Optical storage luminescent material containing high-temperature trap and preparation method and application thereof
阅读说明：本技术 一种含高温陷阱的光存储发光材料及其制备方法和应用 (Optical storage luminescent material containing high-temperature trap and preparation method and application thereof ) 是由 张家骅 廖川 吴昊 张亮亮 于 2021-09-15 设计创作，主要内容包括：本发明提供了一种含高温陷阱的光存储发光材料,属于固体发光材料技术领域,其化学式为：(Y-(1-x-y)Tb-(x)R-(y))-(3)Al-(5)O-(12),其中,R选自Sm、Eu中的至少一种,x和y都是摩尔分数,x的取值范围为0.0001≤x≤0.02,y的取值范围为0.00001≤y≤0.01。本发明还提供了上述含高温陷阱的光存储发光材料的制备方法和应用。本发明的含高温陷阱的光存储发光材料,在300℃-600℃高温区至少存在三个陷阱热释峰,最强热释峰的峰值温度超过370℃,最高温热释峰的峰值超过480℃,克服目前用于光存储的材料陷阱过浅(热释峰值温度小于300℃)导致的存储时间短的问题,经紫外光辐照写入光信息后能够实现室温长期光存储。(The invention provides an optical storage luminescent material containing a high-temperature trap, which belongs to the technical field of solid luminescent materials and has the chemical formula as follows: (Y) 1‑x‑y Tb x R y ) 3 Al 5 O 12 Wherein R is selected from at least one of Sm and Eu, x and y are mole fractions, the value range of x is more than or equal to 0.0001 and less than or equal to 0.02, and the value range of y is more than or equal to 0.00001 and less than or equal to 0.01. The invention also provides a preparation method and application of the light storage luminescent material containing the high-temperature trap. The optical storage luminescent material containing the high-temperature trap at least has three trap heat release peaks in a high-temperature area of 300-600 ℃, the peak temperature of the strongest heat release peak exceeds 370 ℃, the peak temperature of the highest temperature heat release peak exceeds 480 ℃, the problem of short storage time caused by over shallow trap (the heat release peak temperature is less than 300 ℃) of the existing material for optical storage is solved, and the long-term optical storage at room temperature can be realized after optical information is written through ultraviolet irradiation.)
1. An optical storage luminescent material containing a high-temperature trap is characterized by having a chemical formula as follows: (Y)1-x-yTbxRy)3Al5O12Wherein R isAt least one of Sm and Eu, wherein x and y are mole fractions, the value range of x is more than or equal to 0.0001 and less than or equal to 0.02, and the value range of y is more than or equal to 0.00001 and less than or equal to 0.01.
2. The optical storage luminescent material containing the high-temperature trap as claimed in claim 1, wherein x is in a range of 0.0001. ltoreq. x.ltoreq.0.01, and y is in a range of 0.00001. ltoreq. y.ltoreq.0.005.
3. The light-storing luminescent material containing high-temperature traps according to claim 1, wherein the luminescent material has at least three trap heat release peaks in a high-temperature region of 300-600 ℃, the peak temperature of the strongest heat release peak exceeds 370 ℃, and the peak temperature of the highest heat release peak exceeds 480 ℃.
4. The light storage luminescent material containing the high-temperature trap as claimed in claim 1, wherein the peak temperature of the high-temperature trap heat release peak of the luminescent material is adjusted by regulating the doping concentrations of Tb and R.
5. The method for preparing the optical storage luminescent material containing the high-temperature trap as claimed in claim 1, wherein the raw material Y is2O3、Tb4O7、R2O3And Al2O3The mixture is evenly ground and sintered in reducing atmosphere to prepare the material.
6. The light-storing luminescent material containing high-temperature traps according to claim 5, characterized in that R is changed in valence state during preparation.
7. The method according to claim 5, wherein the starting material Y is2O3、Tb4O7、R2O3And Al2O3In a molar ratio of 6 (1-x-y): 3 x: 6 y: 10.
8. the method according to claim 5, wherein the reducing atmosphere is carbon monoxide or hydrogen;
the sintering temperature is 1300-1600 ℃, and the sintering time is 2-8 hours.
9. The use of the optical storage luminescent material containing high-temperature traps according to claim 1, wherein the luminescent material can realize room-temperature long-term optical storage after being irradiated by ultraviolet light to write optical information.
10. Use of an optical storage luminescent material comprising high temperature traps according to claim 1, wherein said luminescent material is capable of reading out the stored information in the form of blue green light by heating means or by red-near infrared excitation means.
Technical Field
The invention belongs to the technical field of solid luminescent materials, and relates to an optical storage luminescent material containing a high-temperature trap, and a preparation method and application thereof.
Background
The development of the information age brings massive digital information, which presents a serious challenge to the traditional data storage mode. The optical storage technology is considered to be a storage technology with a wide application prospect due to the characteristics of small volume, long service life, large capacity, low power consumption and environmental friendliness. In this context, light-excited luminescent materials have attracted attention from researchers. The light-excited luminescent material can absorb ultraviolet photons to excite electrons, then the electrons are captured and stored by traps in the material, and under the excitation of low-energy photons or heat, the electrons can escape from the traps and migrate to a specific luminescent center to emit light. The whole process corresponds to writing, storing and reading data. In this storage technique, the depth of the trap determines the storage time, the deeper the trap, the longer the storage time. The deeper the trap is, the higher the temperature required for releasing electrons, the more the process of releasing electrons is accompanied by luminescence, so that the peak temperature of the trap can be clearly observed by measuring the change curve of the luminescence intensity with the increase of the temperature, that is, the pyroelectric curve. It is clear that a higher peak temperature of the heat release of a trap indicates a longer duration of the trap's ability to store information at room temperature, and such a trap is also called a high temperature trap.
At present, the optical storage luminescent material is widely researched, and table 1 is a statistical table of the heat release peak temperature of the existing optical storage luminescent material. It is clear that none of these materials currently exist with a peak temperature of heat release exceeding 300 ℃. A higher peak temperature of the heat release means a deeper trap, which means a longer optical storage time. In order to increase the time of optical storage, there is an urgent need to develop optical storage luminescent materials containing high-temperature deep traps.
TABLE 1 statistical table of peak temperature of heat release of existing optical storage luminescent materials
Therefore, research on the optical storage luminescent material containing the high-temperature trap, the preparation method and the application thereof is urgently needed, the technical bottleneck that the heat release peak temperature of the optical storage luminescent material does not exceed 300 ℃ is solved, and the optical storage luminescent material containing the high-temperature deep trap is developed to realize permanent optical storage at room temperature.
Disclosure of Invention
In view of the above, the present invention aims to provide a light storage luminescent material containing high temperature traps, and a preparation method and an application thereof, wherein the luminescent material has at least three trap thermolysis peaks in a high temperature region of 300-600 ℃, the peak temperature of the strongest thermolysis peak exceeds 370 ℃, the peak value of the highest thermolysis peak exceeds 480 ℃, and the luminescent material can realize room temperature long-term light storage after being irradiated by ultraviolet light.
In order to achieve the above object, the present invention provides an optical storage luminescent material containing high temperature trap, which has a chemical formula: (Y)1-x-yTbxRy)3Al5O12Wherein R is selected from at least one of Sm and Eu, x and y are mole fractions, the value range of x is more than or equal to 0.0001 and less than or equal to 0.02, and the value range of y is more than or equal to 0.00001 and less than or equal to 0.01.
Furthermore, the value range of x is more than or equal to 0.0001 and less than or equal to 0.01, and the value range of y is more than or equal to 0.00001 and less than or equal to 0.005.
Furthermore, the luminescent material has at least three trap heat release peaks in a high temperature area of 300-600 ℃, the peak temperature of the strongest heat release peak exceeds 370 ℃, and the peak temperature of the highest heat release peak exceeds 480 ℃.
Furthermore, the peak temperature of the high-temperature trap heat release peak is adjusted by regulating the doping concentration of Tb and R.
The invention also provides a preparation method of the light storage luminescent material containing the high-temperature trap, which is prepared from the raw material Y2O3、Tb4O7、R2O3And Al2O3The mixture is evenly ground and sintered in reducing atmosphere to prepare the material.
Further, raw material Y2O3、Tb4O7、R2O3And Al2O3In a molar ratio of 6 (1-x-y): 3 x: 6 y: 10.
further, the reducing atmosphere is carbon monoxide or hydrogen; the sintering temperature is 1300-1600 ℃, and the sintering time is 2-8 hours.
The invention also provides application of the light storage luminescent material containing the high-temperature trap, and the luminescent material can realize long-term light storage at room temperature after information is written in by ultraviolet irradiation.
The invention also provides application of the light storage luminescent material containing the high-temperature trap, wherein the luminescent material can read out stored information in a blue-green light form by heating means or red light-near infrared light excitation means.
The invention adopts the technical scheme that the method has the advantages that:
the light storage luminescent material containing the high-temperature trap has the chemical formula of (Y)1-x-yTbxRy)3Al5O12The trap density is increased by co-doping Tb and R, a new trap is generated, the trap density and the depth are controlled by regulating the concentration of Tb and R, at least three trap heat release peaks exist in a high-temperature region of 300-600 ℃, the peak temperature of the strongest heat release peak exceeds 370 ℃, the peak value of the highest heat release peak exceeds 480 ℃, and the problem of short storage time caused by over shallow trap (the heat release peak temperature is less than 300 ℃) of the existing material for optical storage is solved; the physical and chemical properties are stable, and the paint is not deteriorated after being repeatedly used under the damp and hot conditions; the material is prepared by sintering in a reducing atmosphere of carbon monoxide or hydrogen by adopting a high-temperature solid phase method, and has low requirements on synthesis conditions, simple operation and low cost; the material can realize long-term optical storage at room temperature after information is written in by ultraviolet irradiation, and the stored information can be read in a blue-green light mode by a heating means or a red light-near infrared light excitation means.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows luminescent materials prepared in comparative example 1 and examples 1, 4, 7 and 10X-ray diffraction pattern and Y of the material3Al5O12Standard card PDF # 73-1370;
FIG. 2 shows comparative example 1 (monitoring Tb)3+:5D4→7F5Emission 540nm), comparative example 2 (monitoring Eu)2+:4f65d→4f7Emission 440nm) and example 6 (monitoring of Tb)3+:5D4→7F5540nm) under the same test conditions, respectively exciting the luminescent materials prepared in the step (a) with 254nm ultraviolet light for 5 minutes;
FIG. 3 is a photoexcited emission spectrum of a luminescent material prepared in example 6;
FIG. 4 is a normalized heat release curve (monitoring Tb) for luminescent materials prepared in examples 5-73+:5D3→7F6Emission 384 nm);
fig. 5 is a graph showing the integrated intensity of the pyroelectric emission curve of the luminescent material prepared in example 6 as a function of time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a light storage luminescent material containing a high-temperature trap, which has a chemical formula as follows: (Y)1-x-yTbxRy)3Al5O12Wherein R is selected from at least one of Sm and Eu, x and y are mole fractions, the value range of x is more than or equal to 0.0001 and less than or equal to 0.02, and the value range of y is more than or equal to 0.00001 and less than or equal to 0.01. Preferably, the value range of x is more than or equal to 0.0001 and less than or equal to 0.01, and the value range of y is more than or equal to 0.00001 and less than or equal to 0.005.
The invention is adopted in Y3Al5O12Tb luminescent material with added variable valence rare earth oxide R2O3So as to generate high-temperature deep traps in the matrix material, and the density and the depth of the traps are controlled by regulating the concentration of Tb and R, and the principle is as follows: when sintering in a reducing atmosphere of carbon monoxide or hydrogen, Y is doped3Al5O12R in (1)3+Will be reduced to R2+Since atoms with similar ionic radii can occupy lattice sites in a lattice, R is a group of atoms with similar ionic radii2+Will occupy Y3+But the non-equivalent substitution would present a charge mismatch, and in order to compensate for this charge mismatch, oxygen vacancies, and Tb, would form spontaneously in the composite material3+Incorporation of Y3Al5O12The intrinsic traps formed together constitute different types of traps at different depths in the material. Because different types of traps exist in the material at the same time and have interaction (mutual increase, mutual quenching and the like), the mutual influence among the traps can be controlled by regulating the concentration of Tb and R, and thus the purpose of regulating the depth and the density of the traps is achieved.
The invention also provides a preparation method of the light storage luminescent material containing the high-temperature trap, which is prepared from the raw material Y2O3、Tb4O7、R2O3And Al2O3The mixture is evenly ground and sintered in reducing atmosphere to prepare the material. Wherein, the raw material Y2O3、Tb4O7、R2O3And Al2O3In a molar ratio of 6 (1-x-y): 3 x: 6 y: 10; the reducing atmosphere can be selected from carbon monoxide or hydrogen; the sintering parameters are preferably: the sintering temperature is 1300-1600 ℃, and the sintering time is 2-8 hours.
The optical storage luminescent material containing the high-temperature trap at least has three trap heat release peaks in a high-temperature area of 300-600 ℃, the peak temperature of the strongest heat release peak exceeds 370 ℃, the peak temperature of the highest heat release peak exceeds 480 ℃, and the long-term optical storage at room temperature can be realized after information is written in by ultraviolet light irradiation; the stored information can be read in a blue-green light form by heating means or by adopting red light-near infrared light excitation means.
Comparative example 1
(Y0.998Tb0.002)3Al5O12The preparation process is as follows:
according to the chemical composition: 5.988Y2O3-0.006Tb4O7-10Al2O3Weighing Y in stoichiometric ratio2O3、Tb4O7And Al2O3Mixing and grinding thoroughly, sintering the obtained mixture at 1550 deg.C in carbon monoxide reducing atmosphere for 5 hr, naturally cooling to room temperature, and grinding the sintered body into powder to obtain (Y)0.998Tb0.002)3Al5O12A luminescent material.
Comparative examples 2 to 3
The preparation process is the same as that of comparative example 1, except that the chemical formula of the luminescent material and the composition of the raw materials are different, see table 2.
Example 1
(Y0.9898Tb0.01Eu0.0002)3Al5O12The preparation process is as follows:
according to the chemical composition: 5.9388Y2O3-0.03Tb4O7-0.0012Eu2O3-10Al2O3Weighing Y in stoichiometric ratio2O3、Tb4O7、Eu2O3And Al2O3Mixing and grinding thoroughly, sintering the obtained mixture at 1550 deg.C in carbon monoxide reducing atmosphere for 5 hr, naturally cooling to room temperature, and grinding the sintered body into powder to obtain (Y)0.9898Tb0.01Eu0.0002)3Al5O12A luminescent material.
Examples 2 to 12
The preparation method is the same as that of example 1, except that the chemical formula of the luminescent material, the composition of the raw materials and the preparation conditions are different, see table 2 specifically.
TABLE 2 summary of chemical composition, preparation conditions and pyroelectric data for comparative examples 1-3 and examples 1-12
The luminescent materials prepared in comparative examples 1 to 3 and examples 1 to 12 were subjected to performance tests such as X-ray diffraction analysis, pyroelectric performance test, light-excited luminescence test, and light storage time test, and the results are shown in fig. 1 to 5:
FIG. 1 is an X-ray diffraction pattern and Y of luminescent materials prepared in comparative example 1 and examples 1, 4, 7 and 103Al5O12Standard card PDF # 73-1370;
FIG. 2 shows comparative example 1 (monitoring Tb)3+:5D4→7F5Emission 540nm), comparative example 2 (monitoring Eu)2+:4f65d→4f7Emission 440nm) and example 6 (monitoring of Tb)3+:5D4→7F5540nm emission) under the same test conditions, it can be seen from the graph that the luminescent material of example 6 co-doped with Tb and Eu significantly increases the trap density of traps 1, 2, and 4, generates trap 3, and has no afterglow at room temperature;
FIG. 3 is a graph showing the photoexcited emission spectra of the luminescent materials prepared in example 6, measured by irradiating the luminescent materials with 254nm UV light, and then exciting electrons in material traps with 808nm laser light;
FIG. 4 is a normalized heat release curve (monitoring Tb) for luminescent materials prepared in examples 5-73+:5D3→7F6The emission is 384nm), the peak temperature of the heat release curve can be effectively regulated and controlled by regulating the concentration of Tb and Eu (the trap depth and the peak temperature of the heat release curve are in positive correlation);
fig. 5 shows the variation of the integrated intensity of the thermoluminescence curve of the luminescent material prepared in example 6 with time, the testing process is to irradiate the thermoluminescence curve with 254nm ultraviolet light for 5 minutes (writing information), then place the thermoluminescence curve in a dark environment (storing information), take out an equal amount of luminescent material at intervals (monitoring 384nm emission), measure the thermoluminescence curve (reading information), and draw the curve of the integrated intensity of the thermoluminescence curve with the storage time.
The light storage luminescent material containing the high-temperature trap has the chemical formula of (Y)1-x-yTbxRy)3Al5O12The trap density is increased by co-doping Tb and R, a new trap is generated, the trap density and the depth are controlled by regulating the concentration of Tb and R, at least three trap heat release peaks exist in a high-temperature region of 300-600 ℃, the peak temperature of the strongest heat release peak exceeds 370 ℃, the peak value of the highest heat release peak exceeds 480 ℃, and the problem of short storage time caused by over shallow trap (the heat release peak temperature is less than 300 ℃) of the existing material for optical storage is solved; the physical and chemical properties are stable, and the paint is not deteriorated after being repeatedly used under the damp and hot conditions; the material is prepared by sintering in a reducing atmosphere of carbon monoxide or hydrogen by adopting a high-temperature solid phase method, and has low requirements on synthesis conditions, simple operation and low cost; the material can realize long-term light storage at room temperature after being irradiated by ultraviolet light, and the stored information can be read out in a blue-green light mode by a heating means or a red light-near infrared light excitation means.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
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