CN105466592A - Correction method for down-conversion fluorescence intensity ratio temperature measurement technology - Google Patents
Correction method for down-conversion fluorescence intensity ratio temperature measurement technology Download PDFInfo
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- CN105466592A CN105466592A CN201510801636.0A CN201510801636A CN105466592A CN 105466592 A CN105466592 A CN 105466592A CN 201510801636 A CN201510801636 A CN 201510801636A CN 105466592 A CN105466592 A CN 105466592A
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- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
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Abstract
The invention relates to a correction method for the down-conversion fluorescence intensity ratio temperature measurement technology and solves a problem of inaccurate temperature measurement results existing in the temperature measurement technology in the prior art. The method comprises steps that, excitation light emitted by an excitation source is gathered through a convex lens and irradiates to a temperature-sensitive material, down-conversion fluorescence emitted through the temperature-sensitive material is gathered through the convex lens and enters a spectrometer, the spectrometer is connected with a storage oscilloscope and a computer for data processing, and a correction curve is acquired. Through the correction method, deviation of the down-conversion fluorescence intensity ratio and the Boltzmann distributing law in the prior art is eliminated, advantages of strong anti-interference capability, good stability and high sensitivity of the fluorescence intensity ratio method are kept, and temperature measurement accuracy is further improved. The correction method is applied to the rare earth fluorescence temperature measurement field.
Description
Technical field
The present invention relates to a kind of modification method of down-conversion fluorescent strength ratio thermometry.
Background technology
In order to meet in scientific research and industrial technology some particular surroundings to thermometric needs, the contactless temperature method for sensing of this temperature dependence based on fluorescent material spectral quality of fluorescence temperature sensing technology causes the extensive concern of people, has important practical value.
Fluorescence intensity ratio thermometry (FIR) applies of paramount importance one in fluorescence temperature sensing technology, its principle utilizes two of rare earth ion adjacent excited levels with thermal coupling relation to carry out thermometric to the ratio of the fluorescence intensity of launching during a certain low-lying level transition, and this temp measuring method of ratio that utilizes has anti-interference, that noise is little, cost is low advantage.In FIR technology, the size of two fluorescence intensities is directly proportional to the population of Thermal layout on energy level, and the population of Thermal layout meets ANALOGY OF BOLTZMANN DISTRIBUTION, and therefore the ratio of fluorescence intensity meets formula F IR=Aexp (-Δ E/kT).The difference that in formula, FIR represents fluorescence intensity ratio, Δ E is two thermocouples and energy level, k are Boltzmann constant, T is temperature.Formula can draw thus, and the sensitivity of thermometry of FIR technology is S=Δ E/kT
2.
At present, still there are some problems and make this technology more difficult in actual applications in fluorescence intensity ratio thermometry.In order to obtain higher sensitivity of thermometry, usually need the material selecting energy level difference Δ E large, and when Δ E increases, the fluorescence intensity of the upper energy level radiation that thermal coupling energy level is right is very weak, the signal to noise ratio (S/N ratio) of fluorescence signal is very low, therefore larger temperature measurement error can be caused, in addition, when Δ E reduces, FIR formula not exclusively meets ANALOGY OF BOLTZMANN DISTRIBUTION again, now need in formula to add correction term, the introducing becoming FIR=Aexp (-Δ E/kT)+B, correction term B can cause temperature-measuring results inaccurate.Therefore revising to eliminate correction term to FIR can make FIR technology its thermometric accuracy while the sensitivity of thermometry that maintenance is higher also be guaranteed.
Summary of the invention
The present invention will solve the inaccurate problem of existing thermometry temperature-measuring results, provides a kind of modification method of down-conversion fluorescent strength ratio thermometry.
The modification method of a kind of down-conversion fluorescent strength ratio of the present invention thermometry, carry out according to the following steps: one, the pulse excitation light that excitaton source sends converges through convex lens and is irradiated on rare earth ion doped temperature sensing material, the down-conversion fluorescent that rare earth ion doped temperature sensing material is launched is converged by another convex lens and incides in computer-controlled grating spectrograph, wherein the fluorescence spectrum of computer-controlled grating spectrograph collection has two fluorescence emission peaks, be respectively the fluorescence emission peak that the adjacent and energy level that is that there is thermal coupling relation of rare earth ion two produces to lower energy level radiation transistion, the wavelength of fluorescence that upper energy level A launches is shorter than the wavelength that lower energy level B launches, two, computer-controlled grating spectrograph is connected storage oscilloscope, storage oscilloscope carries out the measurement of Fluorescence decay curve under different temperatures, obtains the lower energy level B Fluorescence decay curve under different temperatures and upper energy level A Fluorescence decay curve, computing machine carries out data processing, provides correction factor, and revised fluorescence intensity ratio is FIR
c=FIRC
2/ (C
1+ C
2), obtain fair curve, described upper energy level A is the adjacent and upper energy level existed in the energy level of thermal coupling relation of rare earth ion two, lower energy level B is the adjacent and lower energy level existed in the energy level of thermal coupling relation of rare earth ion two.
The pulse excitation light that in the present invention, excitaton source sends converges through convex lens and is irradiated on temperature sensing material, and the down-conversion fluorescent that temperature sensing material is launched is converged by convex lens and incides in spectrometer, carries out spectral analysis by spectrometer to detected fluorescence.Measure the decay curve deriving from two down-conversion fluorescent peaks of thermal coupling energy level radiation transistion respectively.Lower radiation level fluorescence intensity I
1in single e index rule decay: I
1=C
0exp (-t/ τ
0), by carrying out e index matching to the Fluorescence decay curve measured, obtain the matching life-span τ under different temperatures
0.Because two energy levels exist thermal coupling relation, upper radiation level fluorescence intensity I
2the Decay Law of t is in two e index decay: I in time
2(t)=C
1exp (-t/ τ
1)+C
2exp (-t/ τ
2), short life τ
1for the energy level intrinsic life-span, long-life τ
2with the matching life-span τ of lower energy level
0unanimously, C
1, C
2for matching weight coefficient; Fixing τ
2=τ
0, two e index matching is carried out to Fluorescence decay curve, obtains Fitted parameter C
1and C
2.Thus by C
2/ (C
1+ C
2) obtaining the correction factor of FIR, revised fluorescence intensity ratio is expressed as FIR
c=FIRC
2/ (C
1+ C
2).This revised fluorescence intensity ratio variation with temperature rule and Boltzmann distributing law do not have deviation.
Modification method of the present invention eliminates the deviation of fluorescence intensity ratio and Boltzmann distributing law, maintaining that fluorescence intensity ratio method antijamming capability is strong, while good stability, highly sensitive advantage, improves the accuracy of its thermometric.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of embodiment 1; 1 be 405nm light emitting diode, 2 be wherein lens, 3 for Eu
3+: CaWO
4temperature sensing material, 4 is another lens, 5 is grating spectrograph, 6 for computing machine;
Fig. 2 is the fluorescence spectrum of rare-earth europium under 405nm laser excitation;
Fig. 3 is the radiation transistion energy level diagram of rare-earth europium under 405nm laser excitation;
Fig. 4 is the schematic diagram of FIR and Boltzmann's distributive law deviation before revising, and "○" is the FIR before correction, and a is Boltzmann's distribution curve;
Fig. 5 is the Fluorescence decay curve synoptic diagram of 594nm in europium ion thermal coupling energy level, and "○" is the Fluorescence decay curve of 594nm, and b is life-span fit line;
Fig. 6 is the Fluorescence decay curve synoptic diagram of 538nm in europium ion thermal coupling energy level, and "○" is the Fluorescence decay curve of 538nm, and b is life-span fit line;
Fig. 7 is corrected parameter variation with temperature rule figure;
Fig. 8 is revised FIR and the agonic schematic diagram of Boltzmann's distributive law, and "○" is the FIR before revising, and a is Boltzmann's distribution curve.
Embodiment
Embodiment one: the modification method of a kind of down-conversion fluorescent strength ratio of present embodiment thermometry, carry out according to the following steps: one, the pulse excitation light that excitaton source sends converges through convex lens and is irradiated on rare earth ion doped temperature sensing material, the down-conversion fluorescent that rare earth ion doped temperature sensing material is launched is converged by another convex lens and incides in computer-controlled grating spectrograph, wherein the fluorescence spectrum of computer-controlled grating spectrograph collection has two fluorescence emission peaks, be respectively the fluorescence emission peak that the adjacent and energy level that is that there is thermal coupling relation of rare earth ion two produces to lower energy level radiation transistion, the wavelength of fluorescence that upper energy level A launches is shorter than the wavelength that lower energy level B launches, two, computer-controlled grating spectrograph is connected storage oscilloscope, storage oscilloscope carries out the measurement of Fluorescence decay curve under different temperatures, obtains the lower energy level B Fluorescence decay curve under different temperatures and upper energy level A Fluorescence decay curve, computing machine carries out data processing, provides correction factor, and revised fluorescence intensity ratio is FIR
c=FIRC
2/ (C
1+ C
2), obtain fair curve, described upper energy level A is the adjacent and upper energy level existed in the energy level of thermal coupling relation of rare earth ion two, lower energy level B is the adjacent and lower energy level existed in the energy level of thermal coupling relation of rare earth ion two.
The pulse excitation light that in present embodiment, excitaton source sends converges through convex lens and is irradiated on temperature sensing material, and the down-conversion fluorescent that temperature sensing material is launched is converged by convex lens and incides in spectrometer, carries out spectral analysis by spectrometer to detected fluorescence.Measure the decay curve deriving from two down-conversion fluorescent peaks of thermal coupling energy level radiation transistion respectively.Lower radiation level fluorescence intensity I
1in single e index rule decay: I
1=C
0exp (-t/ τ
0), by carrying out e index matching to the Fluorescence decay curve measured, obtain the matching life-span τ under different temperatures
0.Because two energy levels exist thermal coupling relation, upper radiation level fluorescence intensity I
2the Decay Law of t is in two e index decay: I in time
2(t)=C
1exp (-t/ τ
1)+C
2exp (-t/ τ
2), short life τ
1for the energy level intrinsic life-span, long-life τ
2with the matching life-span τ of lower energy level
0unanimously, C
1, C
2for matching weight coefficient; Fixing τ
2=τ
0, two e index matching is carried out to Fluorescence decay curve, obtains Fitted parameter C
1and C
2.Thus by C
2/ (C
1+ C
2) obtaining the correction factor of FIR, revised fluorescence intensity ratio is expressed as FIR
c=FIRC
2/ (C
1+ C
2).This revised fluorescence intensity ratio variation with temperature rule and Boltzmann distributing law do not have deviation.
The modification method of present embodiment eliminates the deviation of fluorescence intensity ratio and Boltzmann distributing law, maintaining that fluorescence intensity ratio method antijamming capability is strong, while good stability, highly sensitive advantage, improves the accuracy of its thermometric.
Embodiment two: present embodiment and embodiment one unlike: described excitaton source is 405nm light emitting diode.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: described rare earth ion doped temperature sensing material is Eu
3+doping temperature sensing material.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three are unlike lower energy level B fluorescence intensity I
1in single e index rule decay: I
1=C
0exp (-t/ τ
0), by carrying out e index matching to the lower energy level B Fluorescence decay curve under different temperatures, obtain the matching life-span τ under different temperatures
0; Upper energy level A fluorescence intensity I
2the Decay Law of t is in two e index decay: I in time
2(t)=C
1exp (-t/ τ
1)+C
2exp (-t/ τ
2), short life τ
1for the energy level intrinsic life-span, long-life τ
2with the matching life-span τ of lower energy level
0unanimously, C
1, C
2for matching weight coefficient; Fixing τ
2=τ
0, two e index matching is carried out to the upper energy level A Fluorescence decay curve under different temperatures, obtains Fitted parameter C
1and C
2, then by C
2/ (C
1+ C
2) obtain the correction factor of FIR.Other is identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: described temperature is the temperature range of rare earth ion doped temperature sensing material.Other is identical with one of embodiment one to four.
Beneficial effect of the present invention is verified by following examples:
Embodiment one: the modification method of a kind of down-conversion fluorescent strength ratio of the present embodiment thermometry, carries out: the pulse excitation light that one, 405nm light emitting diode sends converges through convex lens and is irradiated to Eu according to the following steps
3+: CaWO
4on, Eu
3+: CaWO
4the down-conversion fluorescent launched is converged by another convex lens and incides in computer-controlled grating spectrograph, and the fluorescence spectrum of wherein computer-controlled grating spectrograph collection has two fluorescence emission peaks, is respectively Eu
3+the fluorescence emission peak that two adjacent and energy levels that are that there is thermal coupling relation produce to lower energy level radiation transistion, rare earth ion two is adjacent and to there is the wavelength of fluorescence that the upper energy level in the energy level of thermal coupling relation launches be 538nm, and rare earth ion two is adjacent and to there is the wavelength of fluorescence that the lower energy level in the energy level of thermal coupling relation launches be 594nm; Two, computer-controlled grating spectrograph is connected storage oscilloscope, storage oscilloscope carries out the measurement of Fluorescence decay curve under different temperatures, obtains the Fluorescence decay curve of europium ion 538nm under different temperatures and 594nm radiation; Computing machine carries out data processing, provides correction factor, and revised fluorescence intensity ratio is FIR
c=FIRC
2/ (C
1+ C
2), obtain fair curve.
Adjacent and the lower energy level fluorescence intensity I existed in the energy level of thermal coupling relation of the present embodiment Rare Earth Ion two
1in single e index rule decay: I
1=C
0exp (-t/ τ
0), by carrying out e index matching to the lower energy level Fluorescence decay curve measured, obtain the matching life-span τ under different temperatures
0; Upper energy level A fluorescence intensity I
2the Decay Law of t is in two e index decay: I in time
2(t)=C
1exp (-t/ τ
1)+C
2exp (-t/ τ
2), short life τ
1for the energy level intrinsic life-span, long-life τ
2with the matching life-span τ of lower energy level
1unanimously, C
1, C
2for matching weight coefficient; Fixing τ
2=τ
0, two e index matching is carried out to upper energy level A Fluorescence decay curve, obtains Fitted parameter C
1and C
2, then by C
2/ (C
1+ C
2) obtain the correction factor of FIR.
The present embodiment schematic flow sheet as shown in Figure 1, europium ion
5d
1energy level and
5d
0energy level is the adjacent energy levels a pair with thermal coupling relation, its down-conversion fluorescent through convex lens converge be coupled to spectrometer, spectrum shown in Fig. 2 can be obtained through spectrometer analysis, wherein 538nm fluorescent light source in
5d
1→
7f
1, 594nm fluorescence comes from
5d
0→
7f
1(Fig. 3).Fig. 4 is the temperature dependence of FIR before revising, and can find out that the FIR before correction and Boltzmann's distributive law have obvious deviation at low-temperature region; The Fluorescence decay curve synoptic diagram that Fig. 5 and 6 is the europium ion 538nm and 594nm radiation that utilize storage oscilloscope record, 594nm fluorescent light source in lower energy level, in single e index rule decay, 538nm fluorescent light source in upper energy level, in two e index rule decay, τ
2be 0.52 millisecond, τ
1the fall time be 0.014 millisecond, the intrinsic that wherein fast decay is energy level decay, decaying slowly is consistent with the fall time of upper energy level, τ
0it is 0.52 millisecond.Fig. 7 is the fair curve of europium ion 538nm and 594nm fluorescence intensity ratio FIR, and Fig. 8 is the temperature dependence of FIR after revising, and can find out that revised FIR meets the linear relationship of Boltzmann's distributive law.
From embodiment, modification method of the present invention eliminates the deviation of fluorescence intensity ratio and Boltzmann distributing law, maintaining that fluorescence intensity ratio method antijamming capability is strong, while good stability, highly sensitive advantage, improves the accuracy of its thermometric.
Claims (5)
1. the modification method of a down-conversion fluorescent strength ratio thermometry, it is characterized in that it carries out according to the following steps: one, the pulse excitation light that excitaton source sends converges through convex lens and is irradiated on rare earth ion doped temperature sensing material, the down-conversion fluorescent that rare earth ion doped temperature sensing material is launched is converged by another convex lens and incides in computer-controlled grating spectrograph, wherein the fluorescence spectrum of computer-controlled grating spectrograph collection has two fluorescence emission peaks, be respectively the fluorescence emission peak that the adjacent and energy level that is that there is thermal coupling relation of rare earth ion two produces to lower energy level radiation transistion, the wavelength of fluorescence that upper energy level A launches is shorter than the wavelength that lower energy level B launches, two, computer-controlled grating spectrograph is connected storage oscilloscope, storage oscilloscope carries out the measurement of Fluorescence decay curve under different temperatures, obtains the lower energy level B Fluorescence decay curve under different temperatures and upper energy level A Fluorescence decay curve, computing machine carries out data processing, provides correction factor, and revised fluorescence intensity ratio is FIR
c=FIRC
2/ (C
1+ C
2), obtain fair curve, described upper energy level A is the adjacent and upper energy level existed in the energy level of thermal coupling relation of rare earth ion two, lower energy level B is the adjacent and lower energy level existed in the energy level of thermal coupling relation of rare earth ion two.
2. the modification method of a kind of down-conversion fluorescent strength ratio thermometry according to claim 1, is characterized in that described excitaton source is 405nm light emitting diode.
3. the modification method of a kind of down-conversion fluorescent strength ratio thermometry according to claim 1, is characterized in that described rare earth ion doped temperature sensing material is Eu
3+doping temperature sensing material.
4. the modification method of a kind of down-conversion fluorescent strength ratio thermometry according to claim 1, is characterized in that lower energy level B fluorescence intensity I
1in single e index rule decay: I
1=C
0exp (-t/ τ
0), by carrying out e index matching to the lower energy level B Fluorescence decay curve under different temperatures, obtain the matching life-span τ under different temperatures
0; Upper energy level A fluorescence intensity I
2the Decay Law of t is in two e index decay: I in time
2(t)=C
1exp (-t/ τ
1)+C
2exp (-t/ τ
2), short life τ
1for the energy level intrinsic life-span, long-life τ
2with the matching life-span τ of lower energy level
0unanimously, C
1, C
2for matching weight coefficient; Fixing τ
2=τ
0, two e index matching is carried out to the upper energy level A Fluorescence decay curve under different temperatures, obtains Fitted parameter C
1and C
2, then by C
2/ (C
1+ C
2) obtain the correction factor of FIR.
5. the modification method of a kind of down-conversion fluorescent strength ratio thermometry according to claim 1 or 4, is characterized in that described temperature is the responsive to temperature interval of rare earth ion doped temperature sensing material.
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|---|---|---|---|---|
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| CN106500864A (en) * | 2016-11-09 | 2017-03-15 | 哈尔滨工程大学 | A kind of up-conversion fluorescence strength ratio temp measuring method of use high power laser light pumping |
| CN108168726A (en) * | 2016-12-08 | 2018-06-15 | 中国科学院福建物质结构研究所 | A kind of method of gain media internal temperature in measurement solid state laser |
| CN108489632A (en) * | 2018-03-22 | 2018-09-04 | 哈尔滨工业大学 | A method of improving fluorescence intensity ratio technology temperature measurement accuracy |
| CN109540326A (en) * | 2018-11-19 | 2019-03-29 | 哈尔滨工业大学 | A kind of fluorescence intensity ratio temp measuring method based on double-wavelength light source |
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|---|---|---|---|---|
| CN106404211A (en) * | 2016-11-09 | 2017-02-15 | 哈尔滨工程大学 | Upconversion fluorescence intensity ratio temperature measurement method independent of excitation light intensity |
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| CN108168726B (en) * | 2016-12-08 | 2020-10-02 | 中国科学院福建物质结构研究所 | Method for measuring internal temperature of gain medium in solid laser |
| CN108489632A (en) * | 2018-03-22 | 2018-09-04 | 哈尔滨工业大学 | A method of improving fluorescence intensity ratio technology temperature measurement accuracy |
| CN109540326A (en) * | 2018-11-19 | 2019-03-29 | 哈尔滨工业大学 | A kind of fluorescence intensity ratio temp measuring method based on double-wavelength light source |
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