CN104861970B - The near-infrared long after glow luminous material of the perovskite structure of a kind of Cr doping and preparation method - Google Patents
The near-infrared long after glow luminous material of the perovskite structure of a kind of Cr doping and preparation method Download PDFInfo
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Abstract
The invention discloses the near-infrared long after glow luminous material of the perovskite structure of a kind of Cr doping, matrix material is ABO3, described A is Ca, Sr or Ba；Described B is Sn or Ti；The Cr of doping 0.001～5mol% in described matrix material3+.The preparation method that the invention also discloses above-mentioned near-infrared long after glow luminous material, weighs material including (1): weigh respectively containing A compound, containing Ti compound, containing Cr compound；(2) take out after pre-burning in going back air/reducing atmosphere after the ground mixing of material, after regrinding, in firing hour in air/reducing atmosphere.The near-infrared long after glow luminous material of the present invention is launched band and is positioned at 650-850 nanometer, and emission peak is positioned at 760 nanometers, and persistence was up to 100 minutes；The preparation method technique of the present invention is simple, low in raw material price, it is easy to megatechnics is promoted.
Description
Technical field
The present invention relates to nm near-infrared long after glow luminous material, particularly to near-infrared long after glow luminous material and the preparation method of a kind of Cr perovskite structure adulterated.
Background technology
Optical imagery is using photon as information source, and the domain variability representing a quick extension is applied directly to pharmacology, molecular cytobiology and diagnostics.But this technology yet suffers from many limitation, the tissue autofluorescence produced during particularly in internal illumination and weak tissue permeability under shortwave excitation light irradiation.In order to overcome these difficulties, scientist have studied a series of phosphor, launch just 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 wave-length coverage be relative transparent, thus decreasing the difficult problem that internal ambient interferences causes.But owing to the exciting light of many fluorescent materials is all in short wavelength region, thus both it was not easy to excite fluorescent material, more be not easy to observe phenomenon.Therefore there are many research worker to propose to substitute common fluorescent material with near infrared long-afterglow material, thus realizing exciting in vitro, being expelled to the internal twilight sunset yet suffered from afterwards and still can be used to do the fluorescent labeling of biology.Near-infrared fluorescent label is positioned at near-infrared region due to its luminescence, and biomolecule does not have luminescence in this light district, there is no the interference that spectra overlapping causes, detection background is relatively low, near-infrared fluorescent label can use visible ray or the near ultraviolet excitation of shorter wavelength, the Stokes shift of spectrum is big, and this helps avoid the impact of exciting light scattering thus obtaining higher sensitivity.Additionally, nearly outer light is absorbed seldom by the composition in biological vital tissue, near infrared light penetration depth in biological tissues is big, it is possible to produce optical signal at deep tissues, and on tissue itself almost without impact, this information contributing to obtaining more organism.Therefore, near-infrared fluorescent label becomes when previous study hotspot.Long-afterglow material is used as imaging, it is possible to well remove the back end that non-specific imaging spy comes.Long-afterglow material in the past is concentrated mainly on visible region, as night vision material.The long-afterglow material of near infrared region develops and slow, and then limits long-afterglow material application in bio-imaging.Therefore greatly develop near-infrared long-afterglow material and could promote the development of medical imaging, oncotherapy etc. further.
Summary of the invention
In order to overcome disadvantages mentioned above and the deficiency of prior art, it is an object of the invention to provide the near-infrared long after glow luminous material of the perovskite structure of a kind of Cr doping, launch band and be positioned at 650-850 nanometer, emission peak is positioned at 760 nanometers, and persistence was up to 100 minutes.
Another object of the present invention is to the preparation method providing the near-infrared long after glow luminous material of the above-mentioned Cr perovskite structure adulterated, preparation technology is simple, it is easy to megatechnics is promoted.
The purpose of the present invention is achieved through the following technical solutions:
The near-infrared long after glow luminous material of the perovskite structure of a kind of Cr doping, matrix material is ABO3, described A is Ca, Sr or Ba；Described B is Sn or Ti；The Cr of doping 0.001～5mol% in described matrix material3+。
Also adulterate in described matrix material the Bi of 0～20mol%3+。
Singly adulterate Cr3+ATiO3Preparation method comprise the following steps:
(1) material is weighed: weigh respectively containing A compound, containing Ti compound, containing Cr compound；
(2) after the ground mixing of material, in reducing atmosphere, 600～900 DEG C of pre-burnings were taken out after 1～3 hour, after regrinding, fired 2～5 hours in 1300～1450 DEG C in reducing atmosphere.
Described reducing atmosphere is be the H of 5% by percent by volume2It is 95%N with percent by volume2Composition.
Cr3+And Bi3+The ATiO of codope3Preparation method comprise the following steps:
(1) material is weighed: weigh respectively containing A compound, containing Ti compound, containing Cr compound, containing Bi compound；
(2) after the ground mixing of material, 600～900 DEG C of pre-burnings were taken out after 1～3 hour in atmosphere, after regrinding, fired 2～5 hours in 1300～1450 DEG C in atmosphere.
Singly adulterate Cr3+ASnO3Preparation method comprise the following steps:
(1) material is weighed: weigh respectively containing A compound, containing Sn compound, containing Cr compound；
(2) take out after 600～900 DEG C of pre-burnings of reducing atmosphere 1～3 hour after the ground mixing of material, after regrinding, in reducing atmosphere, fire 2～5 hours in 1350～1500 DEG C.
Cr3+And Bi3+The ASnO of codope3Preparation method comprise the following steps:
(1) material is weighed: weigh respectively containing A compound, containing Sn compound, containing Cr compound, containing Bi compound；
(2) after the ground mixing of material, 600～900 DEG C of pre-burnings were taken out after 1～3 hour in atmosphere, after regrinding, fired 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 the Cr doping of the present invention, 3 valency Cr ions are paid attention to widely owing to the long-persistence luminous performance of its brilliance obtains, and calcium titanate host material is widely used in solaode due to the high carrier mobility speed of itself.But exist with 4 valency forms owing to Cr is main in calcium titanate, occupy the octahedral site of Ti atom.Therefore hardly resulting in the long-persistence luminous of 3 valency Cr, 3 valency Cr can be effectively stablized in mixing of Bi, increase the content of 3 valency Cr ions, thus effectively improving the long-persistence luminous of 3 valency Cr.
(2) the near-infrared long after glow luminous material of the perovskite structure of the Cr doping of the present invention, Bi ion occupies the lattice position of Ca ion, also is able to promote the generation of defect new in a large number owing to its non-equivalence substitutes, and is conducive to prolongation long-persistence luminous.
(3) preparation method of the present invention is simple, cheaper starting materials of drawing materials, it 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 long afterglow attenuation 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 long afterglow attenuation 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 long afterglow attenuation 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 long afterglow attenuation curve figure of the sample that Fig. 4 (b) is prepared for embodiments of the invention 4.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
The list doping Cr of the present embodiment3+CaTiO3The preparation method of near-infrared long after glow luminous material as follows:
According to following component: matrix is CaTiO3；Cr3+Doping be 0.001mol%；Weigh titanium oxide, calcium carbonate, chromium oxide (Cr respectively2O3), at reducing atmosphere (5% (percent by volume) H after ground mixing2+ 95% (percent by volume) N2) 900 DEG C of pre-burnings take out after 3 hours, after regrinding, fire 2 hours in 1450 DEG C.
The long afterglow spectrum of near-infrared long after glow luminous material prepared by the present embodiment is such 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.Such as Fig. 1 (b), the near-infrared monitoring 766 nanometers was long-persistence luminous, it has been found that for up to 100 minutes.Illustrate that this kind of material has excellent near-infrared long-persistence luminous.
Embodiment 2
The Cr of the present embodiment3+And Bi3+The SrTiO of codope3The preparation method of near-infrared long after glow luminous material as follows:
According to following component: matrix is SrTiO3；Cr3+Doping be 5mol%, Bi3+Doping be 20mol%；Weigh titanium oxide, strontium carbonate, chromium oxide (Cr respectively2O3), bismuth oxide (Bi2O), after ground mixing, 600 DEG C of pre-burnings were taken out after 1 hour in atmosphere, after regrinding, fired 5 hours in 1300 DEG C.
The long afterglow spectrum of near-infrared long after glow luminous material prepared by the present embodiment is such 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.Such as Fig. 2 (b), the near-infrared monitoring 766 nanometers was long-persistence luminous, it has been found that for up to 100 minutes.Illustrate that this kind of material has excellent near-infrared long-persistence luminous.
Embodiment 3
The list doping Cr of the present embodiment3+BaSnO3The preparation method of near-infrared long after glow luminous material as follows:
According to following component: matrix is BaSnO3；Cr3+Doping be 5mol%；Weigh stannum oxide, brium carbonate, chromium oxide respectively, at reducing atmosphere (5%H after ground mixing2+ 95%N2) 600 DEG C of pre-burnings take out after 1 hour, after regrinding, fire 5 hours in 1350 DEG C.
The long afterglow spectrum of near-infrared long after glow luminous material prepared by the present embodiment is such 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.Such as Fig. 3 (b), the near-infrared monitoring 800 nanometers was long-persistence luminous, it has been found that for up to 100 minutes.Illustrate that this kind of material has excellent near-infrared long-persistence luminous.
Embodiment 4
The Cr of the present embodiment3+And Bi3+The BaSnO of codope3The preparation method of near-infrared long after glow luminous material as follows:
According to following component: matrix is BaSnO3；Cr3+Doping be 0.001mol%, Bi3+Doping be 20mol%；Weighing stannum oxide, brium carbonate, chromium oxide, bismuth oxide respectively, after ground mixing, 900 DEG C of pre-burnings were taken out after 3 hours in atmosphere, after regrinding, fired 2 hours in 1500 DEG C.
The long afterglow spectrum of near-infrared long after glow luminous material prepared by the present embodiment is such 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.Such as Fig. 4 (b), the near-infrared monitoring 800 nanometers was long-persistence luminous, it has been found that for up to 100 minutes.Illustrate that this kind of material has excellent near-infrared long-persistence luminous.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted by the embodiments; the change made under other any spirit without departing from the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (3)
1. the near-infrared long after glow luminous material of the perovskite structure of a Cr doping, it is characterised in that matrix material is ABO3, described A is Ca, Sr or Ba；Described B is Sn or Ti；The Cr of doping 0.001～5mol% in described matrix material3+, the Bi of 20mol%3+。
2. the preparation method of the near-infrared long after glow luminous material of the perovskite structure of the Cr doping described in claim 1, it is characterised in that Cr3+And Bi3+The ATiO of codope3Preparation method comprise the following steps:
(1) material is weighed: weigh respectively containing A compound, containing Ti compound, containing Cr compound, containing Bi compound；
(2) after the ground mixing of material, 600～900 DEG C of pre-burnings were taken out after 1～3 hour in atmosphere, after regrinding, fired 2～5 hours in 1300～1450 DEG C in atmosphere.
3. the preparation method of the near-infrared long after glow luminous material of the perovskite structure of Cr according to claim 1 doping, it is characterised in that Cr3+And Bi3+The ASnO of codope3Preparation method comprise the following steps:
(1) material is weighed: weigh respectively containing A compound, containing Sn compound, containing Cr compound, containing Bi compound；
(2) after the ground mixing of material, 600～900 DEG C of pre-burnings were taken out after 1～3 hour in atmosphere, after regrinding, fired 2～5 hours in 1350～1500 DEG C in atmosphere.
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| 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 |
| CN109943330B (en) * | 2019-03-25 | 2021-05-07 | 常州工程职业技术学院 | Cr (chromium)3+Activated near-infrared fluorescent powder, 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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| 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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| Title |
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| Luminescence of Ba0.77Ca0.23TiO3 Cr;L.Jastrabik et al;《JOURNAL OF LUMINESCENCE》;20031231;第102-103卷;第657-662页 * |
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