CN107384396B - Rare earth doped oxide microtube material with light temperature sensing property and preparation method thereof - Google Patents

Rare earth doped oxide microtube material with light temperature sensing property and preparation method thereof Download PDF

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CN107384396B
CN107384396B CN201710542456.4A CN201710542456A CN107384396B CN 107384396 B CN107384396 B CN 107384396B CN 201710542456 A CN201710542456 A CN 201710542456A CN 107384396 B CN107384396 B CN 107384396B
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CN107384396A (en
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王祥夫
王烨
步妍妍
孟岚
颜晓红
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Nanjing University of Posts and Telecommunications
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    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract

The invention relates to a rare earth doped oxide microtube material with light temperature sensing property and a preparation method thereof, belonging to the technical field of rare earth luminescent materials. With rare earth ions Er3+As luminescent centers, singly or co-doped in Y2O3In the micron tube, multi-frequency strong fluorescence is emitted under the excitation of infrared light, and the micron tube has a high-sensitivity light-temperature sensing characteristic. The preparation method comprises the following steps: (a) selecting raw materials, (b) mixing ingredients, and (c) preparing a micron tube. The fluorescent powder prepared by the invention not only can realize the conversion of infrared light to visible light, but also can realize the light-temperature sensing microtube material with light-temperature sensing performance. The material is suitable for large-area industrial production.

Description

Rare earth doped oxide microtube material with light temperature sensing property and preparation method thereof
Technical Field
The invention relates to a rare earth doped oxide micron tube with light temperature sensing property and a preparation method thereof, belonging to the technical field of rare earth luminescent materials.
Background
The thermometer commonly used in life measures the temperature of the surface of an object by means of contact. However, in many special areas, for example: contact temperature measurement is difficult to realize inside microelectronic devices, in coal mines, in transformation places of high-voltage power stations and the like. Therefore, it is necessary to study a noncontact temperature sensor. Recently, light-temperature sensing behavior based on up-conversion luminescence of rare earth ion doped phosphors has received much attention because they can provide non-contact temperature measurement through two adjacent thermally coupled energy level Fluorescence Intensity Ratios (FIRs). Non-contact FIR techniques have high resolution and high accuracy, superior to conventional temperature measurements. The up-conversion luminescent material is widely applied to the fields of temperature measurement, biological fluorescent probes and the like at present, and has wide market prospect. At present, trivalent rare earth ions such as Er have been used3+，Ho3+，Tm3+，Eu3+And Pr3+As activators toThe light and temperature sensing behavior is studied. Phosphors with high thermal stability are the material of choice for light and temperature sensing. The rare earth ion doped fluoride material is a good visible light emitter and is suitable for being used as a light temperature sensing material. However, fluoride materials are susceptible to oxidation at high temperatures and are not amenable to photothermal performance detection. In order to avoid such limitation, it is necessary to prepare an oxide material having high sensitivity. In contrast to fluoride, Y2O3Has high melting point, wide band gap, high thermal stability, and good transparency in ultraviolet and infrared range, and most importantly Y2O3Crystal lattice and rare earth ion Er3+,Ho3+Has good solid solubility, and can realize high-concentration doping to obtain strong fluorescence emission.
Since the 980nm infrared light is the cheapest and most power-adjustable excitation light source used for light temperature sensing. The invention selects 980nm infrared light as an excitation source, and rare earth ion Er3+Er is prepared as a luminescence center3+、Ho3+Rare earth ion doped Y2O3A microtube having high thermal stability and high luminous intensity. Moreover, we can monitor Er3+、Ho3+The temperature measurement is realized by the change of the fluorescence spectrum of the rare earth ions along with the temperature, the sensitivity of the light-temperature sensing is greatly improved, and the realized sensitivity of the invention is more than the maximum high-temperature sensitivity value (0.0044K) reported by the literature-1427K) (mater. lett.143, 209-211,2015), and realizes a breakthrough in low temperature sensing, and can simultaneously realize measurement of high and low temperatures compared with the previous reports.
Disclosure of Invention
The technical problem solved by the invention is as follows: provides a rare earth doped oxide microtube material with light temperature sensing property and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a rare earth doped oxide microtube material with light temperature sensing property comprises the following components by volume ratio: YCl3:ErCl3:HoCl398.8:1:0.2, 98.5:1:0.5, 98:1:1 or 97.5:1: 1.5.
Preferably, the components and the volume ratio are as follows: YCl3:ErCl3:HoCl3＝98.5:1:0.5。
In order to solve the above technical problem, another technical solution proposed by the present invention is: a method for preparing rare earth doped oxide micron tube material with light temperature sensing property comprises the following steps:
(a) selection of raw materials
The raw materials of the rare earth doped microtube are analytically pure HCl, NaOH and ethanol, rare earth ions are selected from oxides with the purity of 99.99 percent, and the oxides are Y2O3、Er2O3And Ho2O3；
(b) Preparation of micron tube batch
Accurately weighing raw materials according to a ratio, reacting the oxide with hydrochloric acid, adding water, and preparing 0.2mol/L YCl3、ErCl3And HoCl3A solution;
(c) preparation of micron tube
The micron tube is prepared by a hydrothermal method, the solution is dripped into a hydrothermal reaction kettle, NaOH solution is slowly dripped, a magnetic stirrer is used for stirring for half an hour, hydrothermal reaction is carried out for 24 hours at 200 ℃, after the reaction is finished, cooling is carried out, distilled water and ethanol are added for cleaning, a sample is centrifugally separated out, drying is carried out for 6 hours, annealing is carried out, the annealing temperature is 900 ℃, the time is 3 hours, and after the annealing is finished, the powder is ground into powder by an agate mortar.
Has the advantages that:
(1) the preparation method is simple and convenient, has high thermal stability and is suitable for industrial batch production.
(2) The micron tube prepared by the invention has good thermal stability and chemical stability.
(3) According to the invention, the thermal coupling energy level of the rare earth ions follows Boltzmann distribution when the temperature changes, and the Boltzmann formula is used for fitting the fluorescence intensity ratio of the sample to obtain the relation between the fluorescence intensity and the temperature, so that the relative sensitivity curve of the sample to the temperature is obtained. Therefore, we can not only monitor Er3+The temperature measurement is realized by the change of the fluorescence spectrum of the rare earth ions along with the temperature,the maximum sensitivity at high temperature of (0.0057K) can also be obtained based on the relationship between the relative sensitivity and the temperature-1457K) is greatly improved compared with the sensitivity value reported by the prior literature, and the low-temperature sensitivity (0.0529K) is realized-124K) to achieve the performance of a precision light temperature sensor.
Drawings
The invention will be further explained with reference to the drawings.
FIG. 1 is Y2O3：1％Er3+，0.5％Ho3+Morphology of the sample under an electron microscope.
FIG. 2 is Y2O3：1％Er3+，x％Ho3+(x ═ 0,0.2,0.5,1.0,1.5), emission spectrum under 980nm excitation.
FIG. 3 is Y2O3：1％Er3+，0.5％Ho3+Fluorescence intensity ratio of the sample as a function of temperature.
FIG. 4 is Y2O3：1％Er3+，x％Ho3+(x ═ 0,0.2,0.5,1.0,1.5) relative sensitivity of the samples versus temperature.
FIG. 5 is Y2O3：1％Er3+，x％Ho3+(x ═ 0,0.2,0.5,1.0,1.5) relative sensitivity of the samples versus temperature.
Detailed Description
The matrix material is analytically pure HCl, NaOH and ethanol, and the rare earth ion is 99.99% oxide (Y)2O3、Er2O3And Ho2O3) Is prepared from the following main raw materials in percentage by weight: YCl3: the doping ions are: er3+，Ho3+。Er3+The volume ratio of the doping concentration of (A) is as follows: 1% Er3+，Ho3+The volume ratio of the doping concentration of (A) is as follows: weighing raw materials at a ratio of 0,0.2,0.5,1.0, 1.5%, wherein the volume of each raw material solution is shown in Table 1, and mixing YCl of 0.2mol/L3，ErCl3，HoCl3The solution is dropped into a hydrothermal reaction kettle according to a certain proportion, then NaOH (3.5ml) solution is slowly dropped, a magnetic stirrer is used for stirring for half an hour, and hydrothermal reaction is carried out at 200 DEG C24 hours, cooling after the reaction is finished, adding distilled water and ethanol for cleaning, centrifugally separating out a sample, drying for 6 hours at 100 ℃, annealing at 900 ℃ for 3 hours, and grinding into powder by using an agate mortar after the reaction is finished. The spectral test of samples with different doping concentrations under 980nm infrared excitation is carried out, the embodiment 3 with the strongest fluorescence intensity is selected as the sample to carry out the light and temperature sensing test, the relation between the (524+537) nm/552nm fluorescence intensity ratio and the temperature is obtained and is shown in figure 3, and the relation between the relative sensitivity of the sample and the temperature is shown in figure 4; the relationship between the fluorescence intensity ratio of 660nm/680nm and the temperature is shown in FIG. 3, and the relationship between the relative sensitivity of the sample and the temperature is shown in FIG. 5.
TABLE 1 phosphor compositions (unit: ml) of examples 1-5
Figure BDA0001342166350000031
The experimental results are as follows: the embodiment was observed by electron microscopy to obtain the topography of the sample of FIG. 1 as a microtubular with a diameter of about 0.7 μm. The sample of Table 1 was excited by a 980nm infrared light source to obtain the emission spectrum of FIG. 2, the sample with the strongest intensity was selected, example 3 was selected, the fluorescence intensity ratio was performed using the emission intensities of 524nm, 537nm and 552nm to obtain the relationship between the fluorescence intensity ratio of (524+537) nm/552nm and the temperature in FIG. 3, it can be seen from FIG. 4 that the relationship between the fluorescence intensity ratio of (524+537) nm/552nm and the temperature follows Boltzmann's equation, and the relationship between the relative sensitivity and the temperature and the maximum sensitivity of (0.0057K) were obtained using the fluorescence intensity ratio-1457K), as shown in FIG. 4, illustrates that Er can be monitored3+And Ho3+The temperature measurement is realized by the change of the fluorescence spectrum of the rare earth ions along with the temperature. The relationship between the fluorescence intensity ratio of 660nm/680nm and the temperature in FIG. 3 was obtained by performing the fluorescence intensity ratio using the emission light intensity of 660nm and 680nm, and it can be seen from FIG. 5 that the relationship between the fluorescence intensity ratio of 660nm/680nm and the temperature follows the Boltzman equation, and the relationship between the relative sensitivity and the temperature and the maximum sensitivity were obtained using the fluorescence intensity ratio (0.0529K)-124K) as shown in fig. 5, it can be explained by monitoringEr3+And Ho3+The temperature measurement is realized by the change of the fluorescence spectrum of the rare earth ions along with the temperature. By comparing different rare earth ion doping Y reported in international literature2O3The relative sensitivity of the fluorescent powder is better than the prior Y2O3The fluorescent powder improves high-temperature sensing, and especially breaks through low-temperature sensing.
The invention is not limited to the specific technical solutions described in the above embodiments, and all technical solutions formed by equivalent substitutions are within the scope of the claims of the invention.

Claims (1)

1. A preparation method of a rare earth doped oxide microtube material with light temperature sensing property is characterized by comprising the following steps: the method comprises the following steps:
(a) selection of raw materials
The rare earth doped oxide microtube is prepared from analytically pure HCl, NaOH and ethanol, the rare earth material is oxide with purity of 99.99%, and the oxide is Y2O3、Er2O3And Ho2O3；
(b) Preparation of micron tube batch
Accurately weighing raw materials according to a ratio, reacting the oxide with hydrochloric acid, adding water, and preparing 0.2mol/L YCl3、ErCl3And HoCl3A solution;
(c) preparation of micron tube
The micron tube is prepared by hydrothermal method, and YCl is prepared3、ErCl3And HoCl3The solution is dripped into a hydrothermal reaction kettle, and the components and the volume ratio are as follows: YCl3: ErCl3:HoCl3=98.8:1:0.2, 98.5:1:0.5, 98:1:1 or 97.5:1: 1.5; slowly dropwise adding NaOH solution, stirring for half an hour by a magnetic stirrer, carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling after the reaction is finished, adding distilled water, washing by ethanol, centrifugally separating out a sample, drying for 6 hours, annealing at the annealing temperature of 900 ℃ for 3 hours, and grinding into powder by an agate mortar after the reaction is finished.
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CN1687306A (en) * 2005-04-29 2005-10-26 中国科学院上海硅酸盐研究所 Luminescent material converted in nano level with yttrium oxide as matrix and preparation method
CN102172497A (en) * 2011-01-17 2011-09-07 中国科学院苏州纳米技术与纳米仿生研究所 Preparation method of fluorescent coding microspheres based on up-conversion luminous nanocrystalline

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Publication number Priority date Publication date Assignee Title
CN1687306A (en) * 2005-04-29 2005-10-26 中国科学院上海硅酸盐研究所 Luminescent material converted in nano level with yttrium oxide as matrix and preparation method
CN102172497A (en) * 2011-01-17 2011-09-07 中国科学院苏州纳米技术与纳米仿生研究所 Preparation method of fluorescent coding microspheres based on up-conversion luminous nanocrystalline

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Title
Investigation of up-conversion luminescence properties of RE/Yb co-doped Y2O3 transparent ceramic(RE=Er, Ho,Pr,and Tm);Xiaorui Hou等;《Physica B》;20110722;第406卷;第3931-3937页 *

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