CN108168730A - It is a kind of to improve method of the fluorescence intensity ratio technology in high temperature section sensitivity of thermometry using double centre of luminescence strategies - Google Patents
It is a kind of to improve method of the fluorescence intensity ratio technology in high temperature section sensitivity of thermometry using double centre of luminescence strategies Download PDFInfo
- Publication number
- CN108168730A CN108168730A CN201810241597.7A CN201810241597A CN108168730A CN 108168730 A CN108168730 A CN 108168730A CN 201810241597 A CN201810241597 A CN 201810241597A CN 108168730 A CN108168730 A CN 108168730A
- Authority
- CN
- China
- Prior art keywords
- temperature
- calibration curve
- luminescence
- fluorescence intensity
- strategies
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01K11/32—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in transmittance, scattering or luminescence in optical fibres
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
It is a kind of to improve method of the fluorescence intensity ratio technology in high temperature section sensitivity of thermometry using double centre of luminescence strategies, the present invention relates to a kind of method of the fluorescence intensity ratio technology in high temperature section sensitivity of thermometry is improved using double centre of luminescence strategies.The problem of the purpose of the present invention is to solve being difficult to realize realize high-precision temperature survey in higher temperature range using traditional fluorescence intensity ratio thermometry, method：(1) thermometric sample is prepared；(2) traditional Er is utilized in low temperature section3+'s2H11/2‑4I15/2With4S3/2‑4I15/2Fluorescent belt carries out thermometric, and Er is utilized in high temperature section3+'s4S3/2‑4I15/2And Tm3+'s3F3‑3H6Fluorescent belt caused by transition carries out thermometric；The present invention can improve sensitivity of thermometry of the fluorescence intensity ratio technology in higher temperature section conscientiously using double centre of luminescence strategies, and the present invention is applied to rare-earth fluorescent field of temperature measurement.
Description
Technical field
The present invention relates to a kind of sensitive in high temperature section thermometric using double centre of luminescence strategies raising fluorescence intensity ratio technologies
The method of degree.
Background technology
The temperature physical quantity most basic as one, considerable effect is all played in every field.Traditional temperature
Degree sensor is all restricted in more and more fields, thus contactless optical sensor comes into being, wherein, fluorescence
Intensity is than technology since stronger anti-interference is noticeable.
Traditional fluorescence intensity ratio thermometry is all based on the thermal coupling energy level pair of rare earth ion, fluorescence intensity ratio and
Relationship between temperature can be described with the hot statistical distribution theory of following Boltzmann：Δ=Aexp (- Δ E/kT),
Middle Δ is the integrated intensity ratio of two beam fluorescence, and A is constant before index, and Δ E is energy level difference, and k is Boltzmann constant, and T is exhausted
To temperature.In temperature sensor field, relative sensitivity is the parameter of most important method of discrimination quality, its base table
It is up to formula：The hot statistical distribution theory of Boltzmann is brought into the most basic expression formula of relative sensitivity by S=d Δs/dT/ Δs,
It can obtain the further expression formula of relative sensitivity：S=Δs E/kT2, thus formula can learn for a determining Δ E,
Relative sensitivity is only related with temperature, it declines with the raising of temperature；Thus formula is again it can be seen that relative sensitivity and temperature
Square inversely, thus with the quick raising of temperature, relative sensitivity can drastically decline.
We are with most typical Er3+'s2H11/2-4I15/2With4S3/2-4I15/2For thermal coupling energy level pair, the energy level pair is utilized
Thermometric is carried out, is 1%K in the relative sensitivity that room temperature 300K or so can be obtained-1；When temperature is increased to 500K or so, phase
0.36%K is dropped sharply to sensitivity-1, the 36% of relative sensitivity when this refers to only room temperature.Under identical condition, relatively
Sensitivity is bigger, then temperature measurement accuracy is higher, thus is difficult to realize using traditional fluorescence intensity ratio thermometry in higher temperature
It spends and high-precision temperature survey is realized in section, this problem seriously limits the further hair of fluorescence intensity ratio thermometry
Exhibition.
Invention content
The purpose of the present invention is to solve be difficult to realize using traditional fluorescence intensity ratio thermometry in higher temperature
The problem of realizing high-precision temperature survey is spent in section, it is sensitive to provide a kind of raising thulium ion near-infrared up-conversion fluorescence thermometric
The method of degree.
The present invention is a kind of to improve fluorescence intensity ratio technology in high temperature section sensitivity of thermometry using double centre of luminescence strategies
Method is to carry out according to the following steps：
First, Yb is prepared3+-Tm3+-Er3+The NaYF that ion is co-doped with4Then nanocrystal carries out tabletting, obtain thermometric sample；
2nd, thermometric sample is put into cold and hot, using 980nm near-infrared lasers diode as excitation light source, is arrived 298
The temperature range of 350K utilizes Er3+'s2H11/2-4I15/2With4S3/2-4I15/2Fluorescent belt carry out temperature calibration, obtain temperature calibration
Curve A；Er is utilized in the high temperature section of 350K-448K3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6Fluorescent belt caused by transition
Temperature calibration is carried out, obtains temperature calibration curve B；
3rd, thermometric sample is positioned over environment to be measured, is carried out using temperature calibration curve A and temperature calibration curve B to be measured
The measurement of temperature.
The object of the present invention is achieved like this：
(1) Yb is prepared3+-Tm3+-Er3+The NaYF that ion is co-doped with4Nanocrystal and in this, as temperature sensing medium.
(2) sample prepared in step (1) is put into the cold and hot accurate control into trip temperature, determined so as to obtain temperature
Mark song line.
(3) temperature range 298 to 350K utilizes traditional Er3+'s2H11/2-4I15/2With4S3/2-4I15/2Thermal coupling energy
Grade is to carrying out temperature calibration；Er is utilized in the high temperature section more than 350K3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6Transition is produced
Raw fluorescence is to carrying out temperature calibration.
(4) measurement of actual temperature can be carried out using two temperature calibration curves in step (3), due in high temperature
Section utilizes traditional Er3+'s2H11/2-4I15/2With4S3/2-4I15/2Thermal coupling energy level is to carrying out the sensitivity that is obtained of thermometric too
It is small, and utilize the Er in step (3)3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6Fluorescence caused by transition can be with to carrying out thermometric
Sensitivity is increased to original three times.
The beneficial effects of the present invention are：
It is double using a kind of utilization involved in the present invention arrived by introducing second luminescent center ion in sample preparation
Centre of luminescence strategy improves fluorescence intensity ratio technology in the method for high temperature section sensitivity of thermometry, and it is strong can to greatly improve fluorescence
The relative sensitivity than thermometry in higher temperature section is spent, the minimum thermometric obtained within the scope of wider temperature is opposite
Sensitivity is 0.82%K-1, larger relative sensitivity 1.59%K is obtained in higher temperature 448K-1, improve the technology
Temperature measurement accuracy, so as to push its functionization.
Description of the drawings
Fig. 1 is Er3+'s2H11/2-4I15/2With4S3/2-4I15/2And Tm3+'s3F3-3H6The alternating temperature of fluorescence caused by transition
Rule；Wherein a is Er3+'s2H11/2-4I15/2, b Er3+'s4S3/2-4I15/2, c Tm3+'s3F3-3H6；
Fig. 2 is traditional Er3+'s2H11/2-4I15/2With4S3/2-4I15/2Fluorescence intensity ratio with temperature alternating temperature rule；
Fig. 3 is Er3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6Fluorescence intensity ratio with temperature alternating temperature rule；
Fig. 4 is using Er3+'s2H11/2-4I15/2With4S3/2-4I15/2The relative sensitivity and adopt that fluorescence intensity ratio is obtained
Use Er3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6The relative sensitivity that fluorescence intensity ratio is obtained；Wherein d is Er3+, e Er3+-
Tm3+。
Specific embodiment
Specific embodiment one：Present embodiment is a kind of to improve fluorescence intensity ratio technology in height using double centre of luminescence strategies
The method of sensitivity of thermometry between warm area is to carry out according to the following steps：
First, Yb is prepared3+-Tm3+-Er3+The NaYF that ion is co-doped with4Then nanocrystal carries out tabletting, obtain thermometric sample；
2nd, thermometric sample is put into cold and hot, using 980nm near-infrared lasers diode as excitation light source, is arrived 298
The temperature range of 350K utilizes Er3+'s2H11/2-4I15/2With4S3/2-4I15/2Fluorescent belt carry out temperature calibration, obtain temperature calibration
Curve A；Er is utilized in the high temperature section of 350K-448K3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6Fluorescent belt caused by transition
Temperature calibration is carried out, obtains temperature calibration curve B；
3rd, thermometric sample is positioned over environment to be measured, is carried out using temperature calibration curve A and temperature calibration curve B to be measured
The measurement of temperature.
Present embodiment prepares Yb using ripe solvent thermal process3+-Tm3+-Er3+The NaYF that ion is co-doped with4Nanocrystal
And in this, as temperature sensing medium.Traditional Yb3+-Er3+The NaYF that ion is co-doped with4There was only Er in nanocrystal3+One shines
Center, and the basic representation of relative sensitivity is：S=Δs E/kT2, it can thus be concluded that relative sensitivity and temperature square into
Inverse relation, thus with the quick raising of temperature, relative sensitivity can drastically decline, this, which is just determined, utilizes Er3+'s2H11/2-4I15/2With4S3/2-4I15/2The relative sensitivity that thermal coupling energy level is obtained when higher temperature section measures can be very
It is small, which limits fluorescence intensity ratio technology high-temperature field application.And the present invention introduces second in sample preparation
Centre of luminescence Tm3+, this can break the limitation of the smaller relative sensitivity caused by a centre of luminescence.
The advantageous effect of present embodiment is：
It is double using a kind of utilization involved in the present invention arrived by introducing second luminescent center ion in sample preparation
Centre of luminescence strategy improves fluorescence intensity ratio technology in the method for high temperature section sensitivity of thermometry, and it is strong can to greatly improve fluorescence
The relative sensitivity than thermometry in higher temperature section is spent, the minimum thermometric obtained within the scope of wider temperature is opposite
Sensitivity is 0.82%K-1, larger relative sensitivity 1.59%K is obtained in higher temperature 448K-1, improve the technology
Temperature measurement accuracy, so as to push its functionization.
Specific embodiment two：The present embodiment is different from the first embodiment in that：Yb in step 13+-Tm3+-Er3 +The NaYF that ion is co-doped with4The preparation method of nanocrystal is solvent-thermal method.It is other same as the specific embodiment one.
Specific embodiment three：The present embodiment is different from the first and the second embodiment in that：Yb in step 13+-Tm3 +-Er3+The nanocrystal NaYF that ion is co-doped with4Preparation method specifically include following steps：
(1) it is stirred and under conditions of whole logical nitrogen protection gas in continuing magnetic force, by 0.79mmol YbCl3·6H2O、
0.2mmol YbCl3·6H2O He 0.005mmol TmCl3·6H2O and 0.005mmol ErCl3·6H2O is added to 50mL's
In round bottom there-necked flask, and 6mL oleic acid and 10mL octadecylene solvents are added in, then seal there-necked flask and be heated to 160 DEG C of guarantors
Warm 1h；
(2) by 6mmol NaOH and 4mmol NH4F is added in the glass sample bottle of the methanol solution equipped with 20mL,
Continuing magnetic force stirs 0.5h at a temperature of 50 DEG C, obtains mixed solution A；
(3) there-necked flask of step (1) is cooled to 50 DEG C, and mixed solution A is added in there-necked flask, at such a temperature
Keep the temperature 0.5h；
(4) there-necked flask of step (3) is warming up to 70 DEG C and is open and keep the temperature 10min；
(5) there-necked flask of step (4) is warming up to 110 DEG C and is open and keep the temperature 10min；
(6) there-necked flask of step (5) is warming up to 300 DEG C and sealing thermal insulation 1h；
(7) there-necked flask of step (6) is cooled to room temperature, adds in 30mL absolute ethyl alcohols and centrifugation obtains nanocrystal
NaYF4Sample；
(8) by nanocrystal NaYF4Sample stands for 24 hours i.e. completion in 70 DEG C of thermostatic drying chamber.Other and specific implementation
Mode one or two is identical.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three：Institute in step 1
The Yb of preparation3+-Tm3+-Er3+The NaYF that ion is co-doped with4Nanocrystal is nano powder material.Other and specific embodiment one
It is identical to one of three.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four：Powder in step 1
The thickness of last tabletting is 2mm.It is other identical with one of specific embodiment one to four.
Specific embodiment six：Unlike one of present embodiment and specific embodiment one to five：In step 2
The scaling method of temperature calibration curve A is：Thermometric sample is put into cold and hot, using 980nm near-infrared lasers diode as swash
Light emitting source, 298 arrive 350K temperature range, every 5k, to Er3+'s2H11/2-4I15/2With4S3/2-4I15/2Fluorescence band strength
It is integrated, ratio then is carried out to the integrated intensity of two fluorescent belts, the integration for obtaining two fluorescent belts under different temperatures is strong
The ratio of degree, reduced value are fitted to get to temperature calibration curve A；Two fluorescent belt integrated intensities of temperature calibration curve A
Ratio range be 0.274-0.453.It is other identical with one of specific embodiment one to five.
Specific embodiment seven：Unlike one of present embodiment and specific embodiment one to six：In step 2
The scaling method of temperature calibration curve B is：Thermometric sample is put into cold and hot, using 980nm near-infrared lasers diode as swash
Light emitting source, in the high temperature section of 350K-448K, every 5k, to Er3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6Caused by transition
Fluorescence band strength is integrated, and is then carried out ratio to the integrated intensity of two fluorescent belts, is obtained two fluorescence under different temperatures
The ratio of the integrated intensity of band, reduced value are fitted to get to temperature calibration curve B.；Two of temperature calibration curve B are glimmering
The ratio range of light belt integrated intensity is 0.094-0.334.It is other identical with one of specific embodiment one to six.
Specific embodiment eight：Unlike one of present embodiment and specific embodiment one to seven：It is sharp in step 3
It is with the method that testing temperature is treated in temperature calibration curve A and temperature calibration curve B measurements：Monitor the red Er of environment to be measured3+'s2H11/2-4I15/2With4S3/2-4I15/2Fluorescent belt, judge that whether it integrates ratio in 0.274-0.453 sections, temperature then utilized in this section
It spends calibration curve A and carries out thermometric；If Er is not monitored in 0.274-0.453 sections3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6Jump
Generated fluorescent belt is moved, judges that whether it integrates ratio in 0.094-0.334 sections, the progress of this function is then utilized in this section
Thermometric.It is other identical with one of specific embodiment one to seven.
Beneficial effects of the present invention are verified by following embodiment：
Embodiment one：The present embodiment is a kind of to improve fluorescence intensity ratio technology in the survey of high temperature section using double centre of luminescence strategies
The method of warm sensitivity is to carry out according to the following steps：
First, Yb is prepared3+-Tm3+-Er3+The NaYF that ion is co-doped with4Then nanocrystal carries out tabletting, obtain thermometric sample；
2nd, thermometric sample is put into cold and hot, using 980nm near-infrared lasers diode as excitation light source, is arrived 298
The temperature range of 350K utilizes Er3+'s2H11/2-4I15/2With4S3/2-4I15/2Fluorescent belt to carry out temperature calibration, obtain the scale of thermometer
Determine curve A；Er is utilized in the high temperature section of 350K-448K3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6Fluorescence caused by transition
It brings trip temperature calibration into, obtains temperature calibration curve B；
3rd, thermometric sample is positioned over environment to be measured, it can be into using temperature calibration curve A and temperature calibration curve B
The measurement of row actual temperature.
Wherein the thickness of pressed powder sample is 2mm, a diameter of 15mm, weight 0.3g, suppresses pressure used during sample
Power is 8MPa.
Yb in step 13+-Tm3+-Er3+The nanocrystal NaYF that ion is co-doped with4Preparation method specifically include following step
Suddenly：
(1) it is stirred and under conditions of whole logical nitrogen protection gas in continuing magnetic force, by 0.79mmol YbCl3·6H2O、
0.2mmol YbCl3·6H2O He 0.005mmol TmCl3·6H2O and 0.005mmol ErCl3·6H2O is added to 50mL's
In round bottom there-necked flask, and 6mL oleic acid and 10mL octadecylene solvents are added in, then seal there-necked flask and be heated to 160 DEG C of guarantors
Warm 1h；
(2) by 6mmol NaOH and 4mmol NH4F is added in the glass sample bottle of the methanol solution equipped with 20mL,
Continuing magnetic force stirs 0.5h at a temperature of 50 DEG C, obtains mixed solution A；
(3) there-necked flask of step (1) is cooled to 50 DEG C, and mixed solution A is added in there-necked flask, at such a temperature
Keep the temperature 0.5h；
(4) there-necked flask of step (3) is warming up to 70 DEG C and is open and keep the temperature 10min；
(5) there-necked flask of step (4) is warming up to 110 DEG C and is open and keep the temperature 10min；
(6) there-necked flask of step (5) is warming up to 300 DEG C and sealing thermal insulation 1h；
(7) there-necked flask of step (6) is cooled to room temperature, adds in 30mL absolute ethyl alcohols and centrifugation obtains nanocrystal
NaYF4Sample；
(8) by nanocrystal NaYF4Sample stands for 24 hours i.e. completion in 70 DEG C of thermostatic drying chamber.
The scaling method of temperature calibration curve A in step 2 is：Thermometric sample is put into cold and hot, it is closely red with 980nm
Outer laser diode is as excitation light source, in the temperature range that 298 arrive 350K, every 5k, to Er3+'s2H11/2-4I15/2With4S3/2-4I15/2Fluorescence band strength integrated, ratio then is carried out to the integrated intensity of two fluorescent belts, obtains different temperatures
The ratio of the integrated intensity of lower two fluorescent belts, reduced value are fitted to get to temperature calibration curve A；Temperature calibration curve A
Two fluorescent belt integrated intensities ratio range be 0.274-0.453.
The scaling method of temperature calibration curve B in step 2 is：Thermometric sample is put into cold and hot, it is closely red with 980nm
Outer laser diode is as excitation light source, in the high temperature section of 350K-448K, every 5k, to Er3+'s4S3/2-4I15/2And Tm3+
's3F3-3H6Fluorescence band strength is integrated caused by transition, is then carried out ratio to the integrated intensity of two fluorescent belts, is obtained
The ratio of the integrated intensity of two fluorescent belts under to different temperatures, reduced value are fitted to get to temperature calibration curve B；Temperature
The ratio range for spending two fluorescent belt integrated intensities of calibration curve B is 0.094-0.334.
Thermometric sample is put into the cold and hot accurate control into trip temperature, is 298 to 448K between temperature-controlled area, so as to obtain
Obtain Temperature Scaling curve.Attached drawing 1 is Er3+'s2H11/2-4I15/2With4S3/2-4I15/2And Tm3+'s3F3-3H6It is glimmering caused by transition
The alternating temperature rule of light, it can be seen that Er3+'s2H11/2-4I15/2With4S3/2-4I15/2And Tm3+'s3F3-3H6It is glimmering caused by transition
Light has different temperature dependences, thus can utilize Er3+'s2H11/2-4I15/2With4S3/2-4I15/2And Er3+'s4S3/2
-4I15/2And Tm3+'s3F3-3H6Into the characterization of trip temperature.As shown in Figure 1, Er3+'s2H11/2-4I15/2And Tm3+'s3F3-3H6All with
It the raising of temperature and increases, but rate of change is variant.In lower temperature, Er3+'s2H11/2-4I15/2Increase faster,
And continue to increase with temperature, Tm3+'s3F3-3H6Then there is faster rate of rise, this explanation utilizes traditional Er3+'s2H11/2-4I15/2With4S3/2-4I15/2In high temperature section, thermometric will obtain smaller relative sensitivity, and utilize Er3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6Larger relative sensitivity will be obtained.
The present embodiment prepares Yb using ripe solvent thermal process3+-Tm3+-Er3+The NaYF that ion is co-doped with4Nanocrystal is simultaneously
In this, as temperature sensing medium.Traditional Yb3+-Er3+The NaYF that ion is co-doped with4There was only Er in nanocrystal3+During one shines
The heart, and the basic representation of relative sensitivity is：S=Δs E/kT2, it can thus be concluded that relative sensitivity and temperature is square into anti-
Than relationship, thus with the quick raising of temperature, relative sensitivity can drastically decline, this, which is just determined, utilizes Er3+'s2H11/2-4I15/2With4S3/2-4I15/2The relative sensitivity meeting very little that thermal coupling energy level is obtained when higher temperature section measures, this
Limit application of the fluorescence intensity ratio technology in high-temperature field.And the present embodiment introduces second in sample preparation and shines
Center Tm3+, this can break the limitation of the smaller relative sensitivity caused by a centre of luminescence.
As shown in Figure 2, in 298 to 448K temperature range, Er3+'s2H11/2-4I15/2With4S3/2-4I15/2Fluorescence is strong
Degree illustrates that this ratio can be used for than can be well fitted with the hot Statistical Distribution of Boltzmann between temperature
Characterize temperature.
As shown in Figure 3, in 298 to 448K temperature range, Er3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6Fluorescence is strong
It can be well fitted with exponential function between degree ratio and temperature, illustrate to be used for measuring temperature using two centres of luminescence
Degree.
With reference to the accompanying drawings 2 and attached drawing 3 fitting result, can obtain it is attached shown in Fig. 4 as a result, i.e. use Er3+'s2H11/2-4I15/2With4S3/2-4I15/2Relative sensitivity that fluorescence intensity ratio is obtained and using Er3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6The comparison for the relative sensitivity that fluorescence intensity ratio is obtained.It can be seen that Er3+'s2H11/2-4I15/2With4S3/2-4I15/2Phase
Sensitivity is drastically declined with the raising of temperature, when temperature reaches 448K, relative sensitivity only has 0.50%K-1, this is aobvious
So it is unfavorable for high precision measuring temperature.In contrast, Er is utilized3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6Relative sensitivity with temperature
The raising of degree and quickly increase, when temperature reaches 448K, opposite high sensitivity reaches 1.59%K-1, it is Er3+'s4S3/2-4I15/2With
Tm3+'s3F3-3H6Three times of the relative sensitivity obtained.
The present embodiment passes through in Yb3+-Er3+The NaYF of co-doped4Second centre of luminescence of nanocrystalline middle introducing, i.e. Tm3 +, then utilize Er3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6Measurement into trip temperature can obtain up to 1.59%K in 448K-1
Relative sensitivity, this numerical value compared to utilize single centre of luminescence Er3+'s2H11/2-4I15/2With4S3/2-4I15/2It is relatively clever
Sensitivity improves three times.Under square one, relative sensitivity improves, then the measurement accuracy of temperature can also be promoted therewith, because
It is and a kind of clever in high temperature section thermometric using double centre of luminescence strategies raising fluorescence intensity ratio technologies involved by the present embodiment
Fluorescence intensity thermometry can be extended in higher temperature range by the method for sensitivity, so as to obtain the temperature of higher precision
Measurement result.
Claims (8)
1. a kind of improve method of the fluorescence intensity ratio technology in high temperature section sensitivity of thermometry using double centre of luminescence strategies, special
Sign is that be carried out according to the following steps：
First, Yb is prepared3+-Tm3+-Er3+The NaYF that ion is co-doped with4Then nanocrystal carries out tabletting, obtain thermometric sample；
2nd, thermometric sample is put into cold and hot, using 980nm near-infrared lasers diode as excitation light source, arrives 350K's 298
Temperature range utilizes Er3+'s2H11/2-4I15/2With4S3/2-4I15/2Fluorescent belt carry out temperature calibration, obtain temperature calibration curve A；
Er is utilized in the high temperature section of 350K-448K3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6Fluorescent belt caused by transition carries out temperature
Scale is determined, and obtains temperature calibration curve B；
3rd, thermometric sample is positioned over environment to be measured, carries out treating testing temperature using temperature calibration curve A and temperature calibration curve B
Measurement.
2. the double centre of luminescence strategies of a kind of utilization according to claim 1 improve fluorescence intensity ratio technologies and are surveyed in high temperature section
The method of warm sensitivity, it is characterised in that Yb in step 13+-Tm3+-Er3+The NaYF that ion is co-doped with4The preparation side of nanocrystal
Method is solvent-thermal method.
3. the double centre of luminescence strategies of a kind of utilization according to claim 1 improve fluorescence intensity ratio technologies and are surveyed in high temperature section
The method of warm sensitivity, it is characterised in that Yb in step 13+-Tm3+-Er3+The nanocrystal NaYF that ion is co-doped with4Preparation side
Method specifically includes following steps：
(1) it is stirred and under conditions of whole logical nitrogen protection gas in continuing magnetic force, by 0.79mmol YbCl3·6H2O、
0.2mmol YbCl3·6H2O He 0.005mmol TmCl3·6H2O and 0.005mmol ErCl3·6H2O is added to 50mL's
In round bottom there-necked flask, and 6mL oleic acid and 10mL octadecylene solvents are added in, then seal there-necked flask and be heated to 160 DEG C of guarantors
Warm 1h；
(2) by 6mmol NaOH and 4mmol NH4F is added in the glass sample bottle of the methanol solution equipped with 20mL, at 50 DEG C
At a temperature of continuing magnetic force stirring 0.5h, obtain mixed solution A；
(3) there-necked flask of step (1) is cooled to 50 DEG C, and mixed solution A is added in there-necked flask, kept the temperature at such a temperature
0.5h；
(4) there-necked flask of step (3) is warming up to 70 DEG C and is open and keep the temperature 10min；
(5) there-necked flask of step (4) is warming up to 110 DEG C and is open and keep the temperature 10min；
(6) there-necked flask of step (5) is warming up to 300 DEG C and sealing thermal insulation 1h；
(7) there-necked flask of step (6) is cooled to room temperature, adds in 30mL absolute ethyl alcohols and centrifugation obtains nanocrystal NaYF4Sample
Product；
(8) by nanocrystal NaYF4Sample stands for 24 hours i.e. completion in 70 DEG C of thermostatic drying chamber.
4. the double centre of luminescence strategies of a kind of utilization according to claim 1 improve fluorescence intensity ratio technologies and are surveyed in high temperature section
The method of warm sensitivity, it is characterised in that prepared Yb in step 13+-Tm3+-Er3+The NaYF that ion is co-doped with4Nanocrystal
For nano powder material.
5. the double centre of luminescence strategies of a kind of utilization according to claim 1 improve fluorescence intensity ratio technologies and are surveyed in high temperature section
The method of warm sensitivity, it is characterised in that the thickness of pressed powder is 2mm in step 1.
6. the double centre of luminescence strategies of a kind of utilization according to claim 1 improve fluorescence intensity ratio technologies and are surveyed in high temperature section
The method of warm sensitivity, it is characterised in that the scaling method of the temperature calibration curve A in step 2 is：Thermometric sample is put into cold
Thermal station, using 980nm near-infrared lasers diode as excitation light source, 298 arrive 350K temperature range, every 5k, to Er3+
's2H11/2-4I15/2With4S3/2-4I15/2Fluorescence band strength integrated, then the integrated intensity of two fluorescent belts is compared
Value, obtains the ratio of the integrated intensity of two fluorescent belts under different temperatures, and reduced value is fitted to get to temperature calibration curve
A；The ratio range of two fluorescent belt integrated intensities of temperature calibration curve A is 0.274-0.453.
7. the double centre of luminescence strategies of a kind of utilization according to claim 1 improve fluorescence intensity ratio technologies and are surveyed in high temperature section
The method of warm sensitivity, it is characterised in that the scaling method of the temperature calibration curve B in step 2 is：Thermometric sample is put into cold
Thermal station, using 980nm near-infrared lasers diode as excitation light source, in the high temperature section of 350K-448K, every 5k, to Er3+
's4S3/2-4I15/2And Tm3+'s3F3-3H6Fluorescence band strength is integrated caused by transition, then to the integration of two fluorescent belts
Intensity carries out ratio, obtains the ratio of the integrated intensity of two fluorescent belts under different temperatures, and reduced value is fitted to get to temperature
Spend calibration curve B；The ratio range of two fluorescent belt integrated intensities of temperature calibration curve B is 0.094-0.334.
8. the double centre of luminescence strategies of a kind of utilization according to claim 1 improve fluorescence intensity ratio technologies and are surveyed in high temperature section
The method of warm sensitivity, it is characterised in that treat testing temperature using temperature calibration curve A and temperature calibration curve B measurements in step 3
Method be：Monitor the red Er of environment to be measured3+'s2H11/2-4I15/2With4S3/2-4I15/2Fluorescent belt, judge its integrate ratio whether
In 0.274-0.453 sections, then thermometric is carried out using temperature calibration curve A in this section；If not in 0.274-0.453 sections,
Then monitor Er3+'s4S3/2-4I15/2And Tm3+'s3F3-3H6Fluorescent belt caused by transition, judge its integrate ratio whether
0.094-0.334 sections then carry out thermometric in this section using this function.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810241597.7A CN108168730B (en) | 2018-03-22 | 2018-03-22 | A method of fluorescence intensity ratio technology is improved in high temperature section sensitivity of thermometry using double centre of luminescence strategies |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810241597.7A CN108168730B (en) | 2018-03-22 | 2018-03-22 | A method of fluorescence intensity ratio technology is improved in high temperature section sensitivity of thermometry using double centre of luminescence strategies |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108168730A true CN108168730A (en) | 2018-06-15 |
| CN108168730B CN108168730B (en) | 2019-10-08 |
Family
ID=62512223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810241597.7A Active CN108168730B (en) | 2018-03-22 | 2018-03-22 | A method of fluorescence intensity ratio technology is improved in high temperature section sensitivity of thermometry using double centre of luminescence strategies |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108168730B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104019921A (en) * | 2014-06-18 | 2014-09-03 | 东南大学 | Temperature indicating method based on up-conversion luminescent materials |
| US20150362432A1 (en) * | 2013-01-22 | 2015-12-17 | University Of Massachusetts Medical School | Compositions and methods for upconverting luminescence with engineered excitation and applications thereof |
| CN105400516A (en) * | 2015-11-09 | 2016-03-16 | 南京邮电大学 | Novel core-shell structure light and temperature sensing material and preparation method thereof |
| CN107011905A (en) * | 2017-05-12 | 2017-08-04 | 南方科技大学 | Temperature sensing and multichannel imaging method based on up-conversion material |
-
2018
- 2018-03-22 CN CN201810241597.7A patent/CN108168730B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150362432A1 (en) * | 2013-01-22 | 2015-12-17 | University Of Massachusetts Medical School | Compositions and methods for upconverting luminescence with engineered excitation and applications thereof |
| CN104019921A (en) * | 2014-06-18 | 2014-09-03 | 东南大学 | Temperature indicating method based on up-conversion luminescent materials |
| CN105400516A (en) * | 2015-11-09 | 2016-03-16 | 南京邮电大学 | Novel core-shell structure light and temperature sensing material and preparation method thereof |
| CN107011905A (en) * | 2017-05-12 | 2017-08-04 | 南方科技大学 | Temperature sensing and multichannel imaging method based on up-conversion material |
Non-Patent Citations (5)
| Title |
|---|
| 刘丰: "稀土掺杂NaYF_4纳米晶体的上转换荧光特性及应用研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 刘丽欣: "稀土掺杂NaYF_4纳米晶的上转换光动力疗法相关科学问题研究", 《中国博士学位论文全文数据库 医药卫生科技辑》 * |
| 轩岩: "稀土离子掺杂荧光材料的制备及其光温性质研究", 《中国优秀硕士学位论文全文数据库 基础科学辑》 * |
| 高晓阳: "稀土掺杂氟氧微晶玻璃上转换及其温度特性的研究", 《中国优秀硕士学位论文全文数据库 基础科学辑》 * |
| 齐海岳: "基于稀土离子掺杂纳米材料的荧光与温度特性研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108168730B (en) | 2019-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Morassuti et al. | Eu3+-doped alumino-phosphate glass for ratiometric thermometer based on the excited state absorption | |
| CN110146194B (en) | Fluorescence intensity ratio temperature measurement method based on mixed temperature sensing material | |
| Pérez-Rodríguez et al. | Relevance of radiative transfer processes on Nd3+ doped phosphate glasses for temperature sensing by means of the fluorescence intensity ratio technique | |
| León-Luis et al. | Effects of Er3+ concentration on thermal sensitivity in optical temperature fluorotellurite glass sensors | |
| Khalil et al. | Europium beta-diketonate temperature sensors: Effects of ligands, matrix, and concentration | |
| CN102798485B (en) | Temperature sensing method based on upconversion fluorescent powder | |
| CN106495474B (en) | A kind of Eu can be used for temperature sensing2+/Eu3+Codope glass ceramic composite material and its preparation method and application | |
| CN106908168B (en) | A kind of highly sensitive temperature sensing method based on neodymium ion near-infrared fluorescent | |
| CN105198225A (en) | Double active ion doped bicrystal glass ceramic fluorescence temperature probe materials and preparation method thereof | |
| CN108896201A (en) | A kind of high-resolution organism thermometry of high sensitivity | |
| CN105300563B (en) | A kind of modification method of up-conversion fluorescence strength ratio thermometry | |
| US6840669B2 (en) | Methods and devices for sensing temperature and another physical parameter with a single optical probe | |
| Seat et al. | Single-crystal ruby fiber temperature sensor | |
| Zanuto et al. | Two ratiometric thermometry methods based on the interplay between Eu2+ and Eu3+ and single Eu3+ emissions on OH−-free low-silica calcium aluminosilicate glass | |
| CN108168730B (en) | A method of fluorescence intensity ratio technology is improved in high temperature section sensitivity of thermometry using double centre of luminescence strategies | |
| CN108489632B (en) | A method of improving fluorescence intensity ratio technology temperature measurement accuracy | |
| Martins et al. | An overview of luminescent primary thermometers | |
| CN109945987B (en) | Method for realizing high-sensitivity temperature measurement in higher temperature range | |
| Sidiroglou et al. | Effects of high-temperature heat treatment on Nd3+-doped optical fibers for use in fluorescence intensity ratio based temperature sensing | |
| Zhang et al. | Thermal characteristics of alexandrite fluorescence decay at high temperatures, induced by a visible laser diode emission | |
| Shimizu et al. | Fine-temperature-resolution imaging luminescence thermometry demonstrated with Ce3+-doped Y3Al5O12 | |
| CN108426651B (en) | The temp measuring method for carrying out anti-white LED light source interference using purple light is converted on thulium ion | |
| CN110082326A (en) | A kind of wall heat flux density measuring method based on CdTe thin film | |
| CN108489617B (en) | A method of improving thulium ion near-infrared up-conversion fluorescence sensitivity of thermometry | |
| Shen et al. | Characterization of an optical fiber thermometer using Tm3+: YAG crystal, based on the fluorescence lifetime approach |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210120 Address after: Building 9, accelerator, 14955 Zhongyuan Avenue, Songbei District, Harbin City, Heilongjiang Province Patentee after: INDUSTRIAL TECHNOLOGY Research Institute OF HEILONGJIANG PROVINCE Address before: 150001 No. 92 West straight street, Nangang District, Heilongjiang, Harbin Patentee before: HARBIN INSTITUTE OF TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230306 Address after: 150027 Room 412, Unit 1, No. 14955, Zhongyuan Avenue, Building 9, Innovation and Entrepreneurship Plaza, Science and Technology Innovation City, Harbin Hi tech Industrial Development Zone, Heilongjiang Province Patentee after: Heilongjiang Industrial Technology Research Institute Asset Management Co.,Ltd. Address before: Building 9, accelerator, 14955 Zhongyuan Avenue, Songbei District, Harbin City, Heilongjiang Province Patentee before: INDUSTRIAL TECHNOLOGY Research Institute OF HEILONGJIANG PROVINCE |
|
| TR01 | Transfer of patent right |