CN114540027B - Holmium doped up-conversion material and preparation method and application thereof - Google Patents

Holmium doped up-conversion material and preparation method and application thereof Download PDF

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CN114540027B
CN114540027B CN202011368656.0A CN202011368656A CN114540027B CN 114540027 B CN114540027 B CN 114540027B CN 202011368656 A CN202011368656 A CN 202011368656A CN 114540027 B CN114540027 B CN 114540027B
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holmium
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CN114540027A (en
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麻朝阳
曹永革
汪玉珍
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Institute of Physics of CAS
Songshan Lake Materials Laboratory
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Songshan Lake Materials Laboratory
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    • C—CHEMISTRY; METALLURGY
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7701—Chalogenides
    • 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
    • G01K11/20—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using thermoluminescent materials
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Abstract

Holmium doped up-conversion material and preparation method thereofApplication, which belongs to the field of inorganic luminescent materials. The holmium doped up-conversion material has the following general formula: na (Na) 0.5 Bi 0.5‑x TiO 3 Ho x X is more than or equal to 0.002 and less than or equal to 0.006. The up-conversion luminescent material is formed by taking sodium bismuth titanate as a matrix and holmium ions as an activator, and has high chemical and physical stability and high sensitive temperature response under the low-temperature condition.

Description

Holmium doped up-conversion material and preparation method and application thereof
Technical Field
The application relates to the field of inorganic luminescent materials, in particular to a holmium doped up-conversion material, a preparation method and application thereof.
Background
Thermodynamic temperature is one of 7 basic physical quantities of international system of units (SI), which is a physical quantity that is very frequently used by humans. The improvement of the monitoring accuracy level of the temperature has important practical significance in the fields of life science, high-precision machining and the like. The temperature measurement technology based on the fluorescence intensity ratio of the rare earth ions has the outstanding advantages of intrinsic safety, electromagnetic interference resistance, high precision, strong stability, no contact and the like, and in the temperature measurement method based on the fluorescence intensity ratio, absolute sensitivity (Sa) and relative sensitivity (Sr) are used as judgment standards.
In recent years, temperature sensing based on rare earth ion up-conversion luminescence has attracted tremendous research interest as a non-contact temperature measurement. Up-conversion luminescence is a phenomenon of anti-stokes luminescence, and this material can absorb low-energy photons and convert them into high-energy photons for luminescence. The up-conversion material is composed of a matrix, an activator and a sensitizer, wherein the matrix material can be fluoride, oxide and the like, and the activator and the sensitizer are mostly rare earth ions. Among the rare earth ions, holmium ions are widely studied due to their unique energy level structure. However, the existing holmium ion doped up-conversion material has lower sensitivity in terms of optical temperature measurement.
In view of this, the present application is hereby presented.
Disclosure of Invention
The application provides a holmium doped up-conversion material, a preparation method and application thereof, and the holmium doped up-conversion material can effectively solve the technical problems.
Embodiments of the present application are implemented as follows:
in a first aspect, the present examples provide a holmium doped upconverter material having the compositional formula: na (Na) 0.5 Bi 0.5-x TiO 3 Ho x ，0.002≤x≤0.006。
In the implementation process, the sodium bismuth titanate is used as a matrix, holmium ions are used as an activator, and the up-conversion luminescent material with specific phase is formed, so that the up-conversion luminescent material has high chemical and physical stability and high sensitive temperature response under the low-temperature condition.
In combination with the first aspect, in some examples of the present application, the holmium doped upconverting material described above has a relative sensitivity > 6%/K at 167K.
In a second aspect, the present application provides a method for preparing a holmium doped upconverter material, comprising the steps of:
and weighing a sodium source, a bismuth source, a titanium source and a holmium source according to the molar ratio of 0.5 (0.5-x) to 1:x, and crushing to obtain powder.
Presintering the powder, pressing, forming and sintering to obtain the final product.
Wherein x is more than or equal to 0.002 and less than or equal to 0.006.
In the implementation process, the holmium-doped up-conversion material is prepared by adopting a solid phase reaction method, the preparation method is simple, the preparation period is short, mass production can be realized, and the prepared holmium ion-doped up-conversion material has better low-temperature region temperature sensitivity.
With reference to the second aspect, in some examples of the present application, the sodium source includes at least one of sodium carbonate and sodium bicarbonate, the bismuth source is at least one of bismuth oxide or bismuth subcarbonate, the titanium source is titanium dioxide, and the holmium source is holmium oxide.
Optionally, the sodium source is sodium carbonate and the bismuth source is bismuth oxide.
In the implementation process, the solid-phase reaction is carried out by adopting the specific raw materials, so that the introduction of impurities can be effectively avoided, the purity of the finally prepared holmium doped up-conversion material is ensured, an additional impurity removal mode is not needed, and meanwhile, the raw materials are simple and low in cost, can be produced in a large scale and have better commercial application value.
With reference to the second aspect, in some examples of the present application, the step of pulverizing includes: mixing a sodium source, a bismuth source, a titanium source and a holmium source with ethanol, ball milling and drying.
In the implementation process, compared with a direct grinding and crushing mode, a ball milling mode can obtain higher luminous efficiency and purer crystalline state.
Optionally, before the step of presintering, the preparation method further comprises: grinding the powder.
In the implementation process, ethanol is adopted in the ball milling process, so that the powder is further ground after being dried, the uniform dispersion of the powder can be ensured, and the sensitivity and the surface flatness of the up-conversion material can be improved subsequently.
With reference to the second aspect, in some examples of the present application, before the step of press forming, the preparation method further includes: grinding the product obtained after presintering.
In the implementation process, as the presintering can lead to the decomposition of carbonate radicals in sodium carbonate, sodium bicarbonate, bismuth subcarbonate and the like and release carbon dioxide, the internal distribution of the carbonate radicals is uneven, the presintering products are further ground before sintering, and the compression molding is carried out, so that the uniform dispersion of powder can be ensured, and the sensitivity and the surface flatness of the up-conversion material are improved subsequently.
Optionally, the pressure used for compression molding is 5-20MPa.
By adopting the pressure, the powder is ensured to be uniformly pressed into tablets.
With reference to the second aspect, in some examples of the present application, in the step of sintering, the sintering temperature is 1050-1250 ℃ and the sintering time is 1-20h.
Optionally, in the step of sintering, the sintering temperature is greater than 1050 ℃ and less than 1150 ℃.
Optionally, in the step of sintering, the temperature is raised to the sintering temperature at a temperature raising rate of 1-10 ℃/min.
In the implementation process, reasonable temperature is adopted to enable the raw materials to carry out solid phase reaction, so that the holmium doped up-conversion material with uniform particle size and low temperature high sensitivity is obtained.
With reference to the second aspect, in some examples of the present application, the pre-firing step is performed at a temperature of 600-1000 ℃ for a time of 1-10 hours.
In the implementation process, reasonable presintering temperature is adopted, so that carbonate ions in the raw materials are effectively decomposed, and a certain solid phase reaction is carried out.
In a third aspect, the present examples provide the use of the holmium doped upconverting material provided in the first aspect of the present application in an optical temperature measurement sensor.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered limiting the scope, and that other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction pattern of a holmium doped up-conversion luminescent material of example 1 of the present application;
FIG. 2 is a scanning electron microscope image of a holmium doped up-conversion luminescent material of example 1 of the present application;
fig. 3 is an upconversion fluorescence spectrum of the luminescence intensity of the holmium doped upconversion luminescent material according to embodiment 1 of the present application at different temperatures;
FIG. 4 is a graph showing the relationship between the Fluorescence Intensity Ratio (FIR) of the holmium doped up-conversion luminescent material and the temperature change in example 1 of the present application;
fig. 5 is the temperature sensitivity of luminescence of the holmium doped up-conversion luminescent material of example 1 of the present application.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following specifically describes holmium doped up-conversion materials, and preparation methods and applications thereof according to embodiments of the present application:
firstly, the holmium doped up-conversion material is formed by taking sodium bismuth titanate as a matrix and holmium ions as an activator, has a hexagonal crystal structure, and has high chemical and physical stability and high temperature sensitivity.
Specifically, the holmium doped up-conversion material has a general formula: na (Na) 0.5 Bi 0.5-x TiO 3 Ho x X is more than or equal to 0.002 and less than or equal to 0.006. Wherein x is any one value or a range value between any two values of 0.002, 0.0025, 0.003, 0.0035, 0.004, 0.0045, 0.005, 0.0055, or 0.006, for example.
Wherein the holmium doped up-conversion material is obtained by bonding a plurality of particles with uniform particle size, and the particle size of the particles is in the micron order, specifically, the particle size of the particles is 0.3-0.5 mu m.
Further, the relative sensitivity of the holmium doped up-conversion material is > 6%/K at 167K. That is, the holmium doped up-conversion material has high-sensitivity temperature response at low temperature.
The holmium-doped up-conversion material has the advantages, and has great application potential in the field of optical temperature measurement, so that the application of the holmium-doped up-conversion material in an optical temperature measurement sensor is also provided, and the optical temperature measurement sensor with the holmium-doped up-conversion material can be further applied to the fields of life science, high-precision machining and the like.
The preparation method of the holmium doped up-conversion material is simple, short in preparation period and capable of being produced in a large scale, and the prepared holmium ion doped up-conversion material is high in sensitivity in the aspect of optical temperature measurement, particularly in a low-temperature region.
Specifically, the preparation method of the holmium doped up-conversion material comprises the following steps:
s1, weighing a sodium source, a bismuth source, a titanium source and a holmium source according to the molar ratio of sodium, bismuth, titanium and holmium of 0.5 (0.5-x) to 1:x, and crushing to obtain powder. Wherein x is more than or equal to 0.002 and less than or equal to 0.006.
Alternatively, the sodium source comprises at least one of sodium carbonate and sodium bicarbonate, for example, the sodium source is sodium carbonate or sodium bicarbonate, or the sodium source is a mixture of sodium carbonate and sodium bicarbonate. The bismuth source is at least one of bismuth oxide or bismuth subcarbonate, for example, bismuth source is bismuth oxide or bismuth subcarbonate, or bismuth source is a mixture of bismuth oxide and bismuth subcarbonate. The titanium source is titanium dioxide and the holmium source is holmium oxide.
Further alternatively, the sodium source is sodium carbonate and the bismuth source is bismuth oxide.
The raw materials are convenient to obtain and low in price, and as the carbonate in the raw materials can be decomposed in the subsequent presintering step, new impurities are not introduced, subsequent impurity removal is avoided, meanwhile, the purity of the obtained holmium doped up-conversion material is ensured, and the final high sensitivity at low temperature is effectively improved.
It should be noted that, the pulverization may be directly performed by manual grinding, but in order to improve the luminous efficiency and the purer crystalline state, the step of pulverizing may optionally include: mixing a sodium source, a bismuth source, a titanium source and a holmium source with ethanol, ball milling, drying, and crushing by using shearing force and the like generated in the ball milling process.
The ball milling step is carried out in a ball milling tank of a planetary ball mill, wherein zirconia balls are adopted for ball milling, the ball milling time is 12-24 hours, the ball milling rotating speed is 220-250r/min, for example, the ball milling rotating speed is 220r/min, 223r/min, 225r/min, 230r/min, 235r/min, 240r/min or 250r/min and the like, and the reasonable rotating speed selection is utilized, so that friction between the zirconia balls and the wall of the ball milling tank can collide with powder, and a series of changes such as local high temperature, dimensional change shearing and the like are introduced, so that the luminous efficiency of the crushed powder is higher.
And the drying is to transfer the slurry obtained after ball milling into a glass dish for drying, wherein the drying can be air drying in an oven or vacuum oven drying, and air or protective atmosphere can be used in the drying process.
S2, presintering, pressing, forming and sintering the powder to obtain the finished product.
It should be noted that, in the powder obtained by drying after ball milling, because the ethanol is removed during the drying process, the gaps in the powder obtained at this time are larger and the particle distribution is uneven, and therefore, optionally, before the step of presintering, the preparation method further includes: grinding the powder.
The polishing powder may be manually polished in an agate mortar or mechanically polished, and is not limited thereto.
Optionally, in the step of presintering, the presintering temperature is 600-1000 ℃ and the presintering time is 1-10h. For example, the burn-in temperature is 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, or the like. By adopting the presintering temperature and time, carbonate ions in the raw materials can be effectively decomposed, and simultaneously, a certain solid phase reaction can be carried out.
Based on the above pre-sintering step, carbonate ions are decomposed, so that the pre-sintered product has pores with uneven distribution and particles with uneven granularity, so that in order to obtain the holmium doped up-conversion material with even particles, good surface flatness and good temperature measurement sensitivity, optionally, before the step of press forming, the preparation method further comprises: grinding the product obtained after presintering.
The polishing powder may be manually polished in an agate mortar or mechanically polished, and is not limited thereto.
Alternatively, the pressure employed for the press molding is 5 to 20MPa, specifically, for example, the pressure employed for the press molding is in a range composed of any one value or any two values of 5MPa, 10MPa, 15MPa, 17MPa, 20MPa, or the like.
Optionally, in the step of sintering, the sintering temperature is 1050-1250 ℃ and the sintering time is 1-20h; specifically, the sintering temperature is, for example, within a range composed of any one or any two values of 1050 ℃, 1070 ℃, 1090 ℃, 1100, 1130 ℃, 1150 ℃, 1170 ℃, 1200 ℃, 1230 ℃ or 1250 ℃.
Optionally, in the sintering step, the sintering temperature is greater than 1050 ℃ and less than 1150 ℃, so that the purity and structure of the obtained product can be ensured.
Optionally, in the step of sintering, the temperature is raised to the sintering temperature at a heating rate of 1-10 ℃/min, for example at a heating rate of 1 ℃/min, 3 ℃/min, 5 ℃/min, 7 ℃/min, 9 ℃/min or 10 ℃/min.
Optionally, cooling after sintering is completed, wherein the cooling is carried out by cooling to room temperature (15-35 ℃) with a furnace, and then taking out the obtained product.
The holmium doped up-conversion materials of the present application, and methods of making and using the same, are described in further detail below in conjunction with the examples.
Example 1
Doped up-conversion material, which is prepared by the following method:
(1) Sodium carbonate (Na 2 CO 3 ) Bismuth oxide (Bi) 2 O 3 ) Titanium dioxide (TiO) 2 ) And holmium oxide (Ho) 2 O 3 ) Accurately weighing, adding a proper amount of ethanol and zirconia balls into all the weighed raw materials, placing the raw materials into a ball milling tank of a planetary ball mill, ball milling for 24 hours at the rotating speed of 232r/min, transferring the ball-milled slurry into a glass dish, and drying at 60 ℃ to obtain powder.
(2) Grinding the dried powder in an agate mortar, transferring into a closed alumina crucible, and presintering for 2h at 900 ℃ in a box-type furnace.
(3) The presintered product was taken out and reground and pressed into flakes using a hydraulic press at a pressing pressure of 10MPa.
(4) And placing the pressed sheet into a box furnace, sintering for 6 hours at 1100 ℃, wherein the heating rate of heating to the sintering temperature is 5 ℃/min, naturally cooling to room temperature, and taking out a sample to obtain the holmium doped up-conversion luminescent material.
Wherein FIG. 1 is an X-ray diffraction pattern of a holmium doped up-conversion luminescent material, wherein the pattern1 is a holmium doped up-conversion luminescent material provided in this embodiment, the Sample of Sample is standard Na 0.5 Bi 0.5 TiO 3 As can be seen from the X-ray diffraction patterns corresponding to the samples of (a) the preparation of holmium doped up-conversion luminescent material and Na with hexagonal crystal structure 0.5 Bi 0.5 TiO 3 Substantially identical.
Fig. 2 is a scanning electron microscope image of a holmium doped up-conversion luminescent material, wherein it can be seen that the holmium doped up-conversion material is obtained by binding particles, the size of which is 0.3-0.5 μm.
Fig. 3 shows up-conversion fluorescence spectra of luminescence intensities of holmium doped up-conversion luminescent materials at different temperatures.
As shown in fig. 3, under excitation of 980nm laser light source, it can be seen that with increasing temperature, the luminescence of holmium doped up-conversion material is enhanced and then reduced.
Fig. 4 is a graph showing the relationship between the Fluorescence Intensity Ratio (FIR) of holmium doped up-conversion luminescent material and the temperature change. Wherein the FIR is fitted by a function FIR (T) =10.14×exp (-1472.63/T), whereby the corresponding energy levels of the light emission peaks 525nm and 548nm are obtainable according to FIG. 4 5 F 4 ， 5 S 2 At a distance of about 1023.74cm -1 。
Fig. 5 is a schematic diagram of the temperature sensitivity of the luminescence of the holmium doped up-conversion luminescent material, where Sa is the absolute sensitivity and Sr is the relative sensitivity, according to fig. 5 it can be seen that at 167K the highest relative sensitivity reaches 6.14%/K.
From the figures, the holmium doped up-conversion luminescent material has potential for application in optical temperature measurement sensors.
Example 2
Doped up-conversion material, which is prepared by the following method:
(1) Sodium carbonate (Na 2 CO 3 ) Bismuth oxide (Bi) 2 O 3 ) Titanium dioxide (TiO) 2 ) And holmium oxide (Ho) 2 O 3 ) Accurately weighing, adding appropriate amount of ethanol and zirconia pellets into all the weighed materials, and placing in a planetary typeBall milling is carried out for 24 hours in a ball milling tank of a ball mill at a rotating speed of 235r/min, the ball-milled slurry is transferred into a glass dish, and the glass dish is dried at 60 ℃ to obtain powder.
(2) The dried powder was ground in an agate mortar, transferred to a closed alumina crucible, and presintered in a box at 890 ℃ for 2 hours.
(3) The presintered product was taken out and reground and pressed into flakes using a hydraulic press at a pressing pressure of 13MPa.
(4) Placing the pressed sheet in a box furnace, sintering for 6 hours at 1100 ℃, wherein the heating rate of heating to the sintering temperature is 3 ℃/min, naturally cooling to room temperature, and taking out a sample to obtain the holmium doped up-conversion luminescent material.
Example 3
Doped up-conversion material, which is prepared by the following method:
(1) Sodium carbonate (Na 2 CO 3 ) Bismuth oxide (Bi) 2 O 3 ) Titanium dioxide (TiO) 2 ) And holmium oxide (Ho) 2 O 3 ) Accurately weighing, adding a proper amount of ethanol and zirconia balls into all the weighed raw materials, placing the raw materials into a ball milling tank of a planetary ball mill, ball milling for 24 hours at a rotating speed of 235r/min, transferring the ball-milled slurry into a glass dish, and drying at 60 ℃ to obtain powder.
(2) The dried powder was ground in an agate mortar, transferred to a closed alumina crucible, and presintered in a box at 900 ℃ for 2 hours.
(3) The presintered product was taken out and reground and pressed into flakes using a hydraulic press at a pressing pressure of 15MPa.
(4) Placing the pressed sheet in a box furnace, sintering for 10 hours at 1100 ℃, wherein the heating rate of heating to the sintering temperature is 7 ℃/min, naturally cooling to room temperature, and taking out a sample to obtain the holmium doped up-conversion luminescent material.
Example 4
Doped up-conversion material, which is prepared by the following method:
(1) Sodium carbonate (Na 2 CO 3 ) Bismuth oxide (Bi) 2 O 3 ) Titanium dioxide (TiO) 2 ) And holmium oxide (Ho) 2 O 3 ) Accurately weighing, adding a proper amount of ethanol and zirconia balls into all the weighed raw materials, placing the raw materials into a ball milling tank of a planetary ball mill, ball milling for 24 hours at the rotating speed of 232r/min, transferring the ball-milled slurry into a glass dish, and drying at 55 ℃ to obtain powder.
(2) The dried powder was ground in an agate mortar, transferred to a closed alumina crucible, and presintered in a box at 900 ℃ for 3 hours.
(3) The presintered product was taken out and reground and pressed into flakes using a hydraulic press at a pressing pressure of 10MPa.
(4) Placing the pressed sheet in a box furnace, sintering for 6 hours at 1135 ℃, wherein the heating rate of heating to the sintering temperature is 5 ℃/min, naturally cooling to room temperature, and taking out the sample to obtain the holmium doped up-conversion luminescent material.
Comparative example 1
(1) Sodium carbonate (Na 2 CO 3 ) Bismuth oxide (Bi) 2 O 3 ) Titanium dioxide (TiO) 2 ) And holmium oxide (Ho) 2 O 3 ) Accurately weighing, adding a proper amount of ethanol and zirconia balls into all the weighed raw materials, placing the raw materials in a ball milling tank of a planetary ball mill, ball milling for 24 hours, transferring the ball-milled slurry into a glass dish, and drying at 60 ℃ to obtain powder.
(2) The dried powder was ground in an agate mortar, transferred to a closed alumina crucible, and presintered in a box at 900 ℃ for 2 hours.
(3) Taking out the pre-sintered product, regrinding, and pressing into slices by using a hydraulic press, wherein the pressing pressure of the hydraulic press is 10MPa;
(4) Placing the pressed sheet in a box furnace, sintering for 6 hours at 1100 ℃, wherein the temperature rising rate of the sheet rising to the sintering temperature is 5 ℃/min, and taking out the sample after naturally cooling to room temperature to obtain the sample.
Wherein, the doping concentration of Ho ion is too high, and Ho exists in the prepared sample 2 Ti 2 O 7 The relative sensitivity of the hetero-phase is reduced, which is significantly lower than that of example 1.
Comparative example 2
It differs from example 1 only in step (4), specifically as follows:
(4) Placing the pressed sheet in a box furnace, sintering for 10 hours at 1050 ℃, wherein the temperature rising rate of the sheet rising to the sintering temperature is 7 ℃/min, and taking out the sample after naturally cooling to room temperature to obtain the sample.
Under the above conditions, na is produced due to the low sintering temperature 0.5 Bi 0.5 TiO 3 However, the sample contains impurities, and pure Na phase cannot be obtained 0.5 Bi 0.5 TiO 3 。
Comparative example 3
It differs from example 1 only in step (4), specifically as follows:
(4) Placing the pressed sheet in a box furnace, sintering for 6 hours at 1150 ℃, wherein the temperature rising rate of the sheet rising to the sintering temperature is 7 ℃/min, and taking out the sample after naturally cooling to room temperature to obtain the sample.
Under the above conditions, although Na can be produced 0.5 Bi 0.5 TiO 3 However, the sample melts due to the excessively high sintering temperature, so that the shape of the final sample cannot be maintained in a predetermined shape (i.e., even a press-formed shape).
In conclusion, the preparation method of the holmium doped up-conversion material provided by the application is simple to operate, short in preparation period and capable of being produced in a large scale. The holmium doped up-conversion material obtained by the method has high chemical and physical stability, and has better temperature sensitivity at low temperature, and can be effectively applied to an optical temperature measurement sensor.
The foregoing is merely a specific embodiment of the present application and is not intended to limit the application, and various modifications and variations may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims (11)

1.The holmium doped up-conversion material is characterized by comprising the following components in general formula: na (Na) 0.5 Bi 0.5-x TiO 3 Ho x ，0.002≤x≤0.006；
The relative sensitivity of the holmium doped up-conversion material is more than 6 percent/K at 167K.
2. A method for preparing the holmium doped upconverter material according to claim 1, comprising the steps of:
weighing a sodium source, a bismuth source, a titanium source and a holmium source according to the molar ratio of 0.5 (0.5-x) to 1:x, and crushing to obtain powder;
presintering, press forming and sintering the powder to obtain the powder;
wherein x is more than or equal to 0.002 and less than or equal to 0.006, and in the sintering step, the sintering temperature is more than 1050 ℃ and less than 1150 ℃ and the sintering time is 1-20h.
3. The method of claim 2, wherein the sodium source comprises at least one of sodium carbonate and sodium bicarbonate, the bismuth source is at least one of bismuth oxide or bismuth subcarbonate, the titanium source is titanium dioxide, and the holmium source is holmium oxide.
4. A method of preparation according to claim 3 wherein the sodium source is sodium carbonate and the bismuth source is bismuth oxide.
5. A method of preparing as claimed in claim 2 or 3, wherein the step of comminuting comprises: mixing the sodium source, the bismuth source, the titanium source and the holmium source with ethanol, ball milling and drying.
6. A method of preparing as claimed in claim 2 or 3, wherein prior to the step of presintering, the method of preparing further comprises: grinding the powder.
7. A method of producing according to claim 2 or 3, characterized in that, before the step of press forming, the method of producing further comprises: grinding the product obtained after presintering.
8. A method according to claim 2 or 3, wherein the pressure used for the compression molding is 5 to 20MPa.
9. A process according to claim 2 or 3, wherein,
in the sintering step, the temperature is raised to the sintering temperature at a heating rate of 1-10 ℃/min.
10. A method according to claim 2 or 3, wherein in the pre-firing step, the pre-firing temperature is 600-1000 ℃ and the pre-firing time is 1-10 hours.
11. Use of a holmium doped up-conversion material according to claim 1 or a holmium doped up-conversion material prepared by a method according to any of claims 2 to 10 in an optical temperature measurement sensor.
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