CN101289616A - Process for preparing water-soluble up-conversion NaYF4:Er<3+>,Yb<3+> nano-crystalline using glycyl alcohol as solvent - Google Patents
Process for preparing water-soluble up-conversion NaYF4:Er<3+>,Yb<3+> nano-crystalline using glycyl alcohol as solvent Download PDFInfo
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- CN101289616A CN101289616A CN 200810050811 CN200810050811A CN101289616A CN 101289616 A CN101289616 A CN 101289616A CN 200810050811 CN200810050811 CN 200810050811 CN 200810050811 A CN200810050811 A CN 200810050811A CN 101289616 A CN101289616 A CN 101289616A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 84
- 239000002904 solvent Substances 0.000 title claims abstract description 30
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- 229960005150 glycerol Drugs 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 30
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims description 31
- 238000005119 centrifugation Methods 0.000 claims description 25
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- 229910052691 Erbium Inorganic materials 0.000 claims description 2
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- 230000008569 process Effects 0.000 abstract description 6
- SQGMBDQWNFMOIU-UHFFFAOYSA-N propane-1,1,1-triol;propane-1,2,3-triol Chemical compound CCC(O)(O)O.OCC(O)CO SQGMBDQWNFMOIU-UHFFFAOYSA-N 0.000 abstract 4
- 239000002159 nanocrystal Substances 0.000 abstract 2
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to a method for making water-soluble upconversion NaYF4: Er<3+>, Yb<3+> nano crystal through taking glycerol propanetriol as solvent. The method is as follows: NaF is dissolved in glycerol propanetriol solvent to obtain a solution A, and then EDTA is dissolved in glycerol propanetriol to obtain a solution B; Er (NO3) 3, Yb (NO3) 3 and Y (NO3) 3 are dissolved in glycerol propanetriol solvent to obtain a solution C; the solution A and the solution B are mixed to obtain a solution D, and then the solution C is added in the solution D; moreover, n(EDTA)/n(RE) is equal to 1:0.5 to 1:5 (mol), wherein n(EDTA) is the total mol dosage of EDTA, while n(RE) is the sum of the mol dosage of Er<3+>, Yb<3+> and Y<3+>; the solutions are stirred to carry out reaction at the temperature of between 200 and 297 DEG C for 1 to 3 hours; and the product is excitated by 980nm infrared light after drying so as to make the bright fluorescence upconversion NaYF4: Er<3+>, Yb<3+> nano crystal apparent to the naked eye. The method obtains simplified process, energy conservation and improved water solubility.
Description
Technical field
The invention belongs to the preparation method of rare earth ion up-conversion luminescent material, relating to a kind of specifically is that solvent prepares the water-soluble conversion NaYF that goes up with the glycerol
4: Er
3+, Yb
3 +Nanocrystalline method.
Background technology
The rare earth ion up-conversion luminescent material has good application prospects in laser technology and optical fiber communication technology, fibre amplifier, technique of display and many meal such as false proof.Recently, cause people's concern widely as the biomolecules fluorescence labeling probe with up-conversion.Advantages such as up-conversion has the generation of being difficult for photobleaching, and luminous intensity height and laser intensity are low are used in the mark and can improve detection sensitivity and linearity range greatly.
The infrared ray excited polycrystalline ZnS of 960nm just occurs utilizing as far back as nineteen fifty-nine, and observed the report of 525nm green emitting.1962, the up-conversion luminescence phenomenon obtained further confirmation again in selenium compound, and the efficient that infrared radiation converts visible light to has reached quite high level.。Found in 1966 in substrate material, to mix Yb
3+During ion, Er
3+, Ho
3+tAnd Tm
3+Ion is when infrared ray excited, and visible luminous two orders of magnitude that almost improved have formally proposed the viewpoint of " up-conversion luminescence " thus.In the more than ten years after this, but up-conversion just develop into for a kind of infrared light be converted to effective material of light, and reached practical level.Develop the peak first time that up-conversion Development of Materials in 1974 has welcome it.
At the beginning of the nineties, develop the peak second time that up-conversion has welcome it.This is output as ultimate aim to realize room temperature laser, utilize up-conversion to realize that laser output has obtained stem-winding achievement: at room temperature, in crystal of fluoride, also successfully obtained laser operation, light-light conversion efficiency has surpassed 1%, up to 1.4%, thereby make infrared excitation one transition material show practical widely prospect in fields such as demonstration, photometry calculation and work and rest processing.
In recent years, nano material became new research focus in the rare earth ion up-conversion luminescence field.Nano luminescent material has shown characteristics such as small-size effect, high-ratio surface effect, quantum effect.Have special optical property simultaneously, these performances all have very strong dependence with the size of nanoparticle.Except the rare earth ion up-conversion luminescence having been carried out research in field of inorganic materials, people also begin to seek efficient, stable rare earth ion up-conversion luminescent material to satisfy people's requirement in organic field.Nineteen ninety-five, Brodin etc. mix Er in poly-oxyethylene film
3+, observed intensive green glow and faint blue light under the 650nm pumping.2000, Auzel introduced organic precursors when the fluorphosphate glass of preparation doping with rare-earth ions, well improved the characteristic of glass, makes the distribution uniform of rare earth ion in glass.Nanometer ZrO
2, Y
2O
3Be subjected to people's attention Deng material owing to having lower phonon energy, but when being in nano-scale, the H of surface adsorption
2O and CO
2Absorbed more exciting light energy and the luminous efficiency of material is reduced; Simultaneously, the sintering ability crystallization of these material requires above 1000 ℃ consumes energy big and particle is easily reunited, and size is difficult to control.
The nearest higher NaYF of luminous efficiency
4: Er
3+, Yb
3+Last conversion nano crystalline substance is in the news out, and this material can be observed intense fluorescence 500 ℃ of following crystallization, and it is the highest upconverting fluorescent material of luminous efficiency so far.Comparatively Chang Yong preparation method is sol-gel-solid sintering technology, and this method mainly is to react 30～40min to generate precursor under the aqueous phase room temperature, and precursor carries out the retort furnace sintering again, makes its crystallization obtain NaYF
4: Er
3+, Yb
3+The brilliant sample of last conversion nano.
Summary of the invention
The objective of the invention is to overcome the problem that prior art exists, providing a kind of is that solvent prepares the water-soluble conversion NaYF that goes up with the glycerol
4: Er
3+, Yb
3+Nanocrystalline method is saved the retort furnace sintering step, has simplified technology, saves the energy, has improved the dispersiveness of product in the aqueous solution etc.
The objective of the invention is to realize by the following technical solutions
With the glycerol is that solvent prepares the water-soluble conversion NaYF that goes up
4: Er
3+, Yb
3+Nanocrystalline method is dissolved in NaF in the glycerol solvent and obtains solution A; Again complexing agent EDTA is dissolved in the glycerol solvent and obtains solution B; Er (NO3) 3, Yb (NO3) 3, Y (NO3) 3 all are dissolved in the glycerol solvent and obtain solution C; Solution A, solution B mixing are obtained solution D; Again solution C is added in the solution D, heats while stirring, react 1h～3h down in 200 ℃～297 ℃; EDTA and (Y
3++ Er
3++ Yb
3+) ratio of mole dosage sum is 1: 1; Wherein, (Y
3++ Er
3++ Yb
3+) the mole dosage sum is 100, Y wherein
3+Account for 80%, Er
3+Account for 3%, Yb
3+Account for 17%; After reaction finishes,, collect solid product after drying with the reaction mixture centrifugation, infrared ray excited with 980nm, observe with the naked eye bright up-conversion fluorescence.Measure with XRD, ° main peak place in 2 θ=28.1417, peak width at half height is 0.1617 °, calculates grain fineness number according to Scherrer ' s D=K λ/β cos θ formula and is of a size of 88.4nm; Recording the particle mean sizes with transmission electron microscope is 95nm, is consistent with XRD calculation result.
Prepare the water-soluble conversion NaYF that goes up with the glycerol solvent
4: Er
3+, Yb
3+Nanocrystalline method, the product that makes is infrared ray excited through 980nm, is observed visually conversion NaYF
4: Er
3+, Yb
3+Nanocrystalline fluorescence intensity strengthens along with the rising of temperature of reaction.
Above-mentioned is that solvent prepares the water-soluble conversion NaYF that goes up with the glycerol
4: Er
3+, Yb
3 +Nanocrystalline method, NaYF is changed in going up of making
4: Er
3+, Yb
3+Nanocrystalline, infrared ray excited through 980nm, its green fluorescence intensity is along with the Er that mixes
3+Or Yb
3Volumetric molar concentration improve and to diminish gradually, and red fluorescence intensity obviously increases.
The present invention's (hereinafter to be referred as glycerol method) compares with prior art (abbreviation sintering process) has following marked improvement and positively effect:
(1) the present invention is the water-soluble conversion NaYF that goes up of solvent (hereinafter to be referred as the glycerol method) preparation with the glycerol
4: Er
3+, Yb
3+Nanocrystalline, intermediates have saved the retort furnace sintering step in 70 ℃ of dryings, simplify technology;
(2) the present invention is that solvent has significantly reduced energy consumption with the higher glycerol of boiling point;
(3) with 70 ℃ of dry retort furnace sintering that replace, avoided high-temperature calcination product generation particle adhesion, particle diameter increases, thereby has obviously improved the dispersiveness of product in the aqueous solution.
(4) as can be seen: the NaYF that glycerol method of the present invention obtains from Fig. 1 fluorogram
4: Er
3+, Yb
3+Nanocrystalline luminous intensity obviously strengthens.
(5) from Fig. 2 NaYF
4: E
3+, Yb
3+Nanocrystalline XRD figure spectrum is as seen: the present invention has used high boiling point glycerol solvent method more to help obtaining the nanocrystalline material of high-luminous-efficiency, and with the rising of temperature, luminous intensity increase.
Description of drawings
1 is last conversion NaYF
4: Er
3+, Yb
3+Nanocrystalline up-conversion fluorescence spectrogram; Wherein
The NaYF that A-sol-gel-solid sintering technology obtains
4: Er
3+, Yb
3+Nanocrystalline up-conversion fluorescence spectral line;
The NaYF that B-glycerol solvent method obtains
4: Er
3+, Yb
3+Nanocrystalline up-conversion fluorescence spectral line;
Fig. 2 is NaYF
4: E
3+, Yb
3+Nanocrystalline XRD figure spectrum; Wherein
The NaYF that 1-sol-gel-solid sintering technology obtains
4: E
3+, Yb
3+Nanocrystalline XRD spectral line;
2-glycerol solvent method of the present invention makes NaYF
4: E
3+, Yb
3+Nanocrystalline XRD spectral line;
The NaYF of Fig. 3 sol-gel-solid sintering technology preparation
4: E
3+, Yb
3+Nanocrystalline TEM (transmission electron microscope) photo; Scale is 350nm
Fig. 4 is the NaYF of glycerol solvent method preparation of the present invention
4: E
3+, Yb
3+Nanocrystalline TEM figure (diaphotoscope) photo; Scale is 350nm
The present invention is by using transmission electron microscope (TEM), and X-ray powder diffraction (XRD) and fluorescence spectrophotometry meter are to making upper conversion NaYF4:E
3+，Yb
3+The nanometer crystalline substance is measured, and it the results are shown among the upper figure and following described content.
Fig. 1 is that colloidal sol-gel-casting sintering process and glycerine solvent legal system of the present invention get up-conversion fluorescence spectrum line, and excitation source is 980nm, and the green glow corresponding wavelength is about 540nm, and the ruddiness corresponding wavelength is about 660nm. Relatively two spectrums of A, B line is found the present invention standby NaYF of glycerine solvent legal system4:Er
3+，Yb
3+The luminous intensity of nanometer crystalline substance obviously strengthens.
Abscissa is 2 θ among Fig. 2, and ordinate is energy intensity. Spectrum line 1 is NaYF4:Er
3+，Yb
3+Nanometer crystalline substance measured X-ray powder diffraction (XRD) collection of illustrative plates behind 2 ℃ of roasting 3h. Spectrum line 2 is NaYF4:Er
3+，Yb
3+The nanometer crystalline substance prepares measured XRD collection of illustrative plates in glycerine. Spectrum line 1 and spectrum line 2 are compared, and can find out and react 3h in glycerine, are accompanied by a cube crystal (ICDD, No.77-2042) and hexagonal crystal (ICDD, No.28-1192) occurred. NaYF4:Er
3+，Yb
3+The nanometer crystalline substance is proved in brilliant type in the situation of solid-phase sintering along with temperature changes: between 300-℃ for cube and hexagonal crystallographic system mixture, present simple cube phase in the situation of 7 ℃ of sintering, the mixture of cube phase and hexagonal phase appears again during greater than 7 ℃. Because the brilliant type of hexagonal phase is lower than the symmetry of cube phase, cause the Stark division of more Er energy level, more be conducive to switching emission, therefore use higher boiling glycerine solvent method more to be conducive to obtain the material of high-luminous-efficiency, and with the rising of temperature, luminous intensity increases.
Spectrum line 2 among Fig. 2 XRD figure, ° main peak place in 2 θ=28.1417, half-peak breadth is 0.1617 °, instrument is bootstrapped wide 0.09 °, calculates grain size according to Scherrer ' s formula:
D＝Kλ/βcosθ
In the formula, K=0.9, D are crystalline sizes, and λ is the emission wavelength of copper target, value 0.15406nm, and β represents half-peak breadth, calculates crystal grain and is of a size of 88.4nm.
Fig. 3 is the NaYF of colloidal sol-gel-casting sintering process preparation4:Er
3+，Yb
3+The TEM photo scale of nanometer crystalline substance is 350nm; Fig. 4 be by glycerine solvent legal system of the present invention to NaYF4:Er
3+，Yb
3+The TEM photo of nanometer crystalline substance, scale are 350nm. Transmission electron microscope characterizes and records the particle average-size is 95nm, is consistent with XRD result of calculation. Compare discovery by the TEM photo that two kinds of methods is prepared sample, adopt the NaYF of colloidal sol-gel-casting sintering process preparation4:Er
3+，Yb
3+Nanometer is brilliant, and size is inhomogeneous owing to high temperature sintering generation particle adhesion, and adopts the standby sample size uniform of glycerine solvent legal system, and the spherical particle that is easy to get is because avoided solid-phase sintering to cause interparticle contact Cheng Jian.
By the proportionate relationship (other operating procedure and condition with embodiment 1) of the reaction condition that provides in table 1 and the table 2 with the amount of a material, change respectively Er3+，Yb
3+Doping content, by visually observing comparison, find along with the Er that mixes3+The raising of ion concentration, green emission intensity diminishes gradually, and ruddiness is sent out intensity and is obviously increased; Along with the Yb that mixes3+The raising of ion concentration, green emission intensity diminishes gradually, and red emission intensity obviously increases; And no matter be to change Er3+Ion or Yb3+Ion mix concentration, green emission intensity all diminishes gradually with the raising of mixing concentration, red emission intensity then obviously increases.
Embodiment
In conjunction with embodiment, the invention will be further described below by accompanying drawing.
Embodiment 1
Conversion NaYF in the preparation
4: Er
3+, Yb
3+Nanocrystalline method is reacted and is that 1h, temperature of reaction are 220 ℃, and n (EDTA)/n (RE) mol ratio is 1: 1, wherein, the total mole dosage of n (EDTA) expression ETDA, n (RE) represents (Y
3+, Er
3+, Yb
3+) the mole dosage sum; Form by following process and step:
1) gets 1.05g NaF and put into Erlenmeyer flask, add the 150ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution A with electric furnace.
2) get 0.7445g EDTA and put into Erlenmeyer flask, add the 50ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution B with electric furnace.
3) take by weighing 0.0212g Er (NO respectively
3)
3, 0.1221g Yb (NO
3)
3, 0.4198gY (NO
3)
3Put into same Erlenmeyer flask, add the 50ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution C with electric furnace.
4) solution A and solution B mixing are obtained solution D, and move in the there-necked flask.
5) solution C is added in the solution D, with the electric furnace heating, the limit heating edge stirs with electric mixer.
6) strict control reaction temperature is 220 ℃, and reaction continues 1h.
7) with reacted mixing solutions with the dilution of 1000ml deionized water, and then to use whizzer centrifugation, rotating speed be 5000r/min, centrifugation time is 15min.
8) product that centrifugation is gone out is put into baking oven and is dried, and bake out temperature is 70 ℃, and drying time is 24h.
9) product after will drying excites with the semiconductor laser of the 980nm wavelength of 3mW, with the naked eye can observe bright up-conversion fluorescence.
Embodiment 2
Conversion NaYF in the preparation
4: Er
3+, Yb
3+Nanocrystalline, the reaction times is 2h, n (EDTA)/n (RE)=1: 1, and temperature of reaction is 220 ℃.
1) gets 1.05g NaF and put into Erlenmeyer flask, add the 150ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution A with electric furnace.
2) get 0.7445g EDTA and put into Erlenmeyer flask, add the 50ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution B with electric furnace.
3) take by weighing 0.0212g Er (NO respectively
3)
3, 0.1221g Yb (NO
3)
3, 0.4198gY (NO
3)
3Put into same Erlenmeyer flask, add the 50ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution C with electric furnace.
4) solution A and solution B mixing are obtained solution D, and move in the there-necked flask.
5) solution C is added in the solution D, with the electric furnace heating, the limit heating edge stirs with electric mixer.
6) strict control reaction temperature is 220 ℃, and reaction continues 2h.
7) with reacted mixing solutions with the dilution of 1000ml deionized water, and then to use whizzer centrifugation, rotating speed be 5000r/min, centrifugation time is 15min.
8) product that centrifugation is gone out is put into baking oven and is dried, and bake out temperature is 70 ℃, and drying time is 24h.
9) product after will drying excites with the semiconductor laser of the 980nm wavelength of 3mW, with the naked eye can observe bright up-conversion fluorescence.
Embodiment 3
Conversion NaYF in the preparation
4: Er
3+, Yb
3+Nanocrystalline, the reaction times is 3h, n (EDTA)/n (RE)=1: 1, and temperature of reaction is 220 ℃.
1) gets 1.05g NaF and put into Erlenmeyer flask, add the 150ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution A with electric furnace.
2) get 0.7445g EDTA and put into Erlenmeyer flask, add the 50ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution B with electric furnace.
3) take by weighing 0.0212g Er (NO respectively
3)
3, 0.1221g Yb (NO
3)
3, 0.4198gY (NO
3)
3Put into same Erlenmeyer flask, add the 50ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution C with electric furnace.
4) solution A and solution B mixing are obtained solution D, and move in the there-necked flask.
5) solution C is added in the solution D, with the electric furnace heating, the limit heating edge stirs with electric mixer.
6) strict control reaction temperature is 220 ℃, and reaction continues 3h.
7) with reacted mixing solutions with the dilution of 1000ml deionized water, and then to use whizzer centrifugation, rotating speed be 5000r/min, centrifugation time is 15min.
8) product that centrifugation is gone out is put into baking oven and is dried, and bake out temperature is 70 ℃, and drying time is 24h.
9) product after will drying excites with the semiconductor laser of the 980nm wavelength of 3mW, with the naked eye can observe bright up-conversion fluorescence.
Embodiment 4
Conversion NaYF in the preparation
4: Er
3+, Yb
3+Nanocrystalline, the reaction times is 2h, n (EDTA)/n (RE)=1: 1, and temperature of reaction is 200 ℃.
1) gets 1.05g NaF and put into Erlenmeyer flask, add the 150ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution A with electric furnace.
2) get 0.7445g EDTA and put into Erlenmeyer flask, add the 50ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution B with electric furnace.
3) take by weighing 0.0212g Er (NO respectively
3)
3, 0.1221g Yb (NO
3)
3, 0.4198gY (NO
3)
3Put into same Erlenmeyer flask, add the 50ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution C with electric furnace.
4) solution A and solution B mixing are obtained solution D, and move in the there-necked flask.
5) solution C is added in the solution D, with the electric furnace heating, the limit heating edge stirs with electric mixer.
6) strict control reaction temperature is 200 ℃, and reaction continues 2h.
7) with reacted mixing solutions with the dilution of 1000ml deionized water, and then to use whizzer centrifugation, rotating speed be 5000r/min, centrifugation time is 15min.
8) product that centrifugation is gone out is put into baking oven and is dried, and bake out temperature is 70 ℃, and drying time is 24h.
9) product after will drying excites with the semiconductor laser of the 980nm wavelength of 3mW, with the naked eye can observe bright up-conversion fluorescence.
Embodiment 5
Conversion NaYF in the preparation
4: Er
3+, Yb
3+Nanocrystalline, the reaction times is 2h, n (EDTA)/n (RE)=1: 1, and temperature of reaction is 240 ℃.
1) gets 1.05g NaF and put into Erlenmeyer flask, add the 150ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution A with electric furnace.
2) get 0.7445g EDTA and put into Erlenmeyer flask, add the 50ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution B with electric furnace.
3) take by weighing 0.0212g Er (NO respectively
3)
3, 0.1221g Yb (NO
3)
3, 0.4198gY (NO
3)
3Put into same Erlenmeyer flask, add the 50ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution C with electric furnace.
4) solution A and solution B mixing are obtained solution D, and move in the there-necked flask.
5) solution C is added in the solution D, with the electric furnace heating, the limit heating edge stirs with electric mixer.
6) strict control reaction temperature is 240 ± 10 ℃, and reaction continues 2h.
7) with reacted mixing solutions with the dilution of 1000ml deionized water, and then to use whizzer centrifugation, rotating speed be 5000r/min, centrifugation time is 15min.
8) product that centrifugation is gone out is put into baking oven and is dried, and bake out temperature is 70 ℃, and drying time is 24h.
9) product after will drying excites with the semiconductor laser of the 980nm wavelength of 3mW, with the naked eye can observe bright up-conversion fluorescence, but also brighter than 220 ℃ of product fluorescence that make.
Embodiment 6
Conversion NaYF in the preparation
4: Er
3+, Yb
3+Nanocrystalline, the reaction times is 2h, n (EDTA)/n (RE)=1: 1, and temperature of reaction is 260 ℃.
1) gets 1.05g NaF and put into Erlenmeyer flask, add the 150ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution A with electric furnace.
2) get 0.7445g EDTA and put into Erlenmeyer flask, add the 50ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution B with electric furnace.
3) take by weighing 0.0212g Er (NO respectively
3)
3, 0.1221g Yb (NO
3)
3, 0.4198gY (NO
3)
3Put into same Erlenmeyer flask, add the 50ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution C with electric furnace.
4) solution A and solution B mixing are obtained solution D, and move in the there-necked flask.
5) solution C is added in the solution D, with the electric furnace heating, the limit heating edge stirs with electric mixer.
6) strict control reaction temperature is 260 ℃, and reaction continues 2h.
7) with reacted mixing solutions with the dilution of 1000ml deionized water, and then to use whizzer centrifugation, rotating speed be 5000r/min, centrifugation time is 15min.
8) product that centrifugation is gone out is put into baking oven and is dried, and bake out temperature is 70 ℃, and drying time is 24h.
9) product after will drying excites with the semiconductor laser of the 980nm wavelength of 3mW, and with the naked eye can observing up-conversion fluorescence, to make product than 240 ℃ also bright.
Embodiment 7
Conversion NaYF in the preparation
4: Er
3+, Yb
3+Nanocrystalline, the reaction times is 2h, n (EDTA)/n (RE)=1: 1, and temperature of reaction is 290 ℃.
1) gets 1.05g NaF and put into Erlenmeyer flask, add the 150ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution A with electric furnace.
2) get 0.7445g EDTA and put into Erlenmeyer flask, add the 50ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution B with electric furnace.
3) take by weighing 0.0212g Er (NO respectively
3)
3, 0.1221g Yb (NO
3)
3, 0.4198gY (NO
3)
3Put into same Erlenmeyer flask, add the 50ml glycerol and heat, heat while stirring, make its whole dissolvings, obtain solution C with electric furnace.
4) solution A and solution B mixing are obtained solution D, and move in the there-necked flask.
5) solution C is added in the solution D, with the electric furnace heating, the limit heating edge stirs with electric mixer.
6) strict control reaction temperature is 290 ℃, and reaction continues 2h.
7) with reacted mixing solutions with the dilution of 1000ml deionized water, and then to use whizzer centrifugation, rotating speed be 5000r/min, centrifugation time is 15min.
8) product that centrifugation is gone out is put into baking oven and is dried, and bake out temperature is 70 ℃, and drying time is 24h.
9) product after will drying excites with the semiconductor laser of the 980nm wavelength of 3mW, with the naked eye can observe bright up-conversion fluorescence, and 260 ℃ of product fluorescence that make of its strength ratio are also strong.
With transmission electron microscope (TEM), X-ray powder diffraction (XRD) and spectrophotofluorometer are changed NaYF to above going up of making
4: Er
3+, Yb
3+The nanocrystalline measurement, it the results are shown in the content of putting down in writing and explaining in the top accompanying drawing.
The foregoing description 1～7, naked eyes can obviously be observed: along with the raising of temperature of reaction, the NaYF that makes
4: Er
3+, Yb
3+Nanocrystalline fluorescent brightness is along with enhancing.
Embodiment 8～20: remove the table intrinsic parameter, all the other conditions and operation steps are with embodiment 2.
The Er that table 1 is different
3+The doping content table
| Embodiment number | N (EDTA)/n (RE) mol ratio | Temperature of reaction (℃) | Reaction times (h) | Yb 3+Concentration (mol%) | Er 3+Concentration (mol%) |
| 8 | 1∶1 | 220 | 2 | 2 | 0.1 |
| 9 | 1∶1 | 220 | 2 | 2 | 0.2 |
| 10 | 1∶1 | 220 | 2 | 2 | 0.4 |
| 11 | 1∶1 | 220 | 2 | 2 | 0.6 |
| 12 | 1∶1 | 220 | 2 | 2 | 0.8 |
| 13 | 1∶1 | 220 | 2 | 2 | 1.0 |
| 14 | 1∶1 | 220 | 2 | 2 | 1.2 |
| 15 | 1∶1 | 220 | 2 | 2 | 1.4 |
| 16 | 1∶1 | 220 | 2 | 2 | 1.6 |
| 17 | 1∶1 | 220 | 2 | 2 | 1.8 |
| 18 | 1∶1 | 220 | 2 | 2 | 2.0 |
| 19 | 1∶1 | 220 | 2 | 2 | 5.0 |
| 20 | 1∶1 | 220 | 2 | 2 | 10.0 |
Embodiment 21～26: except that the table intrinsic parameter, all the other conditions and operation steps are with embodiment 2.
The Yb that table 2 is different
3+The doping content table
| Embodiment | N (EDTA)/n (RE) mol ratio | Temperature of reaction (℃) | Reaction times (h) | Er 3+Concentration (mol%) | Yb 3+Concentration (mol%) |
| 21 | 1∶1 | 220 | 2 | 0.2 | 1.0 |
| 22 | 1∶1 | 220 | 2 | 0.2 | 2.0 |
| 23 | 1∶1 | 220 | 2 | 0.2 | 3.0 |
| 24 | 1∶1 | 220 | 2 | 0.2 | 4.0 |
| 25 | 1∶1 | 220 | 2 | 0.2 | 6.0 |
| 26 | 1∶1 | 220 | 2 | 0.2 | 10.0 |
From example 8～20 and example 21～26, can obviously with the naked eye clearly observe, along with Er
3+Doping content or Yb
3+The raising of doping content makes NaYF
4: Er
3+, Yb
3+Nanocrystalline green fluorescence brightness dies down gradually, and red fluorescence brightness strengthens gradually.
Comparison example
1) takes by weighing 1.05g NaF and put into Erlenmeyer flask, add the 10ml deionized water, use ultrasonic oscillation,, obtain solution A until whole dissolvings.
2) take by weighing 0.7445g EDTA and put into Erlenmeyer flask, add the 10ml deionized water, use ultrasonic oscillation,, obtain solution B until whole dissolvings.
3) take by weighing 0.0212g Er (NO respectively
3)
3, 0.1221g Yb (NO
3)
3, 0.4198gY (NO
3)
3Put into same Erlenmeyer flask, add the 30ml deionized water, stir and make its whole dissolvings, obtain solution C.
4) solution B and solution C mixing are obtained solution D.
5) under the magnetic agitation condition, fast solution D is added in the solution A room temperature reaction 40min.
6) reacted even colloidal solution is used the whizzer centrifugation, and rotating speed is 3000r/min, and centrifugation time is 15min.
7) the gained gel is at the vacuum drier inner drying.Obtain white powder after the drying, when exciting this white powder with the semiconductor laser of the 980nm wavelength of 3mW, almost not observing has up-conversion fluorescence.
8) sample that obtains after the drying is ground to form very thin powder; under the condition of nitrogen protection; 280 ℃ of roasting 3h; still be cooled to room temperature having under the condition of nitrogen protection then; products therefrom excites with the semiconductor laser of the 980nm wavelength of 3mW, the time can observe with the naked eye bright up-conversion fluorescence.
With transmission electron microscope (TEM), X-ray powder diffraction (XRD) and spectrophotofluorometer, the NaYF that this Comparative Examples is made
4: Er
3+, Yb
3+Nanocrystalline product is measured, and it the results are shown in the above content of putting down in writing about accompanying drawing and literal.
Claims (3)
1, be that solvent prepares the water-soluble conversion NaYF that goes up with the glycerol
4: Er
3+, Yb
3+Nanocrystalline method is dissolved in NaF in the glycerol solvent and obtains solution A; Again complexing agent EDTA is dissolved in the glycerol solvent and obtains solution B; With Er (NO3) 3, Yb (NO3) 3, Y (NO3) 3 all are dissolved in the glycerol solvent and obtain solution C; Solution A, solution B mixing are obtained solution D; Again solution C is added in the solution D, heats while stirring, react 1h～3h down in 200 ℃～297 ℃; EDTA and (Y
3++ Er
3++ Yb
3+) ratio of mole dosage sum is 1: 1; Wherein, (Y
3++ Er
3++ Yb
3+) the mole dosage sum is 100, Y wherein
3+Account for 80%, Er
3+Account for 3%, Yb
3+Account for 17%; After reaction finishes,, collect solid product after drying with the reaction mixture centrifugation, infrared ray excited with 980nm, observe with the naked eye bright up-conversion fluorescence.
2, according to claim 1 is that solvent prepares the water-soluble conversion NaYF that goes up with the glycerol
4: Er
3+, Yb
3+Nanocrystalline method, the product that makes is infrared ray excited through 980nm, is observed visually conversion NaYF
4: Er
3+, Yb
3+Nanocrystalline fluorescence intensity strengthens along with the rising of temperature of reaction.
3, according to claim 1 is that solvent prepares the water-soluble conversion NaYF that goes up with the glycerol
4: Er
3+, Yb
3+Nanocrystalline method, NaYF is changed in going up of obtaining
4: Er
3 +, Yb
3+Nanocrystalline, infrared ray excited through 980nm, its green fluorescence is along with the Er that mixes
3+Or Yb
3+Volumetric molar concentration improve and to diminish, red fluorescence intensity obviously increases.
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