CN105092079B - A kind of nano fluorescence thermometer and preparation method thereof - Google Patents
A kind of nano fluorescence thermometer and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of nano fluorescence thermometer and preparation method thereof；More particularly to a kind of rear-earth-doped nano fluorescence thermometer and preparation method thereof.Nanothermometer designed by the present invention is the fluorescent material that granularity is 50~200nm.Its optimal preparation method is：By the soluble bismuth salt taken by the group distribution of design, soluble erbium salt, TiO2Powder and the NaOH of excess after adding water into raw material, are well mixed and moved in reactor, carry out hydro-thermal reaction more than 12 hours in more than 160 DEG C, washing, drying, obtain the nano fluorescence thermometer as raw material.The temperature detection that the nanothermometer of the present invention can be used under micro, such as the real-time online measuring of living body biological cell, the precision and the scope of application of detection are all greatly improved in biology or other related industries.
Description
Technical field
The present invention relates to a kind of nano fluorescence thermometer and preparation method thereof；More particularly to a kind of rare earth mixing with nano fluorescence
Thermometer and preparation method thereof.
Background technology
Na0.5Bi0.5TiO3It is a kind of potential luminescent ceramic matrix of tool, A positions is particularly substituted with a small amount of rare earth ion
Bi ions when, because chemical valence is identical, ionic radius is close, will not produce defect.Meanwhile and because it belongs to ferroelectric material,
With non-centrosymmetrical structure, so that activator --- the luminous of rare earth ion has very high efficiency.Recently, study
It was found that rare earth Er3+The Na of ion doping0.5Bi0.5TiO3The ceramic block and form of film of material can be applied to optics temperature
Degree sensing, and the very wide range from low temperature to high temperature can be covered.But due to susceptibility not enough cause its application field by
Considerable restraint, such as application in micro-scale environment.
With being deepened continuously in people to the research in the range of micro-scale, the measurement to micro-scale environment temperature is special
For not being the research to biology such as individual cells, viruses, also there is technical sophistication, sensitivity in existing temperature detection means
The problems such as not high enough.
The content of the invention
The present invention carries for existing temperature testing equipment sensitivity is not high, is dfficult to apply to the deficiency of micro-scale environment
For a kind of nano fluorescence thermometer and preparation method thereof.
A kind of nano fluorescence thermometer of the present invention, the nanothermometer are the fluorescent materials that granularity is 50~200nm.
A kind of nano fluorescence thermometer of the present invention, the fluorescent material is rear-earth-doped fluorescent material.
A kind of nano fluorescence thermometer of the present invention, the rear-earth-doped fluorescent nano material is rear-earth-doped ferroelectric material
Granular materials.
A kind of nano fluorescence thermometer of the present invention, the fluorescent nano material of the rear-earth-doped ferroelectric material is rear-earth-doped
Na0.5Bi0.5TiO3Granular materials.
A kind of nano fluorescence thermometer of the present invention, the rear-earth-doped Na0.5Bi0.5TiO3Granular materials be Er3+Doping
Na0.5Bi0.5TiO3Nano particle.
A kind of nano fluorescence thermometer of the present invention, the Er3+Adulterate Na0.5Bi0.5TiO3Nano particle crystalline structure
For ABO3Type perovskite structure.
A kind of nano fluorescence thermometer of the present invention, the Er3+Adulterate Na0.5Bi0.5TiO3Nano particle in Er and Ti
Mol ratio is 0.005-0.03:1.Preferably 0.01-0.02:1.
A kind of nano fluorescence thermometer of the present invention, when the nano fluorescence thermometer is Er3+Adulterate Na0.5Bi0.5TiO3's
During nano particle, it is 0.0045~0.0053/K in 300K~453K sensitivity.
A kind of nano fluorescence thermometer of the present invention, the temperature measurement range of the fluorescence nano thermometer is -170~180
℃。
A kind of nano fluorescence thermometer of the present invention is prepared by hydro-thermal method.
A kind of preparation method of nano fluorescence thermometer of the present invention, when the nano fluorescence thermometer is Er3+Doping
Na0.5Bi0.5TiO3Nano particle when, its preparation method is：By the soluble bismuth salt taken by the group distribution of design, soluble erbium
Salt, TiO2Powder and excess NaOH be used as raw material, into raw material addition water after, be well mixed and move in reactor, in
More than 160 DEG C carry out hydro-thermal reaction more than 12 hours, washing, dry, obtain the nano fluorescence thermometer.
A kind of preparation method of nano fluorescence thermometer of the present invention, the soluble bismuth salt are selected from bismuth nitrate, bismuth chloride etc.
At least one of.
A kind of preparation method of nano fluorescence thermometer of the present invention, the soluble erbium salt are selected from erbium nitrate, erbium chloride etc.
At least one of.
A kind of preparation method of nano fluorescence thermometer of the present invention, matches somebody with somebody in the raw material taken, and titanium elements and bismuth element rub
You are than being 10:4-10:5.
A kind of preparation method of nano fluorescence thermometer of the present invention, after adding water into raw material；NaOH is dense in gained liquid
Degree is more than or equal to 8mol/L.
A kind of preparation method of nano fluorescence thermometer of the present invention, control temperature as 160~220 DEG C during hydro-thermal reaction.
Principle and advantage
The present invention has attempted nano-fluorescent grain material being directly used as thermometer first；And obtain considerable effect；Especially
It is when nano-fluorescent grain material is Er3+Adulterate Na0.5Bi0.5TiO3Nano particle when, its susceptibility obtains significantly
Lifting.The thermometer combination rare earth ion excellent luminance characteristic and the unique texture of ferroelectric material that the present invention is developed, to realize
Temperature in highly sensitive detection micro-scale environment, there is provided necessary condition.
Nano fluorescence thermometer designed by the present invention, when nano-fluorescent grain material is Er3+Adulterate Na0.5Bi0.5TiO3
Nano particle when, according to the fluorescence spectrum of nano particle, both fluorescence intensity ratios vary with temperature near 525nm and 548nm
Can be with the nanothermometer of measuring environment temperature.
The present invention nanothermometer can be used for micro under temperature detection, such as living body biological cell it is real-time
Line is measured, and the precision and the scope of application of detection are all greatly improved in biology or other related industries.
The nanothermometer of the present invention, includes Er3+The Na of ion doping0.5Bi0.5TiO3Nano particle is this to be had, according to
The measurable environment temperature of change of the luminous strength ratio of different energy levels.This application with potential using value, it is based on dilute
The luminous of native ion difference energy level is thermal coupling, meets the Boltzmann regularities of distribution of equilibrium thermodynamics, according to different energy
The measurable environment temperature of changes in contrast of the luminous intensity of level.In the present invention, due to Er3+Ion is as luminous sensitization
Agent, and with Na0.5Bi0.5TiO3As luminescent ceramic matrix, therefore Er3+The Na of ion doping0.5Bi0.5TiO3With fluorescent characteristic.
In the present invention, Na is selected as host material0.5Bi0.5TiO3The reasons why ferroelectric material, it is the Bi of A positions3+Ion
With activator Er3+Ion has similar atomic radius, and identical valence state.In addition, ferroelectric material has non-central pair
Claim structure so that the luminous efficiency of rare earth ion greatly improves.Finally, as the Na of oxide0.5Bi0.5TiO3With good
Chemical stability and temperature stability.
Brief description of the drawings：
Fig. 1 (a) is that the present invention realizes Er prepared by example 13+The Na of ion doping0.5Bi0.5TiO3The scanning electricity of nano particle
Sub- microphotograph；Fig. 1 (b) is distribution diagram of element.
Fig. 2 is that the present invention realizes Er prepared by example 13+The Na of ion doping0.5Bi0.5TiO3Nano particle in 525nm and
The change of luminous strength ratio near 548nm and the graph of a relation of temperature；
Fig. 3 is that the present invention realizes Er prepared by example 13+The Na of ion doping0.5Bi0.5TiO3Nano particle is to temperature control
In the curve of temperature relation.
Embodiment
The present invention provide can combine rare earth ion excellent luminance characteristic and ferroelectric material unique texture completely newly, there is characteristic
The nanothermometer of application.Namely the Er of the present invention3+The Na of ion doping0.5Bi0.5TiO3Nano particle.The nanometer temperature of the present invention
Degree meter, includes Er3+The Na of ion doping0.5Bi0.5TiO3Nano particle is this to be had, according to the luminous strength ratio of different energy levels
Change measurable environment temperature.This application with potential using value, it is to be based on the luminous of rare earth ion difference energy level
Thermal coupling, meet the Boltzmann regularities of distribution of equilibrium thermodynamics, according to the changes in contrast of the luminous intensity of different energy levels
Measurable environment temperature.In the present invention, due to Er3+Ion is as luminous sensitizer, and with Na0.5Bi0.5TiO3As
Luminescent ceramic matrix, therefore Er3+The Na of ion doping0.5Bi0.5TiO3With fluorescent characteristic.
Found through experiment, in this thermometer, the change of luminous strength ratio of the nano particle near 525nm and 548nm
Change the Boltzmann distributions met under thermal equilibrium state.Also, the nanothermometer of the present invention, sensitivity up to 0.0053/K,
Therefore extremely highly sensitive nanothermometer can be realized.
Embodiment 1
1) configuration concentration is the 12mol/L NaOH aqueous solution.It is 1 according to mol ratio：0.48：0.02 weighs respectively
TiO2、Bi(NO3)3、Er(NO3)3, and the NaOH of the above-mentioned concentration aqueous solution is dissolved in, mixed solution is placed in magnetic stirring apparatus and stirred
Mix about 0.5 hour；
2) reaction solution for obtaining step 1) is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, and compactedness is
80%；The reactor of good seal is placed in vacuum drying chamber again, in the case where temperature is 200 DEG C, at the heating of 12 hours of progress
Reason；
3) allow reactor to naturally cool to room temperature in atmosphere after the completion of reacting, obtained product is first carried out with watery hydrochloric acid
Cleaning, is then cleaned, finally dried again repeatedly with deionized water.
4) products therefrom is disperseed on Si pieces, entered under electron microscope (FE-SEM, Hitachi S-4800)
Row analysis.Fig. 1 (a) shows that obtained product is the nano particle that some sizes are distributed in 50~100nm or so.Fig. 1 (b)
Give the element in this nano particle.The peak of rare earth Er is therefrom clear that, illustrates to ultimately produce in thing and contains
Er ions.By carrying out X-ray diffraction analysis, material crystalline Cheng Chun perovskite structure to material., can be with reference to these analyses
Conclude that, i.e. the nano particle in Fig. 1 (a) is Er3+The Na of ion doping0.5Bi0.5TiO3Nano particle, its
Granularity is about 60 nanometers.
5) by the above-mentioned silicon chip for being dispersed with sample, it is put into Microscopic optical test alternating temperature operating desk (Janis ST-500),
And the workbench is fixed under confocal optics microscope (WITec alpha-300), using 980nm semiconductor diode as
Excitation source, carry out alternating temperature spectrum test.
6) under different temperatures, the luminous strength ratio record near 525nm and 548nm, then drawing, as shown in Figure 2.
As can be seen from Fig., the intensity has well linearly than the relation with temperature in Range of measuring temp.For Er3+Ion is sent out
For light, under different temperatures, the luminous strength ratio near 525nm and 548nm can be stated by following formula (1)：
In formula, I526And I548It is energy level4S3/2Arrive4I15/2With4F9/2Arrive4I15/2Transition intensity；C is constant, and Δ E is adjacent
Two energy levels can be poor, K is Boltzmann constants, T absolute temperature.The luminous and temperature of the nano particle obtained in this example
Relation obviously meet with the formula it is fine, so as to play a part of measurement temperature.
7) thermometer is used as, in addition to really can be with measurement temperature, its sensitivity be another important indicator.Fig. 3
Give the Er of preparation3+The Na of ion doping0.5Bi0.5TiO3Nano particle is to temperature control in the curve of temperature relation.From
The optimum sensitivity sensitivity that figure can be seen that the nanothermometer in this example is 0.0053/K, and the temperature of its ceramic formula
The optimum sensitivity sensitivity of meter is 0.0031/K.By having consulted SiO2：Er optimum sensitivity (0.0010/K), it is found that
Nano particle in this example has very high sensitivity.Therefore, inherently more accurately Detection results.
As described above, the invention provides the new of wide temperature range temperature measuring can be carried out under micro/nano-scale environment
The method of type nanothermometer and its this thermometer of manufacture.
Claims (7)
- A kind of 1. nano fluorescence thermometer, it is characterised in that：The nanothermometer is the phosphor that granularity is 50~200nm Material；The fluorescent material is rear-earth-doped fluorescent material；The rear-earth-doped fluorescent nano material is rear-earth-doped ferroelectricity The granular materials of material；The fluorescent nano material of the rear-earth-doped ferroelectric material is rear-earth-doped Na0.5Bi0.5TiO3Granular materials.
- A kind of 2. nano fluorescence thermometer according to claim 1, it is characterised in that：It is described rear-earth-doped Na0.5Bi0.5TiO3Granular materials be Er3+Adulterate Na0.5Bi0.5TiO3Nano particle.
- A kind of 3. nano fluorescence thermometer according to claim 2, it is characterised in that：The Er3+Doping Na0.5Bi0.5TiO3Nano particle in Er and Ti mol ratio be 0.005-0.03:1.
- A kind of 4. nano fluorescence thermometer according to claim 3, it is characterised in that：The nano fluorescence thermometer exists 300K~453K sensitivity is 0.0045~0.0053/K.
- 5. according to a kind of nano fluorescence thermometer described in claim 1-4 any one, it is characterised in that：The fluorescence nano The temperature measurement range of thermometer is -170~180 DEG C.
- A kind of 6. preparation method of the nano fluorescence thermometer as described in claim 1-4 any one, it is characterised in that：The system Preparation Method is hydro-thermal method.
- A kind of 7. preparation method of nano fluorescence thermometer according to claim 6；Characterized in that, when the nanometer is glimmering Light temperature is calculated as Er3+Adulterate Na0.5Bi0.5TiO3Nano particle when, its preparation method is：By by design group distribution take can Dissolubility bismuth salt, soluble erbium salt, TiO2Powder and the NaOH of excess after adding water into raw material, are well mixed as raw material And move in reactor, carry out hydro-thermal reaction more than 12 hours in more than 160 DEG C, washing, dry, obtain the nano fluorescent temperature Degree meter；The soluble bismuth salt is selected from least one of bismuth nitrate, bismuth chloride；The soluble erbium salt is selected from least one of erbium nitrate, erbium chloride；Match somebody with somebody in the raw material taken, the mol ratio of titanium elements and bismuth element is 10:4‐10:5；After water being added into raw material；NaOH concentration is more than or equal to 8mol/L in gained liquid.
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| CN102154008A (en) * | 2011-02-17 | 2011-08-17 | 同济大学 | Red fluorescent material and preparation method thereof |
| FR2952371B1 (en) * | 2009-11-12 | 2012-08-10 | Centre Nat Rech Scient | MATERIALS WITH TRANSITION OF SPIN THERMOCHROMES DOPED BY ONE OR MORE FLUORESCENT AGENTS |
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| CN104379677A (en) * | 2012-07-06 | 2015-02-25 | 三井化学株式会社 | Polymer particles and use thereof |
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| FR2952371B1 (en) * | 2009-11-12 | 2012-08-10 | Centre Nat Rech Scient | MATERIALS WITH TRANSITION OF SPIN THERMOCHROMES DOPED BY ONE OR MORE FLUORESCENT AGENTS |
| CN102154008A (en) * | 2011-02-17 | 2011-08-17 | 同济大学 | Red fluorescent material and preparation method thereof |
| CN104379677A (en) * | 2012-07-06 | 2015-02-25 | 三井化学株式会社 | Polymer particles and use thereof |
| CN104017581A (en) * | 2014-06-18 | 2014-09-03 | 东南大学 | Photothermal conversion nanometer material as well as preparation method and application method thereof |
| CN104371726A (en) * | 2014-11-26 | 2015-02-25 | 中国计量学院 | High-temperature enhanced upconversion fluorescence type nanocrystal for temperature sensing and preparation method and application thereof |
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