CN107384396A - A kind of rear-earth-doped oxide micron tube material with light temperature sensing property and preparation method thereof - Google Patents
A kind of rear-earth-doped oxide micron tube material with light temperature sensing property and preparation method thereof Download PDFInfo
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- CN107384396A CN107384396A CN201710542456.4A CN201710542456A CN107384396A CN 107384396 A CN107384396 A CN 107384396A CN 201710542456 A CN201710542456 A CN 201710542456A CN 107384396 A CN107384396 A CN 107384396A
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- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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Abstract
The present invention relates to a kind of rear-earth-doped oxide micron tube material with light temperature sensing property and preparation method thereof, belong to rare earth luminescent material technical field.With rare earth ion Er3+For the centre of luminescence, it is singly mixed or be co-doped with Y2O3In micron tube, the intense fluorescence of multi-frequency is sent under infrared ray excited, there are highly sensitive light temperature sensing characteristicses.Its preparation method includes：(a) selection of raw material, the mixing of (b) dispensing, (c) micron tube prepare three steps.Fluorescent material prepared by the present invention, which can not only be realized, to be changed infrared light to visible ray but also can realize that the light temperature of light temperature sensing capabilities senses micron tube material.This material is adapted to large area industrial production.
Description
Technical field
The present invention relates to a kind of rear-earth-doped oxide micron tube with light temperature sensing property and preparation method thereof, belong to
Rare earth luminescent material technical field.
Background technology
The thermometer that we generally use in life is the temperature that body surface is measured by the way of contact.But
Many special dimensions, such as：Inside microelectronic component, colliery, the transformation place etc. of high voltage generating station, the temperature survey of contact is difficult
To realize.Therefore, the temperature sensor of studying non-contact type is required.Recently, based on the upper of rare earth ion doped phosphor
The luminous light temperature sensing behavior of conversion receives many concerns, because they can be glimmering by two adjacent thermal coupling energy levels
Light strength ratio (FIR) provides contact-free measurement of temperature.Contactless FIR technologies have high-resolution and high accuracy, better than normal
The temperature survey of rule.Up-conversion luminescent material is now widely used for the fields such as temperature survey, biological fluorescent labeling, market prospects
It is wide.At present, using trivalent rare earth ionses such as Er3+, Ho3+, Tm3+, Eu3+And Pr3+Light temperature sensing is studied as activator
Behavior.Phosphor with high thermal stability is the preferred material for light temperature sensing.Rare earth ion doped fluoride materials
It is good VISIBLE LIGHT EMISSION body, is adapted to do light temperature sensing material.But fluoride materials are easily oxidized at high temperature, it is impossible to
Realize light temperature performance detection.In order to avoid this restricted, it is necessary to prepare with highly sensitive oxide material.With fluoride
Compare, Y2O3High with fusing point, band gap is wide, has high thermal stability, and the transparency is good in ultraviolet and infra-red range, most heavy
That want is Y2O3Lattice and rare earth ion Er3+,Ho3+With good solid fusibleness, and high-concentration dopant can be realized and obtained strongly
Fluorescent emission.
Because 980nm infrared light is most cheap and most power adjustable section the exciting light that is used in light temperature sensing
Source.The present invention is from 980nm infrared lights as excitaton source, rare earth ion Er3+For the centre of luminescence, Er is prepared for3+、Ho3+Rare earth from
The Y of son doping2O3Micron tube, the micron tube have high heat endurance and high luminous intensity.Moreover, we can pass through prison
Control Er3+、Ho3+The fluorescence spectrum variation with temperature of rare earth ion realizes the measurement of temperature, significantly improves light temperature sensing
Sensitivity, the sensitivity realized of the present invention is more than the high temperature peak response value (0.0044K of document report-1, 427K)
(Mater.Lett.143,209-211,2015), and the breakthrough of low temperature sensing is realized, to than conventional report, Neng Goutong
The measurement of Shi Shixian high/low temperatures.
The content of the invention
Present invention solves the technical problem that it is：A kind of rear-earth-doped oxide micron tube with light temperature sensing property is provided
Material and preparation method thereof.
In order to solve the above-mentioned technical problem, technical scheme proposed by the present invention is：It is a kind of to sense the dilute of property with light temperature
Native doping oxide micron tube material, each component and volume ratio are：YCl3:ErCl3:HoCl3=98.8:1:0.2、98.5:1:
0.5、98:1:1 or 97.5:1:1.5.
Preferably, each component and volume ratio are：YCl3:ErCl3:HoCl3=98.5:1:0.5.
In order to solve the above-mentioned technical problem, another technical scheme proposed by the present invention is：One kind has light temperature sensing property
Rear-earth-doped oxide micron tube material preparation method, including following steps：
(a) selection of raw material
The raw material of rear-earth-doped micron tube is analytically pure HCl, NaOH and ethanol, rare earth ion select purity for
99.99% oxide, oxide Y2O3、Er2O3And Ho2O3；
(b) preparation of micron tube batch
Raw material accurately is measured according to proportioning, by oxide and hydrochloric acid reaction, adds water, prepares 0.2mol/L YCl3、
ErCl3And HoCl3Solution；
(c) preparation of micron tube
Micron tube is prepared using hydro-thermal method, and solution is instilled in hydrothermal reaction kettle, NaOH solution, magnetic force is slowly added dropwise
Mixer stirs half an hour, 200 DEG C of hydro-thermal reactions 24 hours, after reaction terminates, cooling, adds distilled water, ethanol cleaning, centrifugation point
Separate out sample, dry 6 hours, then by annealing, annealing temperature is 900 DEG C, the time is 3 hours, after the completion of ground with agate mortar
Clay into power.
Beneficial effect：
(1) preparation method of the present invention is easy, and heat endurance is high, is adapted to industrial mass manufacture.
(2) micron tube produced by the present invention has good heat endurance and chemical stability.
(3) present invention follows Boltzmann's distribution in temperature change using the thermal coupling energy level of rare earth ion, and utilizes
Boltzmann's formula is fitted to fluorescent intensity ratio, obtains the relation of fluorescence intensity and temperature, and then obtain sample pair
The relative sensitivity curves of temperature.Thus we not only can be by monitoring Er3+The fluorescence spectrum of rare earth ion with temperature change
Change to realize the measurement of temperature, be also based on the relation of relative sensitivity and temperature, obtaining high temperature peak response is
(0.0057K-1, 457K), the Sensitirity va1ue of document report greatly improves than ever, and breakthrough realizes low temperature sensitivity and is
(0.0529K-1, 24K), realize the performance of precise light temperature sensor.
Brief description of the drawings
The present invention is described further below in conjunction with the accompanying drawings.
Fig. 1 is Y2O3：1%Er3+, 0.5%Ho3+The pattern of sample under an electron microscope.
Fig. 2 is Y2O3：1%Er3+, x%Ho3+(x=0,0.2,0.5,1.0,1.5), the transmitting light in the case where 980nm is excited
Spectrum.
Fig. 3 is Y2O3：1%Er3+, 0.5%Ho3+The fluorescence intensity ratio of sample and the relation of temperature.
Fig. 4 is Y2O3：1%Er3+, x%Ho3+(x=0,0.2,0.5,1.0,1.5) relative sensitivity of sample and temperature
Relation.
Fig. 5 is Y2O3：1%Er3+, x%Ho3+(x=0,0.2,0.5,1.0,1.5) relative sensitivity of sample and temperature
Relation.
Embodiment
Host material Analysis about Selection pure HCl, NaOH and ethanol, rare earth ion is from the oxide that concentration is 99.99%
(Y2O3、Er2O3And Ho2O3) it is primary raw material, be according to host material proportioning：YCl3：Doped ions are：Er3+, Ho3+。Er3+'s
Doping concentration volume ratio is：1%Er3+, Ho3+Doping concentration volume ratio be：0,0.2,0.5,1.0,1.5% ratio measures
Raw material, each material solution volume such as table 1, by 0.2mol/L YCl3, ErCl3, HoCl3Solution instills hydrothermal reaction kettle in proportion
In, then NaOH (3.5ml) solution is slowly added dropwise, magnetic stirrer stirring half an hour, 200 DEG C of hydro-thermal reactions 24 hours, reaction knot
Shu Hou, cooling, add distilled water, ethanol cleaning, centrifuge out sample, 100 DEG C dry 6 hours, then by annealing, annealing temperature
For 900 DEG C, the time is 3 hours, after the completion of use agate mortar grind into powder.The sample of different levels of doping is subjected to 980nm
Spectrum test under infrared excitation, the most strong embodiment 3 of fluorescence intensity is selected as sample and carries out light temperature sensing testing, is obtained
The relation of (524+537) nm/552nm fluorescence intensity ratios and temperature is as shown in figure 3, the relative sensitivity of sample and the relation of temperature
As shown in Figure 4；Obtain the relation of 660nm/680nm fluorescence intensity ratios and temperature as shown in figure 3, the relative sensitivity of sample with
The relation of temperature is as shown in Figure 5.
The embodiment 1-5 of table 1 fluorescent material composition (unit：Milliliter)
Experimental result：Case study on implementation is observed using electron microscope, obtains Fig. 1 sample topography figure, is micron
Tube, diameter are about 0.7 μm.The sample of table 1 is excited using 980nm infrared light supplies, Fig. 2 emission spectrum is obtained, chooses
The most strong sample of intensity i.e. case study on implementation 3 is selected, fluorescence intensity is carried out using 524nm, 537nm and 552nm emitted luminescence intensity
Than obtaining in Fig. 3 the relation of (524+537) nm/552nm fluorescence intensity ratios and temperature, as seen from Figure 4 (524+537) nm/
The relation of 552nm fluorescence intensity ratios and temperature follows Boltzmann's formula, and using fluorescence intensity ratio obtain relative sensitivity with
The relation and peak response of temperature are (0.0057K-1, 457K), as shown in figure 4, explanation can be by monitoring Er3+With Ho3+
The fluorescence spectrum variation with temperature of rare earth ion realizes the measurement of temperature.Emitted luminescence intensity using 660nm and 680nm enters
Row fluorescence intensity ratio, the relation of 660nm/680nm fluorescence intensity ratios and temperature in Fig. 3 is obtained, as seen from Figure 5 660nm/
The relation of 680nm fluorescence intensity ratios and temperature follows Boltzmann's formula, and using fluorescence intensity ratio obtain relative sensitivity with
The relation and peak response of temperature are (0.0529K-1, 24K), as shown in figure 5, explanation can be by monitoring Er3+With Ho3+
The fluorescence spectrum variation with temperature of rare earth ion realizes the measurement of temperature.The different rare earths reported by contrasting international literature
Ion doping Y2O3, show that the relative sensitivity of fluorescent material of the present invention is better than conventional Y2O3Fluorescent material, high temp sensitive is improved,
Especially breaking through realizes low temperature sensing.
The present invention is not limited to the concrete technical scheme described in above-described embodiment, all technical sides formed using equivalent substitution
Case is the protection domain of application claims.
Claims (3)
- A kind of 1. rear-earth-doped oxide micron tube material with light temperature sensing property, it is characterised in that:Each component and volume Than for：YCl3:ErCl3:HoCl3=98.8:1:0.2、98.5:1:0.5、98:1:1 or 97.5:1:1.5.
- A kind of 2. rear-earth-doped oxide micron tube material with light temperature sensing property, it is characterised in that:Each component and volume Than for：YCl3:ErCl3:HoCl3=98.5:1:0.5.
- 3. a kind of rear-earth-doped oxide micron tube material with light temperature sensing property according to claim 1 or 2 Preparation method, it is characterised in that：Including following steps：(a) selection of raw materialThe raw material of rear-earth-doped micron tube is analytically pure HCl, NaOH and ethanol, and rare earth ion selection purity is 99.99% Oxide, oxide Y2O3、Er2O3And Ho2O3；(b) preparation of micron tube batchRaw material accurately is measured according to proportioning, by oxide and hydrochloric acid reaction, adds water, prepares 0.2mol/L YCl3、ErCl3With HoCl3Solution；(c) preparation of micron tubeMicron tube is prepared using hydro-thermal method, and solution is instilled in hydrothermal reaction kettle, NaOH solution, magnetic agitation is slowly added dropwise Machine stirs half an hour, 200 DEG C of hydro-thermal reactions 24 hours, after reaction terminates, cooling, adds distilled water, ethanol cleaning, centrifuges out Sample, dry 6 hours, then by annealing, annealing temperature be 900 DEG C, the time be 3 hours, after the completion of be ground into agate mortar Powder.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110894425A (en) * | 2019-11-27 | 2020-03-20 | 南京邮电大学 | Rare earth and metal ion doped phosphor with light temperature sensing and multiband light emission functions and preparation method thereof |
Citations (2)
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|---|---|---|---|---|
| CN1687306A (en) * | 2005-04-29 | 2005-10-26 | 中国科学院上海硅酸盐研究所 | Luminescent material converted in nano level with yttrium oxide as matrix and preparation method |
| CN102172497A (en) * | 2011-01-17 | 2011-09-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of fluorescent coding microspheres based on up-conversion luminous nanocrystalline |
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|---|---|---|---|---|
| CN1687306A (en) * | 2005-04-29 | 2005-10-26 | 中国科学院上海硅酸盐研究所 | Luminescent material converted in nano level with yttrium oxide as matrix and preparation method |
| CN102172497A (en) * | 2011-01-17 | 2011-09-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of fluorescent coding microspheres based on up-conversion luminous nanocrystalline |
Non-Patent Citations (1)
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| XIAORUI HOU等: "Investigation of up-conversion luminescence properties of RE/Yb co-doped Y2O3 transparent ceramic(RE=Er, Ho,Pr,and Tm)", 《PHYSICA B》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110894425A (en) * | 2019-11-27 | 2020-03-20 | 南京邮电大学 | Rare earth and metal ion doped phosphor with light temperature sensing and multiband light emission functions and preparation method thereof |
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