CN104861970A - Cr-doped near-infrared long-afterglow luminescent material with perovskite structure and preparation method thereof - Google Patents
Cr-doped near-infrared long-afterglow luminescent material with perovskite structure and preparation method thereof Download PDFInfo
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- CN104861970A CN104861970A CN201510160378.2A CN201510160378A CN104861970A CN 104861970 A CN104861970 A CN 104861970A CN 201510160378 A CN201510160378 A CN 201510160378A CN 104861970 A CN104861970 A CN 104861970A
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Abstract
The invention discloses a Cr-doped near-infrared long-afterglow luminescent material with a perovskite structure. A substrate material of the luminescent material is ABO3, wherein A is Ca, Sr or Ba, B is Sn or Ti, and 0.001 to 5 mol% of Cr<3+> is doped in the substrate material. The invention further discloses a preparation method for the near-infrared long-afterglow luminescent material. The method comprises the following steps: (1) separately weighing a compound containing A, a compound containing Ti and a compound containing Cr; and (2) after grinding and uniform mixing of the above compounds, presintering the obtained mixture in the air/reductive atmosphere, then grinding the mixture again and carrying out sintering in the air/reductive atmosphere for a plurality of hours. The near-infrared long-afterglow luminescent material prepared in the invention has an emission band located at 650 to 850 nm, an emission peak at 760 nm and afterglow time of as long as 100 min. The preparation method is simple, uses cheap raw materials and can easily realize large-scale technical popularization.
Description
Technical field
The present invention relates to nm near-infrared long after glow luminous material, particularly the near infrared long after glow luminous material of perovskite structure that adulterates of a kind of Cr and preparation method.
Background technology
Optical imagery, using photon as information source, represents a domain variability extended fast and is applied directly to pharmacology, molecular cytobiology and diagnostics.But still there is many limitation in this technology, the tissue autofluorescence produced during illumination especially in vivo and the weak tissue permeability under shortwave excitation light irradiation.In order to overcome these difficulties, scientist have studied a series of phosphor, utilizing emitted light is near infrared region (NIR), molecular emission near infrared light (700-1100nm), may be used for the detection of living body molecule target, because organism blood and to be organized in this wavelength region be relative transparent, thus decrease the difficult problem that background interference in body causes.But the exciting light due to many fluorescent materials is all be positioned at short wavelength region, be so just both not easy to excitation fluorescent material, be more not easy to observe phenomena.Therefore have many researchists to propose to carry out alternative common fluorescent material with near infrared long-afterglow material, thus realize exciting in vitro, the twilight sunset still existed after being expelled in body still can be used for doing biological fluorescent mark.Near-infrared fluorescent marker is positioned at near-infrared region due to its luminescence, and biomolecules does not have luminescence in this light district, there is no the interference that spectra overlapping causes, detection background is lower, near-infrared fluorescent marker can use visible ray or the near ultraviolet excitation of shorter wavelength, the Stokes shift of spectrum is large, and this helps avoid the impact of exciting light scattering thus obtains higher sensitivity.In addition, the composition in biological vital tissue is little to nearly outer photoabsorption, and near infrared light in biological tissues penetration depth is large, and can produce optical signal at deep tissues, and almost not affect tissue itself, this contributes to the information obtaining more organisms.Therefore, near-infrared fluorescent marker becomes when previous study hotspot.Long-afterglow material is used as imaging, can well remove the back end that non-specific imaging spy comes.Long-afterglow material in the past mainly concentrates on visible region, as night vision material.The long-afterglow material development of near infrared region and slowly, and then limit the application of long-afterglow material in bio-imaging.Therefore the development that near infrared long-afterglow material could promote medical imaging, oncotherapy etc. is further greatly developed.
Summary of the invention
In order to overcome the above-mentioned shortcoming of prior art with not enough, the near infrared long after glow luminous material of the perovskite structure that the object of the present invention is to provide a kind of Cr to adulterate, emission band is positioned at 650-850 nanometer, and emission peak is positioned at 760 nanometers, reaches 100 minutes time of persistence.
Another object of the present invention is to the preparation method of the near infrared long after glow luminous material of the perovskite structure providing above-mentioned Cr to adulterate, preparation technology is simple, is easy to megatechnics and promotes.
Object of the present invention is achieved through the following technical solutions:
A near infrared long after glow luminous material for the perovskite structure of Cr doping, body material is ABO
3, described A is Ca, Sr or Ba; Described B is Sn or Ti; The Cr of doping 0.001 ~ 5mol% in described body material
3+.
Also adulterate in described body material the Bi of 0 ~ 20mol%
3+.
Singly adulterate Cr
3+aTiO
3preparation method comprise the following steps:
(1) material is weighed: weigh containing A compound, containing Ti compound, containing Cr compound respectively;
(2) material after being ground in reducing atmosphere 600 ~ 900 DEG C of pre-burnings take out after 1 ~ 3 hour, again grinding after, in reducing atmosphere, fire 2 ~ 5 hours in 1300 ~ 1450 DEG C.
Described reducing atmosphere is be the H of 5% by volume percent
2be 95%N with volume percent
2composition.
Cr
3+and Bi
3+the ATiO of codoped
3preparation method comprise the following steps:
(1) material is weighed: weigh containing A compound, containing Ti compound, containing Cr compound, containing Bi compound respectively;
(2) material after being ground in atmosphere 600 ~ 900 DEG C of pre-burnings take out after 1 ~ 3 hour, again grinding after, fire 2 ~ 5 hours in 1300 ~ 1450 DEG C in atmosphere.
Singly adulterate Cr
3+aSnO
3preparation method comprise the following steps:
(1) material is weighed: weigh containing A compound, containing Sn compound, containing Cr compound respectively;
(2) material takes out after 1 ~ 3 hour in reducing atmosphere 600 ~ 900 DEG C of pre-burnings after being ground, and again after grinding, in reducing atmosphere, fires 2 ~ 5 hours in 1350 ~ 1500 DEG C.
Cr
3+and Bi
3+the ASnO of codoped
3preparation method comprise the following steps:
(1) material is weighed: weigh containing A compound, containing Sn compound, containing Cr compound, containing Bi compound respectively;
(2) material after being ground in atmosphere 600 ~ 900 DEG C of pre-burnings take out after 1 ~ 3 hour, again grinding after, fire 2 ~ 5 hours in 1350 ~ 1500 DEG C in atmosphere.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the near infrared long after glow luminous material of the perovskite structure of Cr doping of the present invention, 3 valency Cr ions are paid attention to widely because the long-persistence luminous performance of its brilliance obtains, and calcium titanate substrate material is widely used in solar cell due to the high carrier mobility speed of itself.But because Cr mainly exists with 4 valency forms in calcium titanate, occupy the octahedral site of Ti atom.Therefore be difficult to obtain the long-persistence luminous of 3 valency Cr, mixing of Bi effectively can stablize 3 valency Cr, increases the content of 3 valency Cr ions, thus effective raising 3 valency Cr's is long-persistence luminous.
(2) the near infrared long after glow luminous material of the perovskite structure of Cr doping of the present invention, Bi ion occupies the crystallographic site of Ca ion, because its non-equivalence substitutes the generation that also can promote defect new in a large number, is conducive to prolongation long-persistence luminous
(3) simple, the cheaper starting materials of drawing materials of preparation method of the present invention, is easy to large-scale promotion.
Accompanying drawing explanation
The twilight sunset spectral curve of the sample that Fig. 1 (a) is prepared for embodiments of the invention 1.
The steady persistence extinction curve figure of the sample that Fig. 1 (b) is prepared for embodiments of the invention 1.
The twilight sunset spectral curve of the sample that Fig. 2 (a) is prepared for embodiments of the invention 2.
The steady persistence extinction curve figure of the sample that Fig. 2 (b) is prepared for embodiments of the invention 2.
The twilight sunset spectral curve of the sample that Fig. 3 (a) is prepared for embodiments of the invention 3.
The steady persistence extinction curve figure of the sample that Fig. 3 (b) is prepared for embodiments of the invention 3.
The twilight sunset spectral curve of the sample that Fig. 4 (a) is prepared for embodiments of the invention 4.
The steady persistence extinction curve figure of the sample that Fig. 4 (b) is prepared for embodiments of the invention 4.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
The list doping Cr of the present embodiment
3+caTiO
3the preparation method of near infrared long after glow luminous material as follows:
According to following composition: matrix is CaTiO
3; Cr
3+doping be 0.001mol%; Take titanium oxide, calcium carbonate, chromic oxide (Cr respectively
2o
3), at reducing atmosphere (5% (volume percent) H after being ground
2+ 95% (volume percent) N
2) 900 DEG C of pre-burnings take out after 3 hours, again after grinding, fire 2 hours in 1450 DEG C.
The steady persistence spectrum of near infrared long after glow luminous material prepared by the present embodiment is as shown in Fig. 1 (a), and under 254 nano-ultraviolet lights, irradiation is after 10 minutes, and interval was tested after 30 seconds, obtained near infrared long-persistence luminous, and glow peak is positioned at 766,780 nanometers.As Fig. 1 (b), the near infrared of monitoring 766 nanometers is long-persistence luminous, and discovery time reaches 100 minutes.Illustrate that this kind of material has excellent near infrared long-persistence luminous.
Embodiment 2
The Cr of the present embodiment
3+and Bi
3+the SrTiO of codoped
3the preparation method of near infrared long after glow luminous material as follows:
According to following composition: matrix is SrTiO
3; Cr
3+doping be 5mol%, Bi
3+doping be 20mol%; Take titanium oxide, Strontium carbonate powder, chromic oxide (Cr respectively
2o
3), bismuth oxide (Bi
2o), after being ground, 600 DEG C of pre-burnings were taken out after 1 hour in atmosphere, again after grinding, fired 5 hours in 1300 DEG C.
The steady persistence spectrum of near infrared long after glow luminous material prepared by the present embodiment is as shown in Fig. 2 (a), and under 254 nano-ultraviolet lights, irradiation is after 10 minutes, and interval was tested after 30 seconds, obtained near infrared long-persistence luminous, and glow peak is positioned at 766 nanometers.As Fig. 2 (b), the near infrared of monitoring 766 nanometers is long-persistence luminous, and discovery time reaches 100 minutes.Illustrate that this kind of material has excellent near infrared long-persistence luminous.
Embodiment 3
The list doping Cr of the present embodiment
3+baSnO
3the preparation method of near infrared long after glow luminous material as follows:
According to following composition: matrix is BaSnO
3; Cr
3+doping be 5mol%; Take stannic oxide, barium carbonate, chromic oxide respectively, at reducing atmosphere (5%H after being ground
2+ 95%N
2) 600 DEG C of pre-burnings take out after 1 hour, again after grinding, fire 5 hours in 1350 DEG C.
The steady persistence spectrum of near infrared long after glow luminous material prepared by the present embodiment is as shown in Fig. 3 (a), and under 254 nano-ultraviolet lights, irradiation is after 10 minutes, and interval was tested after 30 seconds, obtained near infrared long-persistence luminous, and glow peak is positioned at 800 nanometers.As Fig. 3 (b), the near infrared of monitoring 800 nanometers is long-persistence luminous, and discovery time reaches 100 minutes.Illustrate that this kind of material has excellent near infrared long-persistence luminous.
Embodiment 4
The Cr of the present embodiment
3+and Bi
3+the BaSnO of codoped
3the preparation method of near infrared long after glow luminous material as follows:
According to following composition: matrix is BaSnO
3; Cr
3+doping be 0.001mol%, Bi
3+doping be 20mol%; Take stannic oxide, barium carbonate, chromic oxide, bismuth oxide respectively, after being ground, 900 DEG C of pre-burnings were taken out after 3 hours in atmosphere, again after grinding, fired 2 hours in 1500 DEG C.
The steady persistence spectrum of near infrared long after glow luminous material prepared by the present embodiment is as shown in Fig. 4 (a), and under 254 nano-ultraviolet lights, irradiation is after 10 minutes, and interval was tested after 30 seconds, obtained near infrared long-persistence luminous, and glow peak is positioned at 800 nanometers.As Fig. 4 (b), the near infrared of monitoring 800 nanometers is long-persistence luminous, and discovery time reaches 100 minutes.Illustrate that this kind of material has excellent near infrared long-persistence luminous.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not limited by the examples; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. a near infrared long after glow luminous material for the perovskite structure of Cr doping, it is characterized in that, body material is ABO
3, described A is Ca, Sr or Ba; Described B is Sn or Ti; The Cr of doping 0.001 ~ 5mol% in described body material
3+.
2. the near infrared long after glow luminous material of the perovskite structure of Cr doping according to claim 1, is characterized in that, the Bi of the 0 ~ 20mol% that also adulterates in described body material
3+.
3. the preparation method of the near infrared long after glow luminous material of the perovskite structure of Cr doping according to claim 1, it is characterized in that, singly adulterate Cr
3+aTiO
3preparation method comprise the following steps:
(1) material is weighed: weigh containing A compound, containing Ti compound, containing Cr compound respectively;
(2) material after being ground in reducing atmosphere 600 ~ 900 DEG C of pre-burnings take out after 1 ~ 3 hour, again grinding after, in reducing atmosphere, fire 2 ~ 5 hours in 1300 ~ 1450 DEG C.
4. the preparation method of the near infrared long after glow luminous material of the perovskite structure of Cr according to claim 3 doping, is characterized in that, described reducing atmosphere is be the H of 5% by volume percent
2be 95%N with volume percent
2composition.
5. the preparation method of the near infrared long after glow luminous material of the perovskite structure of Cr doping according to claim 1, is characterized in that, Cr
3+and Bi
3+the ATiO of codoped
3preparation method comprise the following steps:
(1) material is weighed: weigh containing A compound, containing Ti compound, containing Cr compound, containing Bi compound respectively;
(2) material after being ground in atmosphere 600 ~ 900 DEG C of pre-burnings take out after 1 ~ 3 hour, again grinding after, fire 2 ~ 5 hours in 1300 ~ 1450 DEG C in atmosphere.
6. the preparation method of the near infrared long after glow luminous material of the perovskite structure of Cr doping according to claim 1, it is characterized in that, singly adulterate Cr
3+aSnO
3preparation method comprise the following steps:
(1) material is weighed: weigh containing A compound, containing Sn compound, containing Cr compound respectively;
(2) material takes out after 1 ~ 3 hour in reducing atmosphere 600 ~ 900 DEG C of pre-burnings after being ground, and again after grinding, in reducing atmosphere, fires 2 ~ 5 hours in 1350 ~ 1500 DEG C.
7. the preparation method of the near infrared long after glow luminous material of the perovskite structure of Cr doping according to claim 6, is characterized in that, Cr
3+and Bi
3+the ASnO of codoped
3preparation method comprise the following steps:
(1) material is weighed: weigh containing A compound, containing Sn compound, containing Cr compound, containing Bi compound respectively;
(2) material after being ground in atmosphere 600 ~ 900 DEG C of pre-burnings take out after 1 ~ 3 hour, again grinding after, fire 2 ~ 5 hours in 1350 ~ 1500 DEG C in atmosphere.
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|---|---|---|---|
| CN201510160378.2A CN104861970B (en) | 2015-04-03 | 2015-04-03 | The near-infrared long after glow luminous material of the perovskite structure of a kind of Cr doping and preparation method |
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| CN104861970B CN104861970B (en) | 2016-07-06 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109294573A (en) * | 2018-11-08 | 2019-02-01 | 华南理工大学 | A kind of matrix near-infrared long lad phosphor and preparation method thereof |
| CN109485090A (en) * | 2018-12-28 | 2019-03-19 | 中国科学院上海硅酸盐研究所 | A kind of adjustable chromium doping barium stannate nano-powder of forbidden bandwidth and preparation method |
| CN109943330A (en) * | 2019-03-25 | 2019-06-28 | 常州工程职业技术学院 | A kind of Cr3+The near-infrared fluorescent powder of activation, preparation method and application |
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| CN102557614A (en) * | 2010-12-15 | 2012-07-11 | 颜欢 | Chromium-doped barium strontium titanate ceramic capacitor material |
| CN103897696A (en) * | 2014-03-31 | 2014-07-02 | 华南理工大学 | Cr-doped nano near infrared long-persistence material and preparation method thereof |
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2015
- 2015-04-03 CN CN201510160378.2A patent/CN104861970B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557614A (en) * | 2010-12-15 | 2012-07-11 | 颜欢 | Chromium-doped barium strontium titanate ceramic capacitor material |
| CN103897696A (en) * | 2014-03-31 | 2014-07-02 | 华南理工大学 | Cr-doped nano near infrared long-persistence material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| L.JASTRABIK ET AL: "Luminescence of Ba0.77Ca0.23TiO3 Cr", 《JOURNAL OF LUMINESCENCE》, vol. 102103, 31 December 2003 (2003-12-31) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109294573A (en) * | 2018-11-08 | 2019-02-01 | 华南理工大学 | A kind of matrix near-infrared long lad phosphor and preparation method thereof |
| CN109485090A (en) * | 2018-12-28 | 2019-03-19 | 中国科学院上海硅酸盐研究所 | A kind of adjustable chromium doping barium stannate nano-powder of forbidden bandwidth and preparation method |
| CN109485090B (en) * | 2018-12-28 | 2021-07-13 | 中国科学院上海硅酸盐研究所 | Chromium-doped barium stannate nano powder with adjustable forbidden bandwidth and preparation method thereof |
| CN109943330A (en) * | 2019-03-25 | 2019-06-28 | 常州工程职业技术学院 | A kind of Cr3+The near-infrared fluorescent powder of activation, preparation method and application |
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| CN104861970B (en) | 2016-07-06 |
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