(being generally less than 50%) draws under the lower situation of ionic threshold concentration.In further research, learn, at pure YbF this rule 3In mix suitable luminescence center (this moment Yb 3+Concentration has reached 95%, and YbF 3Become substrate material simultaneously), can suppress the backward energy transmission to a certain extent effectively on the contrary, can strengthen Yb greatly again on the other hand 3+-Yb 3+The cooperation transmission ofenergy probability of ion pair, thus realize going up conversion efficiently.
Summary of the invention
At above-mentioned situation, the purpose of this invention is to provide a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix, it is with YbF 3Make matrix and sensitizing agent, by at purified YbF 3In mix Ho 3+, Er 3+, Tm 3+, Pr 3+At least a ion is as the up-conversion luminescence center in four kinds of ions, realizes that the efficient up-conversion fluorescence output and the moiety of multi-wavelength is simple, synthetic easily, stability is high, cost is low.
For solving above-mentioned task, a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix, its sensitizing agent and matrix are YbF 3, and at YbF 3Middle doping Ho 3+, Er 3+, Tm 3+, Pr 3+In at least a ion make Ho through co-precipitation and solid state reaction 3+, Er 3+, Tm 3+, Pr 3+In the YbF of at least a ion doping 3, excite down at the near infrared light of 930-990nm, realize the output of multiband up-conversion fluorescence, the structural formula of prepared compound is M XYb 1-XF 3
Its further step is:
Structural formula of compound M XYb 1-XF 3In M be at least a in Ho, Er, Tm, the Pr element, the Ho that mixes 3+, Er 3+, Tm 3+, Pr 3+Ionic mole total content is 0.0005＞X＜0.09.
It prepares as follows:
(1) at YbF 3In mix Ho 3+, Er 3+, Tm 3+, Pr 3+As activation center, with the nitrate Ho (NO of Ho, Er, Tm, Pr and Yb 3) 3, Er (NO 3) 3, Tm (NO 3) 3, Pr (NO 3) 3, Yb (NO 3) 3Solution or villaumite HoCl 3, ErCl 3, Tm Cl 3, PrCl 3, Yb Cl 3Solution, by the Ho that mixes 3+, Er 3+, Tm 3+, Pr 3+Ionic mole total content is the mixed of 0.0005＞X＜0.09, uses NH 4F or NH 4HF 2Solution is made precipitation reagent, prepares the precursor powder through coprecipitation method;
(2) with above-mentioned precursor powder in 600-750 ℃ by NH 4F (ammonium fluoride) or NH 4HF 2Calcined 1-3 hour under HF (hydrogen fluoride) the gas shield condition that (hydrogen fluoride ammonia) decomposition provides, get product.
The present invention adopts YbF 3Not only make matrix but also make the sensitizing agent material, at purified YbF 3In mix Ho 3+, Er 3+, Tm 3+, Pr 3+As activation center, with nitrate solution or the chloride solution of Ho, Er, Tm, Pr and Yb, by the Ho that mixes 3+, Er 3+, Tm 3+, Pr 3+Ionic mole total content is the mixed of 0.0005＞X＜0.09, uses NH 4F or NH 4HF 2Make precipitation reagent, NH 4F or NH 4HF 2Consumption can guarantee fully to be precipitated as condition; Prepare precursor by coprecipitation method, prepared powder is promptly got product in calcining under the certain temperature under the HF atmosphere protection, HF atmosphere is by NH 4F or NH 4HF 2Pyrolytic decomposition obtains; Promptly in tube furnace, put into certain NH 4F or NH 4HF 2, with sample heating, discharging HF gas and obtain the technical scheme of HF gas shield, it had both overcome the defective that needs the special arrangement of numerous and diverse supply HF gas in the traditional preparation process of such fluorinated material, had overcome traditional YbF again 3Deficiency that can only the nonoculture sensitized material.
The present invention's beneficial effect compared to existing technology is:
(1) fully excavates YbF 3Infrared ray excited down at 930-990nm, can obtain the potential of multiband fluorescence output;
(2) adopt YbF 3Not only made matrix but also make the sensitizing agent material and can satisfy the demand of fields such as demonstration, infrared acquisition, false proof, biomarker, and can promote the development of this type of material area research this type of material;
(3) moiety is simple, and technology is simple, synthetic easily, stability is high, cost is low.
Material of the present invention can be used for technical fields such as demonstration, infrared acquisition, false proof, biomarker.
The present invention is further detailed explanation below in conjunction with embodiment.
Description of drawings
Fig. 1 is the luminescent spectrum of sample under 930nm laser excitation.
Fig. 2 is the luminescent spectrum of sample under 980nm laser excitation.
Fig. 3 is the luminescent spectrum of sample under 980nm laser excitation.
Fig. 4 is the luminescent spectrum of sample under 990nm laser excitation.
Fig. 5 is the luminescent spectrum of sample under 980nm laser excitation.
Fig. 6 is the luminescent spectrum of sample under 980nm laser excitation.
Fig. 7 is the luminescent spectrum of sample under 980nm laser excitation.
Fig. 8 is the luminescent spectrum of sample under 980nm laser excitation.
Fig. 9 is the luminescent spectrum of sample under 980nm laser excitation.
Figure 10 is the luminescent spectrum of sample under 980nm laser excitation.
Figure 11 is the luminescent spectrum of sample under 980nm laser excitation.
Figure 12 is the luminescent spectrum of sample under 980nm laser excitation.
Figure 13 is the luminescent spectrum of sample under 980nm laser excitation.
Figure 14 is the luminescent spectrum of sample under 980nm laser excitation.
Figure 15 is the luminescent spectrum of sample under 980nm laser excitation.
Figure 16 is the luminescent spectrum of sample under 960nm laser excitation.
Embodiment
Embodiment 1
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Er 0.001Yb 0.999F 3
(1) Er (NO of elder generation's preparation 0.2M 3) 3, Yb (NO 3) 3And NH 4HF 2Solution.(2) accurately take by weighing Er (NO respectively with transfer pipet 3) 30.065 milliliter of solution, Yb (NO 3) 364.94 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 400 milliliters NH again into 4F solution continues to stir, and makes it precipitation.(3) the gained throw out is filtered, put into baking box in 80 ℃ of bakings 2 hours, put it into then in the crucible, move in the tube furnace, in tube furnace, put into a crucible in addition, put into 2 and restrain NH with behind the distilled water flushing 3 times 4HF 2, the tube furnace two ends are sealed with spun yarn.(4) 600 ℃ of calcinings 3 hours, naturally cooling promptly got sample.
The luminescent spectrum of sample under 930nm laser excitation is referring to Fig. 1.
Embodiment 2
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Er 0.01Yb 0.99F 3
(1) ErCl of elder generation's preparation 0.2M 3, YbCl 3And NH 4HF 2Solution.(2) accurately take by weighing ErCl respectively with transfer pipet 30.65 milliliter of solution, YbCl 364.35 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 200 milliliters NH again into 4F solution continues to stir, and makes it precipitation.(3) the gained throw out is filtered, put into baking box in 80 ℃ of bakings 2 hours, put it into then in the crucible, move in the tube furnace, in tube furnace, put into a crucible in addition, put into 4 and restrain NH with behind the distilled water flushing 3 times 4F, the tube furnace two ends are sealed with spun yarn.(4) 750 ℃ of calcinings 1 hour, naturally cooling promptly got sample.
The luminescent spectrum of sample under 980nm laser excitation is referring to Fig. 2.
Embodiment 3
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Er 0.09Yb 0.91F 3(1) Er (NO of elder generation's preparation 0.2M 3) 3, Yb (NO 3) 3And NH 4HF 2Solution.(2) accurately take by weighing Er (NO respectively with transfer pipet 3) 35.88 milliliters of solution, Yb (NO 3) 359.45 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 200 milliliters NH again into 4HF 2Solution continues to stir, and makes it precipitation.(3) the gained throw out is filtered, put into baking box in 80 ℃ of bakings 2 hours, put it into then in the crucible, move in the tube furnace, put into a crucible at tube furnace in addition, put into 2 and restrain NH with behind the distilled water flushing 3 times 4F, the tube furnace two ends are sealed with spun yarn.(4) 600 ℃ of calcinings 2 hours, naturally cooling promptly got sample.
The luminescent spectrum of sample under 980nm laser excitation is referring to Fig. 3.
Embodiment 4
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Ho 0.001Yb 0.999F 3(1) HoCl of elder generation's preparation 0.2M 3, YbCl 3And NH 4HF 2Solution.(2) accurately take by weighing HoCl respectively with transfer pipet 30.065 milliliter of solution, YbCl 364.94 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 210 milliliters NH again into 4HF 2Solution continues to stir, and makes it precipitation.(3) the gained throw out is filtered, put into baking box in 80 ℃ of bakings 2 hours, put it into then in the crucible, move in the tube furnace, put into a crucible at tube furnace in addition, put into 2 and restrain NH with behind the distilled water flushing 3 times 4HF 2, the tube furnace two ends are sealed with spun yarn.(4) 750 ℃ of calcinings 2 hours, naturally cooling promptly got sample.
The luminescent spectrum of sample under 990nm laser excitation is referring to Fig. 4.
Embodiment 5
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Ho 0.005Yb 0.995F 3(1) Ho (NO of elder generation's preparation 0.2M 3) 3, Yb (NO 3) 3And NH 4HF 2Solution.(2) accurately take by weighing Ho (NO respectively with transfer pipet 3) 30.326 milliliter of solution, Yb (NO 3) 364.87 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 190 milliliters NH again into 4HF 2Solution continues to stir, and makes it precipitation.(3) the gained throw out is filtered, put into baking box in 80 ℃ of bakings 2 hours, put it into then in the crucible, move in the tube furnace, put into a crucible at tube furnace in addition, put into 2 and restrain NH with behind the distilled water flushing 3 times 4HF 2, the tube furnace two ends are sealed with spun yarn.(4) 700 ℃ of calcinings 2 hours, naturally cooling promptly got sample.
The luminescent spectrum of sample under 980nm laser excitation is referring to Fig. 5.
Embodiment 6
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Ho 0.012Yb 0.988F 3(1) Ho (NO of elder generation's preparation 0.2M 3) 3, Yb (NO 3) 3And NH 4HF 2Solution.(2) accurately take by weighing Ho (NO respectively with transfer pipet 3) 30.777 milliliter of solution, Yb (NO 3) 364.55 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 190 milliliters NH again into 4HF 2Solution continues to stir, and makes it precipitation.(3) the gained throw out is filtered, put into baking box in 80 ℃ of bakings 2 hours, put it into then in the crucible, move in the tube furnace, put into a crucible at tube furnace in addition, put into 2.5 and restrain NH with behind the distilled water flushing 3 times 4HF 2, the tube furnace two ends are sealed with spun yarn.(4) 750 ℃ of calcinings 2 hours, naturally cooling promptly got sample.
The luminescent spectrum of sample under 980nm laser excitation is referring to Fig. 6.
Embodiment 7
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Tm 0.001Yb 0.999F 3(1) Tm (NO of elder generation's preparation 0.2M 3) 3, Yb (NO 3) 3And NH 4HF 2Solution.(2) accurately take by weighing Tm (NO respectively with transfer pipet 3) 30.065 milliliter of solution, Yb (NO 3) 364.94 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 200 milliliters NH again into 4HF 2Solution continues to stir, and makes it precipitation.(3) the gained throw out is filtered, put into baking box in 80 ℃ of bakings 2 hours, put it into then in the crucible, move in the tube furnace, put into a crucible at tube furnace in addition, put into 2 and restrain NH with behind the distilled water flushing 3 times 4HF 2, the tube furnace two ends are sealed with spun yarn.(4) 750 ℃ of calcinings 1.5 hours, naturally cooling promptly got sample.
The luminescent spectrum of sample under 980nm laser excitation is referring to Fig. 7.
Embodiment 8
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Tm 0.003Yb 0.997F 3(1) Tm (NO of elder generation's preparation 0.2M 3) 3, Yb (NO 3) 3And NH 4HF 2Solution.(2) accurately take by weighing Tm (NO respectively with transfer pipet 3) 30.1957 milliliter of solution, Yb (NO 3) 365.04 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 205 milliliters NH again into 4HF 2Solution continues to stir, and makes it precipitation.(3) the gained throw out is filtered, put into baking box in 80 ℃ of bakings 2 hours, put it into then in the crucible, move in the tube furnace, put into a crucible at tube furnace in addition, put into 2 and restrain NH with behind the distilled water flushing 3 times 4HF 2, the tube furnace two ends are sealed with spun yarn.(4) 750 ℃ of calcinings 2 hours, naturally cooling promptly got sample.
The luminescent spectrum of sample under 980nm laser excitation is referring to Fig. 8.
Embodiment 9
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Tm 0.004Yb 0.996F 3(1) Tm (NO of elder generation's preparation 0.2M 3) 3, Yb (NO 3) 3And NH 4HF 2Solution.(2) accurately take by weighing Tm (NO respectively with transfer pipet 3) 30.26 milliliter of solution, Yb (NO 3) 364.74 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 200 milliliters NH again into 4HF 2Solution continues to stir, and makes it precipitation.(3) the gained throw out is filtered, put into baking box in 80 ℃ of bakings 2 hours, put it into then in the crucible, move in the tube furnace, put into a crucible at tube furnace in addition, put into 2 and restrain NH with behind the distilled water flushing 3 times 4HF 2, the tube furnace two ends are sealed with spun yarn.(4) 700 ℃ of calcinings 2 hours, naturally cooling promptly got sample.
The luminescent spectrum of sample under 980nm laser excitation is referring to Fig. 9.
Embodiment 10
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Tm 0.0005Ho 0.001Yb 0.9985F 3(1) Ho (NO of elder generation's preparation 0.2M 3) 3, Tm (NO 3) 3, Yb (NO 3) 3And NH 4HF 2Solution.(2) accurately take by weighing Tm (NO respectively with transfer pipet 3) 30.0326 milliliter of solution, Ho (NO 3) 30.065 milliliter of solution, Yb (NO 3) 364.9 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 220 milliliters NH again into 4HF 2Solution continues to stir, and makes it precipitation.(3) the gained throw out is filtered, put into baking box in 80 ℃ of bakings 2 hours, put it into then in the crucible, move in the tube furnace, put into a crucible at tube furnace in addition, put into 3 and restrain NH with behind the distilled water flushing 3 times 4HF 2, the tube furnace two ends are sealed with spun yarn.Calcined 2 hours for (4) 750 ℃, naturally cooling promptly gets sample.
The luminescent spectrum of sample under 980nm laser excitation is referring to Figure 10.
Embodiment 11
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Tm 0.001Ho 0.001Yb 0.998F 3(1) Ho (NO of elder generation's preparation 0.2M 3) 3, Tm (NO 3) 3, Yb (NO 3) 3And NH 4HF 2Solution.(2) accurately take by weighing Tm (NO respectively with transfer pipet 3) 30.065 milliliter of solution, Ho (NO 3) 30.065 milliliter of solution, Yb (NO 3) 364.87 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 210 milliliters NH again into 4HF 2Solution continues to stir, and makes it precipitation.(3) the gained throw out is filtered, put into baking box in 80 ℃ of bakings 4 hours, put it into then in the crucible, move in the tube furnace, put into a crucible at tube furnace in addition, put into 2 and restrain NH with behind the distilled water flushing 3 times 4HF 2, the tube furnace two ends are sealed with spun yarn.(4) 650 ℃ of calcinings 2 hours, naturally cooling promptly got sample.
The luminescent spectrum of sample under 980nm laser excitation is referring to Figure 11.
Embodiment 12
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Tm 0.001Ho 0.002Yb 0.997F 3(1) Ho (NO of elder generation's preparation 0.2M 3) 3, Tm (NO 3) 3, Yb (NO 3) 3And NH 4HF 2Solution.(2) accurately take by weighing Tm (NO respectively with transfer pipet 3) 30.065 milliliter of solution, Ho (NO 3) 30.13 milliliter of solution, Yb (NO 3) 364.81 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 220 milliliters NH again into 4HF 2Solution continues to stir, and makes it precipitation.(3) the institute throw out is filtered, put into baking box in 80 ℃ of bakings 2 hours, put it into then in the crucible, move in the tube furnace, put into a crucible at tube furnace in addition, put into 2 and restrain NH with behind the distilled water flushing 3 times 4HF 2, the tube furnace two ends are sealed with spun yarn.(4) 750 ℃ of calcinings 2 hours, naturally cooling promptly got sample.
The luminescent spectrum of sample under 980nm laser excitation is referring to Figure 12.
Embodiment 13
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Tm 0.001Er 0.001Yb 0.998F 3(1) Er (NO of elder generation's preparation 0.2M 3) 3, Tm (NO 3) 3, Yb (NO 3) 3And NH 4HF 2Solution.(2) accurately take by weighing Tm (NO respectively with transfer pipet 3) 30.065 milliliter of solution, Er (NO 3) 30.065 milliliter of solution, Yb (NO 3) 364.87 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 210 milliliters NH again into 4HF 2Solution continues to stir, and makes it precipitation.(3) the gained throw out is filtered, put into baking box in 80 ℃ of bakings 2 hours, put it into then in the crucible, move in the tube furnace, put into a crucible at tube furnace in addition, put into 2 and restrain NH with behind the distilled water flushing 3 times 4HF 2, the tube furnace two ends are sealed with spun yarn.(4) 750 ℃ of calcinings 3 hours, naturally cooling promptly got sample.
The luminescent spectrum of sample under 980nm laser excitation is referring to Figure 13.
Embodiment 14
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Tm 0.001Er 0.002Yb 0.997F 3(1) prepare earlier the Er (NO of 0.2M 3) 3, Tm (NO 3) 3, Yb (NO 3) 3And NH 4HF 2Solution.(2) accurately take by weighing Tm (NO respectively with transfer pipet 3) 30.065 milliliter of solution, Er (NO 3) 30.13 milliliter of solution, Yb (NO 3) 364.81 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 210 milliliters NH again into 4HF 2Solution continues to stir, and makes it precipitation.(3) the gained throw out is filtered, put into baking box in 80 ℃ of bakings 2 hours, put it into then in the crucible, move in the tube furnace, put into a crucible at tube furnace in addition, put into 2 and restrain NH with behind the distilled water flushing 3 times 4HF 2, the tube furnace two ends are sealed with spun yarn.(4) 750 ℃ of calcinings 2 hours, naturally cooling promptly got sample.
The luminescent spectrum of sample under 980nm laser excitation is referring to Figure 14.
Embodiment 15
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Tm 0.001Er 0.004Yb 0.995F 3(1) Er (NO of elder generation's preparation 0.2M 3) 3, Tm (NO 3) 3, Yb (NO 3) 3And NH 4HF 2Solution.(2) accurately take by weighing Tm (NO respectively with transfer pipet 3) 30.065 milliliter of solution, Er (NO 3) 30.26 milliliter of solution, Yb (NO 3) 364.68 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 110 milliliters NH again into 4HF 2Solution continues to stir, and makes it precipitation.(3) the gained throw out is filtered, put into baking box in 80 ℃ of bakings 2 hours, put it into then in the crucible, move in the tube furnace, put into a crucible at tube furnace in addition, put into 2 and restrain NH with behind the distilled water flushing 3 times 4HF 2, the tube furnace two ends are sealed with spun yarn.(4) 750 ℃ of calcinings 2 hours, naturally cooling promptly got sample.
The luminescent spectrum of sample under 980nm laser excitation is referring to Figure 15.
Embodiment 16
The chemical expression of a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix of the present invention is Tm 0.001Pr 0.001Yb 0.998F 3(1) Er (NO of elder generation's preparation 0.2M 3) 3, Tm (NO 3) 3, Yb (NO 3) 3And NH 4HF 2Solution.(2) accurately take by weighing Tm (NO respectively with transfer pipet 3) 30.065 milliliter of solution, Pr (NO 3) 30.065 milliliter of solution, Yb (NO 3) 364.87 milliliters of solution are poured beaker into, after fully stirring under magnetic stirring apparatus, pour 110 milliliters NH again into 4HF 2Solution continues to stir, and makes it precipitation.(3) the gained throw out is filtered, put into baking box in 80 ℃ of bakings 2 hours, put it into then in the crucible, move in the tube furnace, put into a crucible at tube furnace in addition, put into 2 and restrain NH with behind the distilled water flushing 3 times 4HF 2, the tube furnace two ends are sealed with spun yarn.(4) 750 ℃ of calcinings 2 hours, naturally cooling promptly got sample.
The luminescent spectrum of sample under 960nm laser excitation is referring to Figure 16.

Claims (2)

1. the multiband fluorescence infrared up-conversion material based on sensitizing agent matrix is characterized in that its sensitizing agent and matrix are YbF 3, and at YbF 3Middle doping Ho 3+, Er 3+, Tm 3+, Pr 3+In at least a ion make Ho through co-precipitation and solid state reaction 3+, Er 3+, Tm 3+, Pr 3+In the YbF of at least a ion doping 3, excite down at the near infrared light of 930-990nm, realize the output of multiband up-conversion fluorescence, the structural formula of prepared compound is M XYb 1-XF 3, this M XYb 1-XF 3In M be at least a in Ho, Er, Tm, the Pr element, the Ho that mixes 3+, Er 3+, Tm 3+, Pr 3+Ionic mole total content is 0.0005＜X＜0.09.
2. a kind of multiband fluorescence infrared up-conversion material based on sensitizing agent matrix according to claim 1 is characterized in that it prepares as follows:
(1) at YbF 3In mix Ho 3+, Er 3+, Tm 3+, Pr 3+As activation center, with the nitrate Ho (NO of Ho, Er, Tm, Pr and Yb 3) 3, Er (NO 3) 3, Tm (NO 3) 3, Pr (NO 3) 3, Yb (NO 3) 3Solution or villaumite HoCl 3, ErCl 3, TmCl 3, PrCl 3, YbCl 3Solution, by the Ho that mixes 3+, Er 3+, Tm 3+, Pr 3+Ionic mole total content is the mixed of 0.0005＜X＜0.09, uses NH 4F or NH 4HF 2Solution is made precipitation reagent, prepares the precursor powder through coprecipitation method;
(2) with above-mentioned precursor powder in 600-750 ℃ by NH 4F or NH 4HF 2Decompose under the HF gas shield condition that provides and calcined 1-3 hour, get product.
CN2007101926498A 2007-12-18 2007-12-18 Multi-band fluorescent infrared up-conversion material based on sensitizer substrate Expired - Fee Related CN101225304B (en)

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