CN111205866A - Bi-doped visible-near-infrared long-afterglow fluorescent material and preparation method thereof - Google Patents

Bi-doped visible-near-infrared long-afterglow fluorescent material and preparation method thereof Download PDF

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CN111205866A
CN111205866A CN202010102324.1A CN202010102324A CN111205866A CN 111205866 A CN111205866 A CN 111205866A CN 202010102324 A CN202010102324 A CN 202010102324A CN 111205866 A CN111205866 A CN 111205866A
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fluorescent material
infrared long
afterglow
afterglow fluorescent
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彭明营
熊普先
李瑗媛
刘怀陆
郑炽彬
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Wuyi University
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    • C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
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Abstract

The invention relates to the technical field of fluorescent materials, and particularly discloses a Bi-doped visible near-infrared long-afterglow fluorescent material and a preparation method thereof, wherein the fluorescent material takes LiTaO3 as a substrate and Bi ions as active ions, and the chemical general formula of the fluorescent material is Li1-xTaO3: xBi; wherein the molar number x of Bi ions is 0-0.03; bi replaces Li in the crystal; the crystal structure of the crystal belongs to an orthorhombic system; the method comprises the steps of mixing compound raw materials containing lithium, tantalum and bismuth according to a molar ratio of Li to Ta to O to Bi of 1-x to 1 to 3 to x, wherein x is 0-0.03; s, grinding and uniformly mixing the compound raw materials mixed in the step S1, and sintering in an oxidizing atmosphere at 1050-1090 ℃ for 6-10 hours; cooling along with the furnace to obtain the Bi-doped visible near-infrared long-afterglow fluorescent material. The invention is convenient for industrialized mass production; meanwhile, the afterglow emitting performance in a visible near infrared region is achieved.

Description

Bi-doped visible-near-infrared long-afterglow fluorescent material and preparation method thereof
Technical Field
The invention relates to the technical field of fluorescent materials, in particular to a Bi-doped visible-near-infrared long-afterglow fluorescent material and a preparation method thereof.
Background
The long afterglow material, as one kind of energy storing material, can store the excited light energy in the material and release the light energy slowly after the excitation source is turned off. The remaining glow time ranges from a few seconds, minutes, hours, to even days. Because of this "energy storage" property of afterglow materials, they have found applications in fields such as two-dimensional information storage, in vivo bio-imaging, emergency display, anti-counterfeiting and light source display. Afterglow material in visible light region, such as green light afterglow material SrAl2O2:Eu2+And blue light afterglow material CaAl2O4:Eu2+,Nd3+Can be applied to noctilucent products such as working clothes of sanitation workers, luminous paint and the like. The near infrared region, especially afterglow material in the tissue penetrating biological window wave band, may be used as fluorescent mark molecule in biological imaging to in-situ real-time represent medicine carrying release and other process inside living body. At present, luminous ions with afterglow emission of visible near infrared transition are rare.
Disclosure of Invention
The invention aims to provide a Bi-doped visible-near-infrared long afterglow fluorescent material and a preparation method thereof, wherein the visible-near-infrared long afterglow fluorescent material has simple preparation conditions and is convenient for mass production.
In order to solve the technical problem, the invention provides a Bi-doped visible-near-infrared long-afterglow fluorescent material prepared from LiTaO3As a substrate, Bi ions are used as activating ions, and the chemical general formula is Li1-xTaO3xBi; wherein the molar number x of Bi ions is 0-0.03; bi replaces Li in the crystal; the crystal structure belongs to an orthorhombic system.
The preparation method of the Bi-doped visible near-infrared long-afterglow fluorescent material comprises the following specific steps:
s1, mixing the raw materials of the compound containing lithium, tantalum and bismuth according to the mol ratio of Li to Ta to O to Bi of 1-x to 1 to 3 to x, wherein x is 0-0.03;
s2, grinding and uniformly mixing the compound raw materials mixed in the step S1, and sintering the mixture in an oxidizing atmosphere at 1050-1090 ℃ for 6-10 hours; cooling along with the furnace to obtain the Bi-doped visible near-infrared long-afterglow fluorescent material.
Preferably, the oxidizing atmosphere is an air atmosphere or an oxygen atmosphere.
Preferably, the raw material of the lithium-containing compound is any one of lithium carbonate, lithium oxide, lithium nitride and lithium carbide.
Preferably, the tantalum-containing compound raw material is any one of tantalum oxide and tantalum powder.
Preferably, the bismuth-containing compound raw material is any one of bismuth oxide, bismuth powder, bismuth sulfide and bismuth selenide.
Preferably, the sintering temperature is 1070 ℃ and the sintering time is 8 hours.
The principle of the invention is as follows: crystallographic data show, LiTaO3Belonging to orthorhombic system, R3c space group, lattice constant
Figure BDA0002387275900000021
And Z ═ 6. Li has 1 six-coordinate site in the unit cell. In contrast to the difference in ionic radius and charge, the Bi-doped crystals preferentially replace 6-coordinated Li ions.
The invention has the following beneficial effects:
the invention does not adopt rare earth as a luminescence center, does not adopt harsh preparation conditions, and utilizes low-cost Bi as an activator under normal pressure, thereby being convenient for industrialized mass production; meanwhile, the afterglow emitting performance in a visible near infrared region is achieved; the afterglow emission intensity of the near infrared region increases with the reduction time of 2 h.
Drawings
FIG. 1 is a powder X-ray diffraction spectrum of samples of compounding ratios (1) to (7) of example 1.
FIG. 2 is the afterglow emission spectrum of the sample of formulation (3) of example 1.
FIG. 3 is the afterglow emission spectra of the sample of formulation (3) of example 1 after non-reduction and 2h reduction.
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.
Example 1:
selecting lithium carbonate, tantalum oxide and bismuth oxide as starting compound raw materials, and respectively weighing four compound raw materials according to the molar ratio of each element, wherein the four compound raw materials are 6 groups in total and are as follows:
li, Ta, Bi, 1.000:1:0, corresponding to x, 0;
li, Ta, Bi, 0.995:1:0.005, corresponding to x, 0.005;
li, Ta, Bi, 0.990:1:0.010, corresponding to x, 0.010;
li Ta Bi 0.985:1:0.015 corresponding to x 0.015;
li, Ta, Bi, 0.980, 1, 0.020, corresponding to x, 0.020;
li, Ta, Bi, 0.975:1:0.025, corresponding to x, 0.025;
li, Ta and Bi are 0.970:1:0.030, and x is 0.030 correspondingly;
grinding the mixture, uniformly mixing, putting the mixture into a corundum crucible, and putting the crucible into a high-temperature electric furnace. The temperature rise rate is accurately controlled, the sample is sintered for 8 hours at 1070 ℃ and is naturally cooled along with the furnace, and the Bi-doped long afterglow fluorescent material which can see the near infrared is prepared.
Referring to FIG. 1, the powder X-ray diffraction spectra of the samples of the compositions (1) to (6) of this example were measured by a Japanese Rigaku D/max-IIIA X-ray diffractometer at a test voltage of 40kV, a scanning speed of 1.2 DEG/min, a test current of 40mA, and Cu-K α 1X-ray at a wavelength of 40mA
Figure BDA0002387275900000031
X-ray diffraction analysis shows that the mixture ratios (1) to (7) are LiTaO3The phase belongs to an orthorhombic system, and the doping of Bi does not influence the formation of a crystalline phase.
Referring to FIG. 2, the afterglow emission spectrum of the sample of the formulation (3) of this example is obtained by using a U.S. ocean optical QE65Pro fiber spectrometer, the data acquisition integration time is 1 second, and the scanning step length is 1 nm. As can be seen from FIG. 2, after the material sample is excited by light, an afterglow emission signal in the visible to near infrared region appears. Wherein the afterglow peak in the visible light region is 460nm and is blue light. And the afterglow peak of the near infrared is positioned at 836nm and is the near infrared light in the first biological window (780-1000 nm).
Referring to FIG. 3, it is the afterglow emission spectra of the sample of formulation (3) of this example after being unreduced and 2h reduction. The United states ocean optical QE65Pro fiber optic spectrometer is adopted, the data acquisition integration time is 1 second, and the scanning step length is 1 nm. As shown in FIG. 3, after the sample is reduced for 2h, the afterglow emission intensity in the visible region is reduced, and the afterglow emission intensity in the near infrared region is increased.
Example 2:
lithium oxide, tantalum oxide and bismuth oxide are selected as starting compound raw materials, the three raw materials are respectively weighed according to the molar ratio of Li to Ta to Bi of 0.990 to 1 to 0.010 and the corresponding x of 0.010, the mixture is ground and uniformly mixed, then the mixture is placed into a corundum crucible, and then the crucible is placed into a high-temperature electric furnace. Pre-burning the sample at 1050 ℃, 1060 ℃, 1070 ℃, 1080 ℃ and 1090 ℃ for 8h respectively, and naturally cooling along with the furnace to obtain the Bi-doped long afterglow fluorescent powder which can see near infrared. X-ray diffraction analysis shows that the compound is LiTaO3A crystalline phase. The spectral properties of the phosphor are similar to those of the formula (3) in example 1, and the phosphor emits light most intensely at a sintering temperature of 1070 ℃.
Example 3:
lithium oxide, tantalum oxide and bismuth selenide are selected as starting compound raw materials, the three raw materials are respectively weighed according to the molar ratio of Li to Ta to Bi of 0.990 to 1 to 0.010 and the corresponding x of 0.010, the mixture is ground and uniformly mixed, then the mixture is placed into a corundum crucible, and then the crucible is placed into a high-temperature electric furnace. And (3) sintering the sample at 1050 ℃, 1060 ℃, 1070 ℃, 1080 ℃ and 1090 ℃ for 6, 7, 8, 9 and 10 hours respectively, and naturally cooling the sample along with the furnace to obtain the Bi-doped long afterglow fluorescent powder capable of seeing near infrared rays. X-ray diffraction analysis shows that the compound is LiTaO3A crystalline phase. The spectral properties of the phosphor were matched as in example 1The light emission is strongest when the sintering temperature is 1070 ℃ and the time is 8h in a similar way to the (3).
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and substitutions can be made without departing from the technical principle of the present invention, and these modifications and substitutions should also be regarded as the protection scope of the present invention.

Claims (7)

1. A Bi-doped visible-near-infrared long-afterglow fluorescent material is characterized in that: with LiTaO3As a substrate, Bi ions are used as activating ions, and the chemical general formula is Li1-xTaO3xBi; wherein the molar number x of Bi ions is 0-0.03; bi replaces Li in the crystal; the crystal structure belongs to an orthorhombic system.
2. The method for preparing the Bi-doped visible near-infrared long-afterglow fluorescent material as claimed in claim 1, wherein the method comprises the following steps: the method comprises the following steps:
s1, mixing the raw materials of the compound containing lithium, tantalum and bismuth according to the mol ratio of Li to Ta to O to Bi of 1-x to 1 to 3 to x, wherein x is 0-0.03;
s2, grinding and uniformly mixing the compound raw materials mixed in the step S1, and sintering the mixture in an oxidizing atmosphere at 1050-1090 ℃ for 6-10 hours; cooling along with the furnace to obtain the Bi-doped visible near-infrared long-afterglow fluorescent material.
3. The method for preparing the Bi-doped visible-near-infrared long-afterglow fluorescent material as claimed in claim 2, wherein the oxidizing atmosphere is an air atmosphere or an oxygen atmosphere.
4. The method for preparing the Bi-doped visible-near-infrared long-afterglow fluorescent material as claimed in claim 2, wherein the raw material of the lithium-containing compound is any one of lithium carbonate, lithium oxide, lithium nitride and lithium carbide.
5. The method for preparing the Bi-doped visible near-infrared long-afterglow fluorescent material as claimed in claim 2, wherein the tantalum-containing compound is any one of tantalum oxide and tantalum powder.
6. The method for preparing the Bi-doped visible near-infrared long-afterglow fluorescent material as claimed in claim 2, wherein the bismuth-containing compound is selected from any one of bismuth oxide, bismuth powder, bismuth sulfide and bismuth selenide.
7. The method for preparing the Bi-doped visible near-infrared long-afterglow fluorescent material as claimed in claim 2, wherein the sintering temperature is 1070 ℃ and the sintering time is 8 hours.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114437721A (en) * 2020-11-05 2022-05-06 中国科学院上海硅酸盐研究所 Rare earth ion Tb3+Doped LiTaO3Multi-band emission pressure luminescent material and preparation method and application thereof

Citations (1)

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Publication number Priority date Publication date Assignee Title
CN110511754A (en) * 2019-08-23 2019-11-29 同济大学 A kind of tantalic acid alkali photostimulated phosphor and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN110511754A (en) * 2019-08-23 2019-11-29 同济大学 A kind of tantalic acid alkali photostimulated phosphor and preparation method thereof

Non-Patent Citations (1)

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Title
LILI LI ET AL.,: ""Interaction between Bi Dopants and Intrinsic Defects in LiNbO3 from Local and Hybrid Density Functional Theory Calculations"", 《INORG. CHEM.》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114437721A (en) * 2020-11-05 2022-05-06 中国科学院上海硅酸盐研究所 Rare earth ion Tb3+Doped LiTaO3Multi-band emission pressure luminescent material and preparation method and application thereof
CN114437721B (en) * 2020-11-05 2023-04-07 中国科学院上海硅酸盐研究所 Rare earth ion Tb 3+ Doped LiTaO 3 Multi-band emission pressure luminescent material and preparation method and application thereof

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