CN115477946B - Green fluorescent material for non-contact temperature sensor and preparation method thereof - Google Patents
Green fluorescent material for non-contact temperature sensor and preparation method thereof Download PDFInfo
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Abstract
The application discloses a green fluorescent material for a non-contact temperature sensor and a preparation method thereof, wherein the chemical formula of the green fluorescent material is ALa (1‑x) Er x LiTeO 6 Wherein A is any one of Ba, sr, ca or Mg. The fluorescent powder material has high color purity, and the color purity is respectively up to 95%,96%,98% and 97%. In addition, because of two thermally coupled excited state energy levels of rare earth Er ions 2 H 11/2 And 4 S 3/2 ) The special relation with the temperature change, so the series of Er ion doped fluorescent powder materials can be used for researching a non-contact temperature sensor.
Description
Technical Field
The application relates to the technical fields of rare earth luminescent materials and non-contact temperature sensors, in particular to a green fluorescent material for a non-contact temperature sensor and a preparation method thereof.
Background
Temperature plays an important role as a thermodynamic physical quantity in biomedical science, industrial production, and human daily life. Conventional contact thermometers, such as liquid filled glass thermometers, thermocouples, thermal resistors, etc., have been the primary temperature measuring device for recent decades. Conventional contact thermometers based on the principle of thermal equilibrium between the sensor and the object typically require convective heat transfer to effect temperature measurement, which may cause local temperature changes in the measured object during the measurement process.
Moreover, these thermometers are not easily miniaturized and cannot be used for temperature measurement of batteries, minute electronic components, fast moving objects, and the like. In addition, the existing thermometer cannot meet the temperature control and measurement requirements under extreme conditions such as corrosive environments and electromagnetic interference environments. Therefore, the development of the non-contact temperature sensor with high precision and high sensitivity has important practical significance.
Non-contact optical temperature sensors are an effective method of making temperature measurements under extreme conditions, microscale environments, and other special conditions. In the noncontact optical thermometer, various optical temperature sensing methods based on characteristics of fluorescence intensity, emission bandwidth, fluorescence lifetime, fluorescence Intensity Ratio (FIR), and the like have been used for measuring temperature of rare earth ion doped phosphor. In addition, sensors based on the FIR principle have higher durability, higher spatial resolution and large-scale real-time monitoring imaging functions compared to conventional thermal sensors.
The rare earth fluorescent material not only can be used for white light LED illumination, but also can be applied to the field of temperature sensing when a specific functional relation exists between the fluorescent characteristic and the temperature.
Due to the two thermally coupled excited states of the rare earth Er ions 2 H 11/2 And 4 S 3/2 ) To the ground state% 4 I 15/2 ) The transition emission results in two very strong green emission bands and a suitable energy difference between the two excited states (ΔE≡700 cm) -1 ) The Er ion is potentially useful in non-contact temperature sensors.
At present, a plurality of Er ion doped green luminescent materials applicable to the field of temperature sensing have been synthesized and reported at home and abroad. For example, in 2018, J.Manam et al synthesized BaTiO 3 Er up-conversion green luminescent material with absolute sensitivity of 0.0032K -1 . In 2020, zhang et al synthesized GaTaO 4 Er up-conversion green luminescent material with absolute sensitivity and relative sensitivity of 0.0041K -1 And 0.0112K -1 . In 2021, hua et al reported a La 2 MgTiO 6 Er green luminescent material with absolute sensitivity and relative sensitivityCan not reach 0.00963K -1 And 0.01107K -1 Can be applied to an optical temperature sensor.
The prior art CN201911057720.0 discloses a near ultraviolet excited green phosphor for a non-contact temperature detector. The chemical expression of the green fluorescent powder is SrLa 1-x Er x AlO 4 Wherein x is more than or equal to 0.01 and less than or equal to 0.07. The fluorescent powder has a relatively abundant excitation spectrum, has relatively strong excitation peaks at 356nm, 365nm, 377nm and 488nm, has the highest luminous intensity of the excitation peak at 377nm, and has the obtained emission peak at 528nm and 548nm, and is suitable for being used as green fluorescent powder excited by near ultraviolet. In addition, due to the two thermally coupled excited states of Er ions 2 H 11/2 And 4 S 3/2 ) Thus can be used as a non-contact temperature detector, but the sensitivity claimed in this technology can reach 1.42% K -1 Whether the sensitivity is absolute or relative is not indicated, and the color purity data of the obtained phosphor is not disclosed.
Disclosure of Invention
The application provides a green fluorescent material for a non-contact temperature sensor and a preparation method thereof, the color purity of the obtained green fluorescent material is up to 95%,96%,98% and 97% respectively, and the two thermally coupled excitation state energy levels of Er ions in the material are [ ] 2 H 11/2 And 4 S 3/2 ) To the ground state% 4 I 15/2 ) The absolute sensitivity of the series of materials can be achieved by the existence of a specific functional relationship between the transition emission and the temperature: 0.0103K -1 ，0.0120K -1 ，0.00706K -1 ，0.00603K -1 The relative sensitivity can be achieved: 0.0107K -1 ，0.0120K -1 ，0.0112K -1 ，0.0115K -1 The series of materials can be used in the field of non-contact temperature sensing.
The application provides a green fluorescent material for a non-contact temperature sensor, wherein the chemical formula of the green fluorescent material is ALa (1-x) Er x LiTeO 6 Wherein A is any one of Ba, sr, ca or Mg; wherein x is more than or equal to 0.01 and less than or equal to 0.15.
Preferably, x=0.06.
Specifically, the chemical formula of the green fluorescent material is BaLa 0.94 LiTeO 6 :6％Er 3+ (BLLT:6％Er 3+ )，SrLa 0.94 LiTeO 6 :6％Er 3+ (SLLT:6％Er 3+ )，CaLa 0.94 LiTeO 6 :6％Er 3+ (CLLT:6％Er 3+ )，MgLa 0.94 LiTeO 6 :6％Er 3+ (MLLT:6％Er 3+ ). The series of green fluorescent materials are all prepared by adopting a high-temperature solid phase method.
The green fluorescent material with the structure can obtain strong green light emission at 526nm and 547nm under the excitation of 379nm near ultraviolet light, and the fluorescent powder can be used as a green luminescent fluorescent powder raw material of a white light-emitting LED. Two thermally coupled excited state energy levels of Er ions in the fluorescent powder 2 H 11/2 And 4 S 3/2 ) To the ground state% 4 I 15/2 ) There is a specific functional relationship between the transition emission capability and the temperature, and the transition emission capability and the temperature can be used in a non-contact temperature sensor.
Meanwhile, the obtained fluorescent powder has high color purity and absolute sensitivity can reach: 0.0103K -1 ，0.0120K -1 ，0.00706K -1 ，0.00603K -1 The relative sensitivity can be achieved: 0.0107K -1 ，0.0120K -1 ，0.0112K -1 ，0.0115K -1 The sensor is used as a raw material of a non-contact temperature sensor, and has high sensitivity and high detection accuracy.
In another aspect, the present application further provides a method for preparing the fluorescent material, including the following steps: the raw materials are weighed according to the mole ratio and then uniformly mixed, and the high-temperature solid phase synthesis method is adopted for preparing the catalyst.
Preferably, the raw material substance comprises: la source, li source, te source, er source and A source; the source A is one of Ba source, sr source, ca source and Mg source.
Preferably, the La source substance is La 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The Li source material is Li 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the Te source substance is TeO 2 The method comprises the steps of carrying out a first treatment on the surface of the The Er source material is Er 2 O 3 。
Preferably, the Ba source is BaCO 3 The method comprises the steps of carrying out a first treatment on the surface of the The Sr source substance is SrCO 3 The method comprises the steps of carrying out a first treatment on the surface of the Ca source material is CaCO 3 The method comprises the steps of carrying out a first treatment on the surface of the The Mg source substance is MgCO 3 。
Preferably, the raw material is BaCO 3 、La 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，BaCO 3 ：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 The molar ratio of (2) is 1:0.47:0.5:1:0.03.
preferably, the raw material is SrCO 3 、La 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，SrCO 3 ：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 The molar ratio of (2) is 1:0.47:0.5:1:0.03.
preferably, the raw material substance is CaCO 3 、La 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，CaCO 3 ：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 The molar ratio of (2) is 1:0.47:0.5:1:0.03.
preferably, the raw material is MgO, la 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，MgO：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 The molar ratio of (2) is 1:0.47:0.5:1:0.03.
the raw materials are mixed according to the molar ratio, and the green fluorescent powder material with better color purity and higher sensitivity can be prepared by adopting a high-temperature solid-phase synthesis method.
The molar ratios calculated above are accurately weighed according to the stoichiometric ratio respectively: baCO 3 ，SrCO 3 ，CaCO 3 ，MgCO 3 ，La 2 O 3 ，Li 2 CO 3 ，TeO 2 And Er 2 O 3 。
Preferably, the high temperature solid phase synthesis method comprises the steps of:
(1) Grinding: uniformly mixing the raw materials, and fully grinding the mixture in an agate mortar for 30min to obtain a reactant;
(2) Presintering: placing the reactant into a corundum crucible and placing the corundum crucible into a muffle furnace, heating the corundum crucible for 300min, then heating the corundum crucible to 600 ℃ in the muffle furnace, and preserving the heat for 360min;
(3) And (3) sintering: continuously heating for 500min, heating to 1000-1050 ℃, preserving heat for 300-600 min, and cooling to room temperature along with a furnace to obtain the fluorescent material.
Preferably, when the source a is a source Ba, the temperature is raised to 1000 ℃ in step (3).
Preferably, when the source A is one of the source Sr, the source Ca or the source Mg, the temperature is raised to 1050℃in the step (3).
In the pre-sintering and re-sintering stages, in order to ensure that the raw materials can fully react under the high-temperature reaction condition, the grinding times and time in the step (1) can be increased, so that the powder reaction is more uniform, and finally, the target powder sample is obtained.
The beneficial effects that this application can produce include:
1) The green fluorescent material for the non-contact temperature sensor, provided by the application, has the color purity of 95%,96%,98% and 97% respectively, and is favorable for improving the measurement sensitivity of the fluorescent powder when the fluorescent powder is used as a raw material for preparing the non-contact temperature sensor. And the two thermal coupling excited state energy levels of Er ions in the obtained fluorescent powder material 2 H 11/2 And 4 S 3/2) to the ground state% 4 I 15/2 ) The functional relation between the transition emission and the temperature meets the requirements of non-contact temperature sensing raw materials, and the absolute sensitivity of the fluorescent powder obtained in each embodiment can be achieved: 0.0103K -1 ，0.0120K -1 ，0.00706K -1 ，0.00603K -1 The relative sensitivity can be achieved: 0.0107K -1 ，0.0120K -1 ，0.0112K -1 ，0.0115K -1 The series of materials can be usedIn the field of non-contact temperature sensing, the sensor is used as a raw material for preparing the sensor, and the temperature measurement sensitivity and accuracy of the obtained sensor can be effectively improved.
2) The green fluorescent material for the non-contact temperature sensor provided by the application can obtain strong green light emission at 526nm and 547nm under the excitation of 379nm near ultraviolet light, and can be used as a green fluorescent powder light emitting part of a white light emitting LED.
3) The green fluorescent material for the non-contact temperature sensor is prepared by adopting a high-temperature solid phase method, and can be obtained by grinding, presintering and sintering.
Drawings
FIG. 1 shows the BLLT:6% Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ An XRD pattern of (a);
FIG. 2 shows the BLLT:6% Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ At 298-573K, the wavelength range is 500-600 nm, wherein (a) is BLLT:6% Er 3+ The variable-temperature emission spectrum of (b) is SLLT (6%Er) 3+ And (c) is CLLT (6% Er) 3+ The variable-temperature emission spectrum of (d) is MLLT (multi-layer liquid crystal display) with the content of Er being 6 percent 3+ Is a variable-temperature emission spectrum;
FIG. 3 shows the BLLT:6% Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ A fluorescence intensity ratio profile of (2);
FIG. 4 shows the BLLT:6% Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ Is a pattern of absolute sensitivity of (2);
FIG. 5 shows the BLLT:6% Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ Is a relatively sensitive map of (2).
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
Technical means which are not described in detail in the application and are not used for solving the technical problems of the application are all arranged according to common general knowledge in the field, and various common general knowledge arrangement modes can be realized.
Examples
The materials used in the examples below were commercially available unless otherwise specified.
The fluorescent powder is BLLT (BLLT: 6% Er) 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ All samples were synthesized using high temperature solid phase synthesis.
Example 1 preparation of BLLT 6% Er 3+ Fluorescent powder:
(1) Weighing: 0.7067g BaCO is accurately weighed according to stoichiometric ratio 3 (99.0％)、0.5484gLa 2 O 3 (99.99％)、0.1323gLi 2 CO 3 (99.99％)、0.5715gTeO 2 (99.99％)、0.0411gEr 2 O 3 (99.99％)；
(2) Grinding: mixing all the raw materials, fully grinding for 30min in an agate mortar, and placing reactants into a corundum crucible after grinding;
(3) Pre-sintering: placing the corundum crucible containing the reactant into a muffle furnace, heating to 600 ℃ for 300min, and preserving heat for 360min;
(4) And (3) a re-sintering stage: and (3) placing the corundum crucible containing the reactant into a muffle furnace, heating for 500min to 1000 ℃, preserving heat for 600min, and then cooling to room temperature along with the furnace to finally obtain the target powder sample.
EXAMPLE 2 preparation of SLLT 6% Er 3+ Fluorescent powder:
(1) Weighing: 0.5803gSrCO is accurately weighed according to stoichiometric ratio 3 (99％)、0.6020gLa 2 O 3 (99.99％)、0.1452gLi 2 CO 3 (99.99％)、0.6274gTeO 2 (99.99％)、0.0451gEr 2 O 3 (99.99％)；
(2) Grinding: mixing all the raw materials, fully grinding for 30min in an agate mortar, and placing reactants into a corundum crucible after grinding;
(3) Pre-sintering: placing the corundum crucible containing the reactant into a muffle furnace, heating for 300min, then heating the inside of the muffle furnace to 600 ℃ and preserving heat for 360min;
(4) And (3) a re-sintering stage: and (3) placing the corundum crucible containing the reactant into a muffle furnace, heating for 500min to 1050 ℃, preserving heat for 300min, and then cooling to room temperature along with the furnace to finally obtain the target powder sample.
EXAMPLE 3 preparation of CLLT:6% Er 3+ Fluorescent powder:
(1) Weighing: 0.4340g CaCO is accurately weighed according to stoichiometric ratio 3 (99.0％)、0.6640gLa 2 O 3 (99.99％)、0.1602gLi 2 CO 3 (99.99％)、0.6920gTeO 2 (99.99％)、0.0498gEr 2 O 3 (99.99％)；
(2) Grinding: mixing all the raw materials, fully grinding for 30min in an agate mortar, and placing reactants into a corundum crucible after grinding;
(3) Pre-sintering: placing the corundum crucible containing the reactant into a muffle furnace, heating for 300min, then heating the inside of the muffle furnace to 600 ℃ and preserving heat for 360min;
(4) And (3) a re-sintering stage: and (3) placing the corundum crucible containing the reactant into a muffle furnace, heating for 500min to 1050 ℃, preserving heat for 300min, and then cooling to room temperature along with the furnace to finally obtain the target powder sample.
EXAMPLE 4 preparation of MLLT:6% Er 3+ Fluorescent powder:
(1) Weighing: 0.3785g MgCO is accurately weighed according to stoichiometric ratio 3 (98％)、0.6875gLa 2 O 3 (99.99％)、0.1659gLi 2 CO 3 (99.99％)、0.7166gTeO 2 (99.99％)、0.0515gEr 2 O 3 (99.99％)；
(2) Grinding: mixing all the raw materials, fully grinding for 30min in an agate mortar, and placing reactants into a corundum crucible after grinding;
(3) Pre-sintering: placing the corundum crucible containing the reactant into a muffle furnace, heating for 300min, then heating the inside of the muffle furnace to 600 ℃ and preserving heat for 360min;
(4) And (3) a re-sintering stage: and (3) placing the corundum crucible containing the reactant into a muffle furnace, heating for 500min to 1050 ℃, preserving heat for 300min, and then cooling to room temperature along with the furnace to finally obtain the target powder sample.
EXAMPLE 5 preparation of BaLa 0.99 Er 0.01 LiTeO 6
The difference from example 1 is that: 0.7085g BaCO is accurately weighed according to the stoichiometric ratio in the step (1) 3 (99.0％)、0.5790gLa 2 O 3 (99.99％)、0.1326gLi 2 CO 3 (99.99％)、0.5730gTeO 2 (99.99％)、0.0069gEr 2 O 3 (99.99％)。
EXAMPLE 6 preparation of BaLa 0.85 Er 0.15 LiTeO 6
The difference from example 1 is that: 0.7035g BaCO is accurately weighed according to the stoichiometric ratio in the step (1) 3 (99.0％)、0.4936gLa 2 O 3 (99.99％)、0.1317gLi 2 CO 3 (99.99％)、0.5689gTeO 2 (99.99％)、0.1023gEr 2 O 3 (99.99％)。
EXAMPLE 7 preparation of SrLa 0.99 Er 0.01 LiTeO 6
The difference from example 2 is that: in the step (1), 0.5819gSrCO is accurately weighed according to the stoichiometric ratio 3 (99％)、0.6357gLa 2 O 3 (99.99％)、0.1456gLi 2 CO 3 (99.99％)、0.6291gTeO 2 (99.99％)、0.0075gEr 2 O 3 (99.99％)。
EXAMPLE 8 preparation of SrLa 0.85 Er 0.15 LiTeO 6
The difference from example 2 is that: in the step (1), 0.5774gSrCO is accurately weighed according to the stoichiometric ratio 3 (99％)、0.5416gLa 2 O 3 (99.99％)、0.1445gLi 2 CO 3 (99.99％)、0.6243gTeO 2 (99.99％)、0.1122gEr 2 O 3 (99.99％)。
EXAMPLE 9 preparation of Cala 0.99 Er 0.01 LiTeO 6
The difference from example 3 is that: 0.4353g CaCO is accurately weighed according to the stoichiometric ratio in the step (1) 3 (99.0％)、0.7015gLa 2 O 3 (99.99％)、0.1607gLi 2 CO 3 (99.99％)、0.6942gTeO 2 (99.99％)、0.0083gEr 2 O 3 (99.99％)。
EXAMPLE 10 preparation of Cala 0.85 Er 0.15 LiTeO 6
The difference from example 3 is that: accurately weighing 0.4316g CaCO according to the stoichiometric ratio in the step (1) 3 (99.0％)、0.5971gLa 2 O 3 (99.99％)、0.1593gLi 2 CO 3 (99.99％)、0.6882gTeO 2 (99.99％)、0.1237gEr 2 O 3 (99.99％)。
EXAMPLE 11 preparation of MgLa 0.99 Er 0.01 LiTeO 6
The difference from example 4 is that: 0.3797g of MgCO is accurately weighed according to the stoichiometric ratio in the step (1) 3 (98％)、0.7264gLa 2 O 3 (99.99％)、0.1664gLi 2 CO 3 (99.99％)、0.7188gTeO 2 (99.99％)、0.0086gEr 2 O 3 (99.99％)。
EXAMPLE 12 preparation of MgLa 0.85 Er 0.15 LiTeO 6
The difference from example 4 is that: 0.3764g of MgCO is accurately weighed according to the stoichiometric ratio in the step (1) 3 (98％)、0.6181gLa 2 O 3 (99.99％)、0.1649gLi 2 CO 3 (99.99％)、0.7125gTeO 2 (99.99％)、0.1281gEr 2 O 3 (99.99％)。
Each property of the phosphors obtained in examples 1 to 4 was examined and the results obtained were:
samples of the phosphors obtained in examples 1-4 were prepared according to Li Xiangping, zhong Haiyang, cheng Ligong, sun Jiadan, zhang Jinsu, wang Yizhuo, chen Bao, respectively, red phosphor NaGdTiO for white light LEDs 4 :Eu 3+ Preparation and optical Properties of [ J ]]138-143 XRD detection, variable temperature emission detection and variable temperature emission spectrogram detection are carried out; according to Wu Zhongli, wu Gongmei, yao Zhen, tang Lidan, dai Xiaochun, guo Yu. GdNBO 4 :Er 3+ /Yb 3+ Up-conversion luminescence and temperature characteristic of phosphor powder [ J]The method disclosed in the luminous journal 2017,38 (09): 1129-1135, is used for absolute sensitivity detection and relative sensitivity detection.
The results are shown in Table 1 and FIGS. 1 to 5.
Analysis of the detection results of the fluorescent powders obtained in examples 1 to 4:
the results obtained in examples 5 to 12 are similar to those obtained in examples 1 to 4, and are not described here.
FIG. 1 shows the BLLT:6% Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ Is a XRD pattern of (C). From the figure, it can be seen that BLLT is 6% Er 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ The position of the diffraction peak and BaLaLiTeO 6 (JCCPDSCardNo. 80-0077, the figure is the pattern of PDF#80-0077) standard card consistency, the example 1-4 obtained samples are pure phase.
The applicationBLLT 6% Er obtained in examples 1 to 4 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ Color coordinates and color purity of (c).
TABLE 1
As can be seen from the color coordinates (CIE color coordinates) of Table 1 of (0.2426,0.7176), (0.2450,0.7193), (0.2608,0.7153) and (0.2691,0.7097), the phosphors obtained in each example were located in the green region of the CIE color coordinates, and the color purity was as high as 95%,96%,98% and 97%, respectively.
FIG. 2 shows the BLLT:6% Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ And at 298-573K, the temperature-changing emission spectrum with the wavelength range of 500-600 nm. As the intensity of the emission peak of the rare earth Er ion at the 526nm position is increased along with the temperature rise at 298-573K, the intensity of the emission peak is continuously enhanced, and the result of the intensity of the emission peak at the 547nm position is opposite. Such materials can be applied to research of non-contact temperature sensing performance based on fluorescence intensity ratio, and the series of fluorescent powders can be applied to green light emitting part of white light LED.
FIG. 3 shows the BLLT:6% Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ Fluorescence intensity ratio spectra at 526nm and 547nm in 298-573K temperature range, and non-linear fitting was performed on the data. The energy difference (DeltaE) between the two excited states was calculated to be 658cm -1 ，739cm -1 ，694cm -1 ，708cm -1 . Due to the proper energy difference (delta E) between the two excited states, the luminescence characteristic meets the energy level of the two thermally coupled excited states of Er ions 2 H 11/2 And 4 S 3/2) to the ground state% 4 I 15/2 ) The transition emission energy of the series of materials is a function of temperature, so the series of materials can be used for researching a temperature sensor.
FIG. 4 shows the BLLT:6% Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ Is a pattern of absolute sensitivity of (c). BLLT 6% Er 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3 + Absolute sensitivities at different temperatures, the maximum of which is 0.0103K respectively -1 ，0.0120K -1 ，0.00706K -1 ，0.00603K -1 . The series of fluorescent powder has higher absolute sensitivity, and can effectively improve the detection accuracy and sensitivity of the obtained sensor when being used for a non-contact temperature sensor.
FIG. 5 shows the BLLT:6% Er obtained in examples 1 to 4 of the present application 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3+ Is a relatively sensitive map of (2). BLLT 6% Er 3+ ，SLLT:6％Er 3+ ，CLLT:6％Er 3+ And MLLT:6% Er 3 + The relative sensitivity at different temperatures has a maximum value of 0.0107K respectively -1 ，0.0120K -1 ，0.0112K -1 ，0.0115K -1 . The series of fluorescent powder has higher relative sensitivity, is used for a non-contact temperature sensor, and can effectively improve the detection accuracy and sensitivity of the obtained sensor.
Although the present invention has been described with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements and changes may be made without departing from the spirit and principles of the present invention.
Claims (13)
1. A green fluorescent material for a non-contact temperature sensor is characterized in thatThe chemical formula is ALa (1-x) Er x LiTeO 6 Wherein A is any one of Ba, sr, ca or Mg; wherein x is more than or equal to 0.01 and less than or equal to 0.15.
2. The green fluorescent material of claim 1, wherein x = 0.06.
3. A method for producing the green fluorescent material for a non-contact temperature sensor according to any one of claims 1 or 2, comprising the steps of: the raw materials are weighed according to the mole ratio and then uniformly mixed, and the high-temperature solid phase synthesis method is adopted for preparing the catalyst.
4. A method of preparing as claimed in claim 3, wherein the starting materials comprise: la source, li source, te source, er source and A source;
the source A is one of Ba source, sr source, ca source and Mg source.
5. The method according to claim 4, wherein the La source substance is La 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The Li source material is Li 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the Te source substance is TeO 2 The method comprises the steps of carrying out a first treatment on the surface of the The Er source material is Er 2 O 3 。
6. The method according to claim 3, wherein the Ba source is BaCO 3 The method comprises the steps of carrying out a first treatment on the surface of the The Sr source substance is SrCO 3 The method comprises the steps of carrying out a first treatment on the surface of the Ca source material is CaCO 3 The method comprises the steps of carrying out a first treatment on the surface of the The Mg source substance is MgCO 3 。
7. A process according to claim 3, wherein the starting material is BaCO 3 、La 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，BaCO 3 ：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 The molar ratio of (2) is 1:0.47:0.5:1:0.03.
8. the method according to claim 3, wherein the raw material is SrCO 3 、La 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，SrCO 3 ：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 The molar ratio of (2) is 1:0.47:0.5:1:0.03.
9. the method according to claim 3, wherein the raw material is CaCO 3 、La 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，CaCO 3 ：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 The molar ratio of (2) is 1:0.47:0.5:1:0.03.
10. the method according to claim 3, wherein the raw material is MgCO 3 、La 2 O 3 、Li 2 CO 3 、TeO 2 、Er 2 O 3 ，MgCO 3 ：La 2 O 3 ：Li 2 CO 3 ：TeO 2 ：Er 2 O 3 The molar ratio of (2) is 1:0.47:0.5:1:0.03.
11. the method according to claim 4, wherein the high-temperature solid phase synthesis method comprises the steps of:
(1) Grinding: uniformly mixing the raw materials, and fully grinding the mixture in an agate mortar for 30min to obtain a reactant;
(2) Presintering: placing the reactant into a corundum crucible and placing the corundum crucible into a muffle furnace, heating the corundum crucible for 300min, then heating the corundum crucible to 600 ℃ in the muffle furnace, and preserving the heat for 360min;
(3) And (3) sintering: and continuously heating for 500min, heating to 1000-1050 ℃, preserving heat for 300-600 min, and cooling to room temperature along with a furnace to obtain the fluorescent material.
12. The method according to claim 11, wherein when the source a is a source Ba, the temperature is raised to 1000 ℃ in step (3).
13. The production method according to claim 11, wherein when the a source is any one of the Sr source, the Ca source, and the Mg source, the temperature is raised to 1050 ℃ in the step (3).
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