CN110982529A - High brightness KLu2F7 scintillator for X-ray imaging and preparation method thereof - Google Patents
High brightness KLu2F7 scintillator for X-ray imaging and preparation method thereof Download PDFInfo
- Publication number
- CN110982529A CN110982529A CN201911313857.8A CN201911313857A CN110982529A CN 110982529 A CN110982529 A CN 110982529A CN 201911313857 A CN201911313857 A CN 201911313857A CN 110982529 A CN110982529 A CN 110982529A
- Authority
- CN
- China
- Prior art keywords
- klu
- scintillator
- ray imaging
- brightness
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000003384 imaging method Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 12
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 10
- 150000002910 rare earth metals Chemical class 0.000 abstract description 7
- -1 rare earth ions Chemical class 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract 2
- 239000013590 bulk material Substances 0.000 abstract 1
- 238000004020 luminiscence type Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 34
- 239000002244 precipitate Substances 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004875 x-ray luminescence Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 238000011503 in vivo imaging Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
- Measurement Of Radiation (AREA)
Abstract
本发明公开了一种用于X射线成像的高亮度KLu2F7闪烁体，其化学式为KLu2F7:xTb3+，其中0≤x≤0.50，属于稀土发光材料技术领域；传统的闪烁体材料由于其稳定性和发光亮度等问题限制其在X射线成像领域的应用，本发明采用水热法并通过稀土离子的掺杂合成了微米级别的高亮度KLu2F7闪烁体；且反应条件温和，操作简单，得到的粉体是一种亲水性粉体，通过稀土离子的掺杂合成了微米级别的高亮度KLu2F7闪烁体，可吸收X射线并发出明亮的绿光，稳定性高和高亮度的特性使得制备的KLu2F7闪烁体有望在X射线成像技术中得到广泛应用。The invention discloses a high-brightness KLu 2 F 7 scintillator for X-ray imaging, the chemical formula of which is KLu 2 F 7 :xTb 3+ , wherein 0≤x≤0.50, belongs to the technical field of rare earth luminescent materials; traditional scintillation The bulk material is limited in its application in the field of X - ray imaging due to its stability and luminescence brightness. The conditions are mild and the operation is simple. The obtained powder is a hydrophilic powder. The micron-level high-brightness KLu 2 F 7 scintillator is synthesized by doping with rare earth ions, which can absorb X-rays and emit bright green light. The characteristics of high stability and high brightness make the prepared KLu 2 F 7 scintillator expected to be widely used in X-ray imaging technology.
Description
Technical Field
The invention relates to a high brightness KLu for X-ray imaging2F7Preparation method of scintillatorThe method belongs to the technical field of rare earth luminescent materials.
Background
The rare earth luminescent material has low toxicity, high light stability and high color purity, and is widely applied to the fields of medical treatment, in vivo imaging and the like, and the luminescent performance is an important index for measuring the rare earth luminescent material.
The scintillator material emits visible light under X-ray radiation, serves as a core element in X-ray technical application, and can convert high-energy X photons into low-energy visible photons to realize X-ray detection and imaging. Rare earth fluoride is widely researched due to low phonon energy, stable physicochemical property, high laser damage resistance threshold and the like, but the traditional scintillator material mainly has insufficient chemical stability and thermal stability or has low biocompatibility and luminous intensity, so that the application of the rare earth fluoride in the field of biological imaging is limited. Thus, KLu was prepared2F7Scintillator and design and development of different kinds of rare earth doped KLu2F7The scintillator has important practical application value in the fields of biological marking, displaying, infrared detection and the like.
Disclosure of Invention
The invention provides a high brightness KLu for X-ray imaging2F7The scintillator and the preparation method thereof provide a thought for the rare earth conversion luminescent material to be applied to X-ray imaging.
High-brightness KLu for X-ray imaging2F7The chemical formula of the scintillator is KLu2F7:xTb3+Wherein x is more than or equal to 0 and less than or equal to 0.50.
High brightness KLu for X-ray imaging as described above2F7The preparation method of the scintillator comprises the following steps:
(1) sequentially adding the Lu salt solution, the Tb salt solution, the KF solution, absolute ethyl alcohol and deionized water into a container, and stirring for 1-2 hours at room temperature to obtain a white turbid solution;
(2) placing the white turbid liquid in a reaction kettle to perform hydrothermal reaction for 20-24 hours at 180-240 ℃;
(3) after the hydrothermal reaction is finished, naturally cooling toAt room temperature, sequentially centrifuging the reaction product, washing with absolute ethyl alcohol and dispersing with deionized water to obtain KLu2F7:Tb3+A scintillator.
The Lu salt is Lu (NO)3)3Tb salt is Tb (NO)3)3。
The Lu3+And Tb3+The molar ratio of (a) to (b) is 1-x: x, wherein x is more than or equal to 0 and less than or equal to 0.50.
The molar ratio of the Lu salt to KF is 0.5-1: 70.
The centrifugal rotating speed is 5500-6000 rpm, and the centrifugal time is 5-7 min.
The invention has the following beneficial effects:
(1) tb of the invention3+Doped KLu2F7The scintillator emits strong green light under the irradiation of an X-ray excitation light source, and the green light is emitted and emitted at about 545 nm;
(2) the invention has simple process, less rare earth doping amount and low cost, and the prepared KLu2F7The scintillator is a single phase;
(3) tb of the invention3+Doped KLu2F7The scintillator can be applied to X-ray detection and imaging, biomedicine and the like.
Drawings
FIG. 1 shows KLu prepared according to the invention2F7An XRD pattern of (a); curve KLu2F7：0.08Tb3+、0.12Tb3+、0.16Tb3+、0.20Tb3+Corresponding to examples 1 to 4, respectively, of the present invention; the figure shows no miscellaneous peaks compared to the standard PDF cards 27-0459, indicating that the resultant scintillator material is a single phase;
FIG. 2 shows KLu prepared in example 3 of the present invention2F7：0.16Tb3+Emission spectrum under excitation of light with wavelength of 370 nm;
FIG. 3 shows KLu prepared in example 3 of the present invention2F7：0.16Tb3+X-ray luminescence spectrum of (1).
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: this example high brightness KLu for X-ray imaging2F7The scintillator has the formula KLu2F7:0.08Tb3+；
KLu for X-ray imaging as described above2F7The preparation method of the scintillator comprises the following steps:
(1) mixing Lu and Tb at a molar ratio of 0.92:0.082O3(99.99%)、Tb4O7(99.99%) 2mmol of Lu (NO) in the total are added into a 100mL beaker, 10mL of concentrated nitric acid is added, the beaker is placed on a heating table at 180 ℃ to react until the mixture is transparent and colloidal, the beaker is taken down and 30mL of deionized water is added to prepare the Lu (NO) containing solution3)3、Tb(NO3)3Putting the solution in an ultrasonic machine for ultrasonic treatment for 10min to make the solution uniform; adding KF (99.5%) into another 100mL beaker, and adding deionized water ultrasonic machine for ultrasonic treatment for 10min to obtain KF solution2O3KF in a molar ratio of 0.92: 70;
(2) will contain Lu (NO)3)3、Tb(NO3)3Magnetically stirring the solution for 10min, adding a KF solution, magnetically stirring for 10min for the second time, adding 25mL of absolute ethanol solution and 10mL of deionized water, and magnetically stirring for 60min for the third time to form a white turbid solution;
(3) transferring the white turbid liquid into a reaction kettle with a lining, carrying out hydrothermal reaction for 20 hours in a drying oven at 180 ℃, cooling the reaction kettle to room temperature along with the furnace after the reaction is finished, and taking out the reaction kettle;
(4) centrifuging the reactant after the hydrothermal reaction at 6000 r/min for 7min, washing the precipitate with absolute ethyl alcohol, and dispersing the precipitate in deionized water to obtain KLu2F7:0.08Tb3+A scintillator; KLu2F7:0.08Tb3+The XRD pattern of the scintillator is shown in FIG. 1, which shows no clutter compared to standard PDF cards 27-0459, indicating that the resulting scintillator material is a single phase.
Example 2: this example is for X-rayHigh brightness KLu for imaging2F7The scintillator has the chemical formula KLu2F7:0.12Tb3 +；
KLu for X-ray imaging as described above2F7The preparation method of the scintillator comprises the following steps:
(1) mixing Lu and Tb at a molar ratio of 0.88:0.122O3(99.99%)、Tb4O7(99.99%) 2mmol of Lu (NO) in the total are added into a 100mL beaker, 10mL of concentrated nitric acid is added, the beaker is placed on a heating table at 180 ℃ to react until the mixture is transparent and colloidal, the beaker is taken down and 30mL of deionized water is added to prepare the Lu (NO) containing solution3)3、Tb(NO3)3Putting the solution in an ultrasonic machine for ultrasonic treatment for 10min to make the solution uniform; adding KF (99.5%) into another 100mL beaker, and adding deionized water ultrasonic machine for ultrasonic treatment for 10min to obtain KF solution2O3KF in a molar ratio of 0.88: 70;
(2) will contain Lu (NO)3)3、Tb(NO3)3Magnetically stirring the solution for 15min, adding a KF solution, magnetically stirring for 15min for the second time, adding 25mL of absolute ethanol solution and 10mL of deionized water, and magnetically stirring for 60min for the third time to form a white turbid solution;
(3) transferring the white turbid liquid into a reaction kettle with a lining, carrying out hydrothermal reaction for 22 hours at 190 ℃ in a drying oven, cooling the reaction kettle to room temperature along with a furnace after the reaction is finished, and taking out the reaction kettle;
(4) centrifuging the reaction product after the hydrothermal reaction for 7min at 5500 r/min, washing the precipitate with absolute ethyl alcohol, and dispersing the precipitate in deionized water to obtain KLu2F7:0.12Tb3+Scintillator, KLu2F7:0.12Tb3+The XRD pattern of the scintillator is shown in FIG. 1, which shows no clutter compared to standard PDF cards 27-0459, indicating that the resulting scintillator material is a single phase.
Example 3: this example high brightness KLu for X-ray imaging2F7The scintillator has the chemical formula KLu2F7:0.16Tb3 +；
The above-mentioned application in X-ray imagingKLu of images2F7The preparation method of the scintillator comprises the following steps:
(1) mixing Lu and Tb at a molar ratio of 0.84:0.162O3(99.99%)、Tb4O7(99.99%) 2mmol of Lu (NO) in the total are added into a 100mL beaker, 10mL of concentrated nitric acid is added, the beaker is placed on a heating table at 180 ℃ to react until the mixture is transparent and colloidal, the beaker is taken down and 30mL of deionized water is added to prepare the Lu (NO) containing solution3)3、Tb(NO3)3Putting the solution in an ultrasonic machine for ultrasonic treatment for 10min to make the solution uniform; adding KF (99.5%) into another 100mL beaker, and adding deionized water ultrasonic machine for ultrasonic treatment for 10min to obtain KF solution2O3KF in a molar ratio of 0.84: 70;
(2) will contain Lu (NO)3)3、Tb(NO3)3Magnetically stirring the solution for 15min, adding a KF solution, magnetically stirring for 15min for the second time, adding 25mL of absolute ethanol solution and 10mL of deionized water, and magnetically stirring for 60min for the third time to form a white turbid solution;
(3) transferring the white turbid liquid into a reaction kettle with a lining, carrying out hydrothermal reaction for 20 hours in a drying oven at 200 ℃, cooling the reaction kettle to room temperature along with the furnace after the reaction is finished, and taking out the reaction kettle;
(4) centrifuging the reactant after the hydrothermal reaction at 6000 r/min for 6min, washing the precipitate with absolute ethyl alcohol, and dispersing the precipitate in deionized water to obtain KLu2F7:0.16Tb3+Scintillator, KLu2F7:0.16Tb3+The XRD pattern of the scintillator is shown in FIG. 1, which shows no peaks compared to standard PDF cards 27-0459, indicating that the resulting scintillator material is a single phase; KLu obtained in this example2F7：0.16Tb3+The emission spectrum under the excitation of light with 370nm wavelength is shown in FIG. 2, and the X-ray luminescence spectrum is shown in FIG. 3.
Example 4: this example high brightness KLu for X-ray imaging2F7The scintillator has the chemical formula KLu2F7:0.20Tb3 +；
KLu for X-ray imaging as described above2F7The preparation method of the scintillator comprises the following steps:
(1) mixing Lu and Tb at a molar ratio of 0.8:0.22O3(99.99%)、Tb4O7(99.99%) 2mmol of Lu (NO) in the total are added into a 100mL beaker, 10mL of concentrated nitric acid is added, the beaker is placed on a heating table at 180 ℃ to react until the mixture is transparent and colloidal, the beaker is taken down and 30mL of deionized water is added to prepare the Lu (NO) containing solution3)3、Tb(NO3)3Putting the solution in an ultrasonic machine for ultrasonic treatment for 10min to make the solution uniform; adding KF (99.5%) into another 100mL beaker, and adding deionized water ultrasonic machine for ultrasonic treatment for 10min to obtain KF solution2O3KF is 0.8:70 in a molar ratio;
(2) will contain Lu (NO)3)3、Tb(NO3)3Magnetically stirring the solution for 15min, adding a KF solution, magnetically stirring for 15min for the second time, adding 25mL of absolute ethanol solution and 10mL of deionized water, and magnetically stirring for 60min for the third time to form a white turbid solution;
(3) transferring the white turbid liquid into a reaction kettle with a lining, carrying out hydrothermal reaction for 20 hours in a drying oven at 220 ℃, cooling the reaction kettle to room temperature along with the furnace after the reaction is finished, and taking out the reaction kettle;
(4) centrifuging the reactant after the hydrothermal reaction at 6000 r/min for 6min, washing the precipitate with absolute ethyl alcohol, and dispersing the precipitate in deionized water to obtain KLu2F7:0.20Tb3+Scintillator, KLu2F7:0.20Tb3+The XRD pattern of the scintillator is shown in FIG. 1, which shows no clutter compared to standard PDF cards 27-0459, indicating that the resulting scintillator material is a single phase.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911313857.8A CN110982529A (en) | 2019-12-19 | 2019-12-19 | High brightness KLu2F7 scintillator for X-ray imaging and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911313857.8A CN110982529A (en) | 2019-12-19 | 2019-12-19 | High brightness KLu2F7 scintillator for X-ray imaging and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110982529A true CN110982529A (en) | 2020-04-10 |
Family
ID=70095766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911313857.8A Pending CN110982529A (en) | 2019-12-19 | 2019-12-19 | High brightness KLu2F7 scintillator for X-ray imaging and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110982529A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103975042A (en) * | 2011-09-22 | 2014-08-06 | 圣戈班晶体及检测公司 | Scintillation compound including a rare earth element and a process of forming the same |
| CN105001866A (en) * | 2015-06-30 | 2015-10-28 | 中山大学 | Lutetium-base fluoride up-conversion luminescence nanocrystal and preparation method thereof |
| CN106479501A (en) * | 2016-09-13 | 2017-03-08 | 厦门理工学院 | Up-conversion luminescence rare earth Lu base fluoride materials and preparation method thereof |
| CN108165269A (en) * | 2017-12-06 | 2018-06-15 | 中山大学 | A kind of fluorination lutetium potassium that phase change delay and Up-conversion Intensity greatly improve is nanocrystalline and preparation method thereof |
-
2019
- 2019-12-19 CN CN201911313857.8A patent/CN110982529A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103975042A (en) * | 2011-09-22 | 2014-08-06 | 圣戈班晶体及检测公司 | Scintillation compound including a rare earth element and a process of forming the same |
| CN105001866A (en) * | 2015-06-30 | 2015-10-28 | 中山大学 | Lutetium-base fluoride up-conversion luminescence nanocrystal and preparation method thereof |
| CN106479501A (en) * | 2016-09-13 | 2017-03-08 | 厦门理工学院 | Up-conversion luminescence rare earth Lu base fluoride materials and preparation method thereof |
| CN108165269A (en) * | 2017-12-06 | 2018-06-15 | 中山大学 | A kind of fluorination lutetium potassium that phase change delay and Up-conversion Intensity greatly improve is nanocrystalline and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| CAO CHUNYAN等: "Synthesis, optical properties, and energy transfer of Ce3+, Tb3+ doped KLu2F7", 《JOURNAL OF RARE EARTHS》 * |
| XIE AN等: "Eu3+ doped K-Lu-F system optical materials: controlling synthesis, phase evolution, and optical properties", 《JOURNAL OF RARE EARTHS》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111286332B (en) | A class of rare earth-based multimodal luminescent perovskite materials and their preparation methods and applications | |
| CN113025327A (en) | Multi-mode luminous lead-free double perovskite material and preparation method thereof | |
| Yan et al. | Ultraviolet-C persistent luminescence from the Lu 2 SiO 5: Pr 3+ persistent phosphor for solar-blind optical tagging | |
| CN105754598A (en) | Rare earth-doped nano-spherical TiO2 upconversion compound and preparation method thereof | |
| CN112940726B (en) | Blue-violet and near-infrared two-region dual-mode luminescent nanocrystal and preparation method thereof | |
| CN107226914B (en) | A kind of terbium organic framework complex and preparation method thereof | |
| Lin et al. | Sol–gel synthesis and characterization of Zn2SiO4: Mn phosphor films | |
| CN104449731A (en) | Composite nanostructure based on rare earth up-conversion luminescent material as well as preparation method and application of composite nanostructure | |
| Xin et al. | Hydrothermal synthesis and multi-color photoluminescence of GdVO 4: Ln 3+(Ln= Sm, Dy, Er) sub-micrometer phosphors | |
| CN109943336A (en) | A kind of rare earth ion doped bismuth oxychloride semiconductor material and preparation method thereof | |
| CN103436263B (en) | Preparation method of water-soluble red-green light tunable rare-earth doped up-conversion nano-material | |
| Zhou et al. | Enhanced photoluminescence of K7CaY2 (B5O10) 3: Eu3+, Sm3+/Gd3+ phosphors through energy transfer and their applications in LED lights for plant growth | |
| Luo et al. | Bi3+ ion doping: An effective strategy to significantly enhance luminescence performances of NaGdF4: Eu3+ red-emitting nanocrystals | |
| CN111040764A (en) | Fluoride high-brightness X-ray scintillator and preparation method thereof | |
| Czajka et al. | Physicochemical Characterization of the Hybrid Molybdate–Tungstate Materials for Solid-State Lighting | |
| CN110982529A (en) | High brightness KLu2F7 scintillator for X-ray imaging and preparation method thereof | |
| Xu et al. | Up and down-conversion photoluminescence energy demonstration of Ho3+/Yb3+ co-doped double perovskites microcrystals | |
| CN111253941A (en) | Temperature-division-area nanometer fluorescence thermometer, preparation method thereof and fluorescence temperature measuring method | |
| Fan et al. | Achieving multi-excitation in lanthanide-based Cs2NaTbCl6: Ce/Yb double perovskite single crystals for anti-counterfeiting | |
| Liu et al. | Optical thermometry and heating based on the upconversion fluorescence from Yb3+/Er3+ co-doped NaLa (MoO4) 2 phosphor | |
| CN108929686B (en) | Preparation method of polychromatic luminescent europium and gadolinium co-doped hydroxyapatite/carbon dots | |
| CN101560389A (en) | Method for preparing terbium-doped yttria green-light luminescent powder | |
| CN107337688A (en) | A kind of europium organic backbone complex and preparation method thereof | |
| Feng et al. | Hydrothermal synthesis and luminescence of NaGd (WO 4) 2: RE 3+(RE= Eu, Tb, Tm) phosphors | |
| CN111303876A (en) | Rare earth ion doped Ba2RAlO5 up-conversion luminescent material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200410 |