CN114806565B - Chromium ion doped antimonate near infrared long afterglow fluorescent material - Google Patents
Chromium ion doped antimonate near infrared long afterglow fluorescent material Download PDFInfo
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Abstract
The invention provides a Mg as formula 2‑2x‑y Zn y InSbO 6 :xCr 3+ ,xR + The invention also provides a preparation method of the antimonate near-infrared long-afterglow fluorescent material. The antimonate fluorescent material provided by the application has an excitation band extending from 240nm to 650nm, can be effectively excited by near ultraviolet light, and has internal quantum efficiency as high as 70.8%; the near infrared light is emitted under the irradiation of the excitation light, and the near infrared long afterglow luminous effect can last for 24 hours after the excitation light source is removed. The manufacturing method adopted by the invention is simple, has strong operability, does not need calcination in a reducing atmosphere, has no waste water and waste gas emission, is environment-friendly, has good reproducibility, stable product quality and is easy to operate and realize industrial production.
Description
Technical Field
The invention relates to the technical field of rare earth luminescent materials, in particular to a chromium ion doped antimonate near infrared long afterglow fluorescent material.
Background
The long afterglow luminescent material is a novel energy-saving weak light illumination material, can effectively absorb ultraviolet or visible light, stores energy and releases the energy in a light form, and is widely used in the fields of weak sight illumination, building flaw detection, luminous indication, alternating current LED, anti-counterfeiting, bioluminescence imaging and the like.
In the field of biological fluorescence imaging, the imaging technology using near infrared long afterglow luminescent materials as fluorescent probes realizes in-vitro excitation and delayed detection, can effectively avoid phototoxicity to biological tissues caused by in-situ excitation, and reduces harm to organisms; therefore, the method overcomes the interference of the excitation light stray light and the biological autofluorescence on the detection signal, improves the signal to noise ratio of the detection result, solves the key problem of restricting the development and application of the fluorescent biological imaging technology at present, is considered as one of the light-emitting biological imaging technologies with the most application prospect at present, is applied to the research fields of tumor cell detection, identification, drug tracing and the like, and has important significance for early detection and treatment of tumor diseases.
The preparation of near infrared material with luminous wavelength in optimal transmission window of biological tissue and its biological imaging application technology are the research hot spot in this field at home and abroad. The current near infrared long afterglow luminescent material is mainly Cr 3+ Ion activated gallate or germanate is high in cost due to the fact that compounds containing gallium and germanium are used as raw materials, and large-scale preparation and application are not facilitated. Therefore, development of near infrared long afterglow luminescent materials with low cost and excellent afterglow performance is needed.
Disclosure of Invention
The invention solves the technical problem of providing a chromium ion doped antimonate near infrared long afterglow fluorescent material which has high quantum efficiency and better long afterglow phenomenon.
In view of the above, the application provides a chromium ion doped antimonate near infrared long afterglow fluorescent material shown in a formula (I),
Mg 2-2x-y Zn y InSbO 6 ：xCr 3+ ，xR + (Ⅰ)；
wherein R is selected from one or more of Li, na and K;
0＜x≤0.100，0≤y≤1.20。
preferably, the R is selected from Li, na or K.
Preferably, x is more than or equal to 0.0005 and less than or equal to 0.050,0 and y is more than or equal to 1.0.
Preferably, the molecular formula of the antimonate near infrared long afterglow fluorescent powder is as follows: mg of 1.998 InSbO 6 :0.001Cr 3+ ,0.001Li + ；Mg 1.994 InSbO 6 :0.003Cr 3+ ,0.003Li + ；Mg 1.900 InSbO 6 :0.050Cr 3+ ,0.050Li + ；Mg 1.800 InSbO 6 :0.100Cr 3+ ,0.100Li + ；Mg 1.998 InSbO 6 :0.001Cr 3+ ,0.001K + ；Mg 1.994 InSbO 6 :0.003Cr 3+ ,0.003K + ；Mg 1.900 InSbO 6 :0.050Cr 3+ ,0.050K + ；Mg 1.800 InSbO 6 :0.100Cr 3+ ,0.100K + ；Mg 1.998 InSbO 6 :0.001Cr 3+ ,0.001Na + ；Mg 1.994 InSbO 6 :0.003Cr 3+ ,0.003Na + ；Mg 1.900 InSbO 6 :0.050Cr 3+ ,0.050Na + ；Mg 1.800 InSbO 6 :0.100Cr 3+ ,0.100Na + ；Mg 1.194 Zn 0.8 InSbO 6 :0.003Cr 3+ ,0.003Li + ；Mg 1.194 Zn 0.8 InSbO 6 :0.003Cr 3+ ,0.003K + ；Mg 1.194 Zn 0.8 InSbO 6 :0.003Cr 3+ ,0.003Na + ；Mg 0.794 Zn 1.2 InSbO 6 :0.003Cr 3+ ,0.003Li + ；Mg 0.794 Zn 1.2 InSbO 6 :0.003Cr 3+ ,0.003K + Or Mg (Mg) 0.794 Zn 1.2 InSbO 6 :0.003Cr 3+ ,0.003Na + 。
The application also provides a preparation method of the chromium ion doped antimonate near-infrared long-afterglow fluorescent material, which comprises the following steps:
mixing a magnesium source, a zinc source, an indium source, an antimony source, a chromium source and an R source, and grinding to obtain a mixture;
and (3) calcining and secondarily grinding the mixture in sequence to obtain the chromium ion doped antimonate near infrared long afterglow fluorescent material.
Preferably, the magnesium source is selected from one or more of magnesium-containing oxides, carbonates, nitrates, oxalates, citrates and acetates; the zinc source is selected from any one or more of zinc-containing oxide, carbonate, nitrate, oxalate, citrate and acetate; the indium source is selected from one or more of indium-containing oxides, hydroxides, carbonates, oxalates, acetates and nitrates; the antimony source is selected from one or more of oxides, oxalates, acetates and nitrates containing antimony; the chromium source is selected from one or more of chromium-containing oxides, hydroxides, halides, oxalates, acetates and nitrates; the R is selected from one or more of oxides, hydroxides, halides, oxalates, acetates and nitrates containing R elements.
Preferably, the grinding time is 5-120 min, and the regrinding time is 5-120 min.
Preferably, the calcination temperature is 1000-2000 ℃ and the time is 0.5-24 h.
Preferably, the atmosphere for calcination is air, nitrogen, argon or oxygen.
The application provides a chromium ion doped antimonate near infrared long afterglow fluorescent material, the molecular formula of which is shown as the formula Mg 2-2x-y Zn y InSbO 6 ：xCr 3+ ，xR + Shown; in this application, mg and Zn are part of the matrix, providing a strong crystal field environment for the luminescence center, so that Cr emits narrowband near infrared light at 698nm, and the matrix has a suitable trap, which can store the energy of the excitation light, and when the illumination is removed, the luminescent material still has a luminescence phenomenon, which can last for 24 hours. Therefore, the antimonate near infrared long afterglow fluorescent material doped with chromium ions has high quantum efficiency and better long afterglow phenomenon.
Drawings
FIG. 1 is an X-ray diffraction spectrum of near infrared long afterglow powder and standard card prepared in examples 1 to 4;
FIG. 2 is a near infrared long persistence phosphor Mg prepared in example 2 1.994 InSbO 6 :0.003Cr 3+ ,0.003Li + Excitation emission spectrum of the powder;
FIG. 3 is a near infrared long persistence phosphor Mg prepared in example 2 1.994 InSbO 6 :0.003Cr 3+ ,0.003Li + Quantum efficiency of the powder;
FIG. 4 shows the near infrared long persistence phosphor Mg prepared in example 2 1.994 InSbO 6 :0.003Cr 3+ ,0.003Li + Afterglow spectra of the powder;
FIG. 5 shows the near infrared long persistence phosphor Mg prepared in example 2 1.994 InSbO 6 :0.003Cr 3+ ,0.003Li + An afterglow decay curve of the powder;
FIG. 6 is a graph showing the effect of Cr doping amount on the luminous intensity of phosphor;
FIG. 7 is an X-ray diffraction spectrum of the phosphor prepared in comparative example 1.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
In view of the requirements of the long-afterglow luminescent materials in the prior art, the invention provides a chromium ion doped antimonate near-infrared long-afterglow luminescent material, which has higher quantum efficiency and better long-afterglow phenomenon due to doping of chromium ions. Specifically, the embodiment of the invention discloses a chromium ion doped antimonate near infrared long afterglow fluorescent material shown in a formula (I),
Mg 2-2x-y Zn y InSbO 6 ：xCr 3+ ，xR + (Ⅰ)；
wherein R is selected from one or more of Li, na and K;
0＜x≤0.100，0≤y≤1.20。
in the present application, the R is more specifically selected from Li, na or K; x is more than or equal to 0.0005 and less than or equal to 0.050,0, y is more than or equal to 1.0.
More specifically, the molecular formula of the antimonate near-infrared long-afterglow luminescent material is as follows: mg of 1.998 InSbO 6 :0.001Cr 3+ ,0.001Li + ；Mg 1.994 InSbO 6 :0.003Cr 3+ ,0.003Li + ；Mg 1.900 InSbO 6 :0.050Cr 3+ ,0.050Li + ；Mg 1.800 InSbO 6 :0.100Cr 3+ ,0.100Li + ；Mg 1.998 InSbO 6 :0.001Cr 3+ ,0.001K + ；Mg 1.994 InSbO 6 :0.003Cr 3+ ,0.003K + ；Mg 1.900 InSbO 6 :0.050Cr 3+ ,0.050K + ；Mg 1.800 InSbO 6 :0.100Cr 3+ ,0.100K + ；Mg 1.998 InSbO 6 :0.001Cr 3+ ,0.001Na + ；Mg 1.994 InSbO 6 :0.003Cr 3+ ,0.003Na + ；Mg 1.900 InSbO 6 :0.050Cr 3+ ,0.050Na + ；Mg 1.800 InSbO 6 :0.100Cr 3+ ,0.100Na + ；Mg 1.194 Zn 0.8 InSbO 6 :0.003Cr 3+ ,0.003Li + ；Mg 1.194 Zn 0.8 InSbO 6 :0.003Cr 3+ ,0.003K + ；Mg 1.194 Zn 0.8 InSbO 6 :0.003Cr 3+ ,0.003Na + ；Mg 0.794 Zn 1.2 InSbO 6 :0.003Cr 3+ ,0.003Li + ；Mg 0.794 Zn 1.2 InSbO 6 :0.003Cr 3+ ,0.003K + Or Mg (Mg) 0.794 Zn 1.2 InSbO 6 :0.003Cr 3+ ,0.003Na + 。
The application also provides a preparation method of the chromium ion doped antimonate near infrared long afterglow fluorescent material, which comprises the following steps:
mixing a magnesium source, a zinc source, an indium source, an antimony source, a chromium source and an R source, and grinding to obtain a mixture;
and calcining and secondary grinding the mixture in sequence to obtain the chromium ion doped antimonate near infrared long afterglow fluorescent material.
In the preparation method of the antimonate near infrared long afterglow luminescent material, the magnesium source compound is selected from any one of magnesium-containing oxide, carbonate, nitrate, oxalate, citrate or acetateMeaning one or a combination of at least two; more preferably MgO, mgCO 3 One or more of the following.
Preferably, the zinc source compound is selected from any one or a combination of at least two of magnesium-containing oxide, carbonate, nitrate, oxalate, citrate or acetate; more preferably ZnO, znCO 3 One or more of the following.
Preferably, the indium source compound is selected from one or more of indium-containing oxides, hydroxides, carbonates, oxalates, acetates and nitrates; more preferably In 2 O 3 And In (OH) 3 One or two of them.
The antimony source compound is selected from one or more of antimony-containing oxides, oxalates, acetates and nitrates; more preferably Sb 2 O 3 And Sb (Sb) 2 O 5 One or two of them.
The chromium element-containing compound is selected from one or more of chromium-containing oxides, hydroxides, halides, oxalates, acetates and nitrates; more preferably Cr 2 O 3 And Cr (NO) 3 ) 3 One or two of them.
The R-element-containing compound is selected from one or more of an oxide, a hydroxide, a halide, an oxalate, an acetate and a nitrate of an R-element-containing compound; more preferably from Li 2 CO 3 、K 2 CO 3 、Na 2 CO 3 One or more of the following.
After the above raw materials are mixed, the mixture is ground for 5-120 min, including but not limited to 5min, 10min, 20min, 30min, 50min, 80min, 100min or 120min, etc.
According to the invention, the obtained mixture is calcined and ground for the second time in sequence, and the chromium ion doped antimonate near infrared long afterglow luminescent material is obtained. The calcining temperature is 1000-1600 ℃, more preferably 1100-1500 ℃; including but not limited to 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, 1600 ℃, etc.; the calcination time is preferably 0.5 to 24 hours; including but not limited to 0.5h, 6h, 12h, 24h, etc. The sintering atmosphere is preferably air, nitrogen, argon or oxygen; more preferably air. The secondary grinding time is respectively 5-120 min; including but not limited to 5, 10, 20, 30, 50, 80, 100, or 120 minutes, etc.
In the invention, preferably, the primary grinding device and the secondary grinding device are agate mortar.
As a preferred embodiment of the present invention, the preparation method comprises the steps of:
(1) Mixing a magnesium source compound, an indium source compound, an antimony source compound, a chromium element-containing compound and an R element-containing compound, and grinding for 5-120 min to obtain a raw material mixture;
(2) Calcining the raw material mixture obtained in the step (1) for 0.5-24 h under the air condition of 1100-1500 ℃ and grinding for 5-120 min to obtain the near infrared long afterglow fluorescent powder.
The preparation method disclosed by the invention is simple, low in raw material and equipment cost, nontoxic, pollution-free, free of radioactivity, environment-friendly, good in reproducibility, stable in product quality, easy to operate and industrialize, and suitable for general popularization and use.
For further understanding of the present invention, the following examples are provided to illustrate the chromium ion doped antimonate near infrared long afterglow fluorescent material of the present invention in detail, and the scope of the present invention is not limited by the following examples.
Example 1
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.998:1:1:0.001: mgO, in of 0.001 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And Li (lithium) 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Grinding the sintered body obtained in step a) into powder,can obtain the chemical composition Mg 1.998 InSbO 6 :0.001Cr 3 + ,0.001Li + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 2
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.994:1:1:0.003: mgO, in of 0.003 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And Li (lithium) 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 1.994 InSbO 6 :0.003Cr 3 + ,0.003Li + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 3
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.900:1:1:0.050: mgO, in 0.050 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And Li (lithium) 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 1.900 InSbO 6 :0.050Cr 3 + ,0.050Li + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 4
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.800:1:1:0.100: mgO, in of 0.100 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And Li (lithium) 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 1.800 InSbO 6 :0.100Cr 3 + ,0.100Li + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 5
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.998:1:1:0.001: mgO, in of 0.001 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And K 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 1.998 InSbO 6 :0.001Cr 3 + ,0.001K + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 6
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.994:1:1:0.003: mgO, in of 0.003 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And K 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Will beGrinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 1.994 InSbO 6 :0.003Cr 3 + ,0.003K + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 7
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.900:1:1:0.050: mgO, in 0.050 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And K 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 1.900 InSbO 6 :0.050Cr 3 + ,0.050K + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 8
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.800:1:1:0.100: mgO, in of 0.100 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And K 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 1.800 InSbO 6 :0.100Cr 3 + ,0.100K + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 9
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.998:1:1:0.001: mgO, in of 0.001 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And Na (Na) 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 1.998 InSbO 6 :0.001Cr 3 + ,0.001Na + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 10
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.994:1:1:0.003: mgO, in of 0.003 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And Na (Na) 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 1.994 InSbO 6 :0.003Cr 3 + ,0.003Na + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 11
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.900:1:1:0.050: mgO, in 0.050 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And Na (Na) 2 CO 3 As raw materials, put into an agate mortar for mixing evenly and grinding for about 30min, put into an alumina crucible, calcined for 24h at 1350 ℃ under the air condition, cooled to room temperature along with the furnace；
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 1.900 InSbO 6 :0.050Cr 3 + ,0.050Na + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 12
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.800:1:1:0.100: mgO, in of 0.100 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And Na (Na) 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 1.800 InSbO 6 :0.100Cr 3 + ,0.100Na + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 13
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.194:0.8:1:1:0.003: mgO, znO, in of 0.003 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And Li (lithium) 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 1.194 Zn 0.8 InSbO 6 :0.003Cr 3+ ,0.003Li + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 14
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.194:0.8:1:1:0.003: mgO, znO, in of 0.003 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And K 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 1.194 Zn 0.8 InSbO 6 :0.003Cr 3+ ,0.003K + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 15
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.194:0.8:1:1:0.003: mgO, znO, in of 0.003 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And Na (Na) 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 1.194 Zn 0.8 InSbO 6 :0.003Cr 3+ ,0.003Na + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 16
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) Taking a molar ratio of 0.794:1.2:1:1:0.003: mgO, znO, in of 0.003 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And Li (lithium) 2 CO 3 As raw materials, put into an agate mortar for uniform mixingGrinding for about 30min, then placing into an alumina crucible, continuously calcining for 24h at 1350 ℃ under the air condition, and cooling to room temperature along with a furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 0.794 Zn 1.2 InSbO 6 :0.003Cr 3+ ,0.003Li + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 17
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) Taking a molar ratio of 0.794:1.2:1:1:0.003: mgO, znO, in of 0.003 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And K 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 0.794 Zn 1.2 InSbO 6 :0.003Cr 3+ ,0.003K + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Example 18
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) Taking a molar ratio of 0.794:1.2:1:1:0.003: mgO, znO, in of 0.003 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And Na (Na) 2 CO 3 As a raw material, placing the raw materials in an agate mortar for uniform mixing and grinding for about 30min, then placing the raw materials in an alumina crucible, continuously calcining the raw materials at 1350 ℃ for 24h under the air condition, and cooling the raw materials to room temperature along with a furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 0.794 Zn 1.2 InSbO 6 :0.003Cr 3+ ,0.003Na + Cr of (2) 3+ Doped antimonate moietiesInfrared long afterglow fluorescent powder.
Example 19
This example differs from example 2 only in that the magnesium source compound of step (a) is MgCO 3 Other conditions and parameters were exactly the same as in example 2.
Example 20
This example differs from example 2 only In that the indium source compound of step (a) is In (OH) 3 Other conditions and parameters were exactly the same as in example 2.
Example 21
This example differs from example 2 only in that the compound of the antimony source in step (a) is Sb 2 O 5 Other conditions and parameters were exactly the same as in example 2.
Example 22
This example differs from example 2 only in that the chromium source compound of step (a) is Cr (NO) 3 ) 3 Other conditions and parameters were exactly the same as in example 2.
Example 23
This example differs from example 13 only in that the zinc source compound of step (a) is ZnCO 3 Other conditions and parameters were exactly the same as in example 13.
Example 24
This example differs from example 2 only in that the calcination temperature in step (a) is 1000 ℃, the other conditions and parameters being exactly the same as in example 2.
Example 25
This example differs from example 2 only in that the calcination temperature in step (a) is 1500 ℃, the other conditions and parameters being exactly the same as in example 2.
Example 26
This example differs from example 2 only in that the calcination temperature in step (a) is 1600 ℃, the other conditions and parameters being exactly the same as in example 2.
Example 27
The difference between this example and example 2 is that the polishing time in step (a) is 120min, and the other conditions and parameters are exactly the same as those in example 2.
Example 28
This example differs from example 2 only in that the grinding time in step (a) is 60min, and other conditions and parameters are exactly the same as in example 2.
Example 29
This example differs from example 2 only in that the grinding time in step (a) is 5min, and other conditions and parameters are exactly the same as in example 2.
Example 30
This example differs from example 2 only in that the calcination time in step (a) is 0.5h, the other conditions and parameters being exactly the same as in example 2.
Example 31
This example differs from example 2 only in that the calcination time in step (a) is 12h, the other conditions and parameters being exactly the same as in example 2.
Example 32
This example differs from example 2 only in that the sintering atmosphere in step (a) is oxygen, and other conditions and parameters are exactly the same as in example 2.
Example 33
This example differs from example 21 only in that the sintering atmosphere in step (a) is nitrogen, and other conditions and parameters are identical to those in example 21.
Example 34
This example differs from example 21 only in that the sintering atmosphere in step (a) is argon, and other conditions and parameters are identical to those of example 21.
Comparative example 1
The embodiment provides a chromium ion doped antimonate near infrared long afterglow fluorescent powder, which is prepared by the following steps:
a) The molar ratio is 1.600:1:1:0.200: mgO, in of 0.200 2 O 3 、Sb 2 O 3 、Cr 2 O 3 And Li (lithium) 2 CO 3 The raw materials are put into an agate mortar for uniform mixing and grinding for about 30min, and then put into an alumina crucible under the air conditionContinuously calcining at 1350 ℃ for 24 hours, and cooling to room temperature along with the furnace;
b) Grinding the sintered body obtained in the step a) into powder to obtain the chemical composition Mg 1.600 InSbO 6 :0.200Cr 3 + ,0.200Li + Cr of (2) 3+ Doped antimonate near infrared long afterglow fluorescent powder.
Performance test:
the powder obtained in examples 1 to 4 was subjected to X-ray diffraction, and the test results are shown in FIG. 1, and Cr can be seen 3+ And Li (lithium) + Doping of ions with Mg 2 InSbO 6 The phase purity of the host material has little significant effect. Thus, it can be inferred that Cr 3+ And Li (lithium) + Ions are almost completely dissolved into Mg 2 InSbO 6 In the host lattice.
Taking the near infrared long afterglow fluorescent powder Mg prepared in the example 2 1.994 InSbO 6 :0.003Cr 3+ ,0.003Li + The powder was subjected to fluorescence spectrum testing, the excitation and emission spectra of which are shown in fig. 2, and it can be seen from fig. 2 that the excitation band of the material extends from 240nm to 650nm, and can be effectively excited by near ultraviolet light, and the emission band has a peak value at about 698 nm. As can be seen from FIG. 3, mg 1.994 InSbO 6 :0.003Cr 3+ ,0.003Li + The quantum efficiency of the powder is as high as 70.8%.
Taking the near infrared long afterglow fluorescent powder Mg prepared in the example 2 1.994 InSbO 6 :0.003Cr 3+ ,0.003Li + The powder was subjected to afterglow spectrum and fluorescence attenuation test after irradiation with 365nm ultraviolet lamp for 3min, the rest glow spectrum is shown in FIG. 4, and its spectrum shape is similar to excitation spectrum, showing afterglow and Cr 3+ Related to the following. As can be seen from FIG. 5, mg 1.994 InSbO 6 :0.003Cr 3+ ,0.003Li + The afterglow of the powder can last 24 hours.
The powder prepared in comparative example 1 was taken for X-ray diffraction, and the test result is shown in fig. 7, the main material has significant impurity peaks, and the sample purity is not high.
In the comparison of examples 1 to 4 and comparative example 1, in which the doping amounts of Cr and Li were changed only without changing other elements, the effect of the doping amounts on the light intensity was as shown in fig. 6, it was seen that the near infrared light emitting effect was greatly reduced when x was out of the range of the present application.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A chromium ion doped antimonate near infrared long afterglow fluorescent material shown in formula (I),
Mg 2-2x-y Zn y InSbO 6 ：xCr 3+ ，xR + (Ⅰ)；
wherein R is selected from one or more of Li, na and K;
0＜x≤0.100，0≤y≤1.20。
2. the antimonate near infrared long persistence fluorescent material of claim 1, wherein R is selected from Li, na, or K.
3. The antimonate near infrared long persistence fluorescent material of claim 1, wherein x is greater than or equal to 0.0005 and less than or equal to 0.050,0 and y is greater than or equal to 1.0.
4. The antimonate near infrared long persistence fluorescent material of claim 1 whichIs characterized in that the molecular formula of the antimonate near infrared long afterglow fluorescent powder is as follows: mg of 1.998 InSbO 6 :0.001Cr 3+ ,0.001Li + ；Mg 1.994 InSbO 6 :0.003Cr 3+ ,0.003Li + ；Mg 1.900 InSbO 6 :0.050Cr 3+ ,0.050Li + ；Mg 1.800 InSbO 6 :0.100Cr 3+ ,0.100Li + ；Mg 1.998 InSbO 6 :0.001Cr 3+ ,0.001K + ；Mg 1.994 InSbO 6 :0.003Cr 3+ ,0.003K + ；Mg 1.900 InSbO 6 :0.050Cr 3+ ,0.050K + ；Mg 1.800 InSbO 6 :0.100Cr 3+ ,0.100K + ；Mg 1.998 InSbO 6 :0.001Cr 3+ ,0.001Na + ；Mg 1.994 InSbO 6 :0.003Cr 3+ ,0.003Na + ；Mg 1.900 InSbO 6 :0.050Cr 3+ ,0.050Na + ；Mg 1.800 InSbO 6 :0.100Cr 3+ ,0.100Na + ；Mg 1.194 Zn 0.8 InSbO 6 :0.003Cr 3+ ,0.003Li + ；Mg 1.194 Zn 0.8 InSbO 6 :0.003Cr 3+ ,0.003K + ；Mg 1.194 Zn 0.8 InSbO 6 :0.003Cr 3+ ,0.003Na + ；Mg 0.794 Zn 1.2 InSbO 6 :0.003Cr 3+ ,0.003Li + ；Mg 0.794 Zn 1.2 InSbO 6 :0.003Cr 3+ ,0.003K + Or Mg (Mg) 0.794 Zn 1.2 InSbO 6 :0.003Cr 3+ ,0.003Na + 。
5. The method for preparing the chromium ion doped antimonate near infrared long afterglow fluorescent material of claim 1, comprising the following steps:
mixing a magnesium source, a zinc source, an indium source, an antimony source, a chromium source and an R source, and grinding to obtain a mixture;
and (3) calcining and secondarily grinding the mixture in sequence to obtain the chromium ion doped antimonate near infrared long afterglow fluorescent material.
6. The method of claim 5, wherein the magnesium source is selected from one or more of an oxide, carbonate, nitrate, oxalate, citrate, and acetate containing magnesium; the zinc source is selected from any one or more of zinc-containing oxide, carbonate, nitrate, oxalate, citrate and acetate; the indium source is selected from one or more of indium-containing oxides, hydroxides, carbonates, oxalates, acetates and nitrates; the antimony source is selected from one or more of oxides, oxalates, acetates and nitrates containing antimony; the chromium source is selected from one or more of chromium-containing oxides, hydroxides, halides, oxalates, acetates and nitrates; the R is selected from one or more of oxides, hydroxides, halides, oxalates, acetates and nitrates containing R elements.
7. The method according to claim 5, wherein the grinding time is 5 to 120min and the regrinding time is 5 to 120min.
8. The method according to claim 5, wherein the calcination is carried out at a temperature of 1000 to 2000 ℃ for a time of 0.5 to 24 hours.
9. The method according to claim 5, wherein the calcined atmosphere is air, nitrogen, argon or oxygen.
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| Liu Yuanyuan.Novel doubleperovskite Mg2InSbO6:Sm3+ phosphor with excellent heat-resistant performance and high color purity used in white LEDs.《Journal of The Ameican Ceramic Sociey》.2021,第10卷(第11期),全文. * |
| Xie Yan.An efficient far-red emission Sr2InSbO6:Mn4+, M (M = Li+ ,Na+ , and K+ ) phosphors for plant cultivation LEDs.《Journal of The Ameican Ceramic Sociey》.2021,第105卷(第2期),全文. * |
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