CN104673312A - Chromium and neodymium co-doped gadolinium gallate near-infrared long-afterglow material and preparation method thereof - Google Patents
Chromium and neodymium co-doped gadolinium gallate near-infrared long-afterglow material and preparation method thereof Download PDFInfo
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- CN104673312A CN104673312A CN201410803569.1A CN201410803569A CN104673312A CN 104673312 A CN104673312 A CN 104673312A CN 201410803569 A CN201410803569 A CN 201410803569A CN 104673312 A CN104673312 A CN 104673312A
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Abstract
The invention discloses a chromium and neodymium co-doped gadolinium gallate near-infrared long-afterglow material. The general structural formula is Gdx-mGay-nO(1.5x+1.5y):nCr, mNd, wherein x is more than or equal to 1 and less than or equal to 3, y is more than or equal to 1 and less than or equal to 7, n is more than or equal to 0.001 and less than or equal to 0.02, and m is more than or equal to 0.001 and less than or equal to 0.02. The invention also discloses a method for preparing the near-infrared long-afterglow material. The near-infrared long-afterglow material disclosed by the invention emits near-infrared long afterglow at the wave band of 650-1400nm, and the emission peaks are respectively positioned at 710nm and 1064nm and have a certain afterglow luminous time.
Description
Technical field
The present invention relates to a kind of near infrared long after glow luminous material, particularly gallic acid gadolinium near infrared long-afterglow material of mixing altogether of a kind of chromium, neodymium and preparation method thereof.
Background technology
Long-persistence luminous phenomenon is commonly called as noctilucence phenomenon, is a kind of by high-energy radiation particularly ultraviolet radiation and still can a kind of optical phenomena of continuous illumination after radiation stops.Since 20 beginning of the century long-persistence luminous phenomenons are found, due to the illumination effect that it is special, the development of long-afterglow material achieves considerable progress.Especially in recent years, along with continuous discovery and the performance raising of new long after glow luminous material, its Application Areas was increasingly extensive, also achieved some breakthroughs to the research of long after glow luminous material and luminescence feature thereof.Achieve royal purple at aluminates system, bluish-green, yellowish green, yellowish-orange is luminous, bluish-green, yellowish green two kinds of long-afterglow materials are wherein the best long-afterglow materials of current luminescent properties.Achieve indigo plant, bluish-green, green, yellowish green, Yellow luminous at silicate systems, and chemical property comparatively aluminates system stablize.The development of red long afterglow material also achieves very much progress, achieves red luminous at present in multiple system.The best red long afterglow material luminosity of performance reaches more than 6 times of CaS class red long afterglow material, and time of persistence reaches 6-8 hour.The applied research of long-afterglow material is also in progress rapidly.This kind of material industrial and agricultural production, military affairs, fire-fighting and people life many in be used widely, as the serial noctilucence products such as luminous paint, luminous printing ink, light-emitting film, luminescent fibre, luminescent ceramic, luminescent plastics can be made, be applied to building decoration, communications and transportation, military installations, fire-fighting emergent and daily necessities etc.
But the luminescence band major part of long-afterglow material rests on visibility region so far, it is fewer that near-infrared luminous long-afterglow material is studied.And long-afterglow material has the performance of its uniqueness, especially at biology through window (650-1400nm), it is long that it has the life-span, low autofluorescence, high s/n ratio, the good characteristics such as dark penetration into tissue.Near infrared long-afterglow material, due to the advantage of its uniqueness, is considered to the most potential replacer of fluorescent marker at biological Second Window.Research near infrared long-afterglow material is for the resolving power improving optical imagery, and weaken light interference effect, the structure and function of analysis of cells, tissue and other complex systems is of great importance.
Summary of the invention
In order to overcome the above-mentioned shortcoming of prior art with not enough, the object of the present invention is to provide a kind of chromium, gallic acid gadolinium near infrared long-afterglow material that neodymium is mixed altogether, its long-persistence luminous wavelength region is positioned at 650nm-1400nm, there are two obvious near infrared emission wave bands, lay respectively near 710nm and 1064nm.
Another object of the present invention is to provide above-mentioned chromium, the preparation method of gallic acid gadolinium near infrared long-afterglow material that neodymium is mixed altogether.
Object of the present invention is achieved through the following technical solutions:
The gallic acid gadolinium near infrared long-afterglow material that chromium, neodymium are mixed altogether, its general structure is Gd
x-mga
y-no
(1.5x+1.5y): nCr, mNd, wherein, 1≤x≤3,1≤y≤7,0.001≤n≤0.02,0.001≤m≤0.02.
The preparation method of the gallic acid gadolinium near infrared long-afterglow material that described chromium, neodymium are mixed altogether, comprises the following steps:
(1) material is weighed: choosing containing gadolinium compound, containing gallium compound, containing chromium cpd, containing neodymium compound is respectively raw material, and weighs;
(2) material takes out after 3 ~ 5 hours 800 ~ 1000 DEG C of pre-burnings after being ground, and again after grinding, fires 3 ~ 5 hours in 1300 ~ 1500 DEG C.
Described is gadolinium sesquioxide, Gadolinium trinitrate or gadolinium fluoride containing gadolinium compound.
Described is gallium oxide, gallium nitrate or gallium fluoride containing gallium compound.
Described is chromic oxide or chromium fluoride containing chromium cpd.
The described compound containing neodymium is Neodymium trioxide or neodymium fluoride.
Compared with prior art, the present invention has the following advantages and beneficial effect:
Singly Nd is mixed in gallic acid gadolinium
3+, the fluorescence of Nd can only be realized, can not steady persistence be realized, and singly mix Cr
3+, the steady persistence near 710nm can only be realized, the near infrared steady persistence of 1064nm can not be realized.And of the present inventionly mix in the gallic acid gadolinium material of Cr and Nd altogether, the near infrared steady persistence of 710nm can be realized, the near infrared steady persistence near 1064nm can also be realized.The near infrared long-afterglow material that the present invention prepares, can launch the near infrared steady persistence of 650-1400nm wave band, its emission peak lays respectively at 710nm and 1064nm, and all possesses certain afterglow time.Material of the present invention two obvious emission band are all near infrared region, more can well for biomarker imaging.
Accompanying drawing explanation
Fig. 1 is near infrared spectroscopy and the excitation spectrum of sample prepared by embodiments of the invention 1.
Fig. 2 is the near infrared steady persistence emmission spectrum of sample prepared by embodiments of the invention 1.
Fig. 3 is the long-persistence luminous extinction curve of near infrared of sample prepared by embodiments of the invention 1.
Fig. 4 is the Visible-to-Near InfaRed steady persistence emmission spectrum of sample prepared by embodiments of the invention 1.
Fig. 5 is the near infrared steady persistence extinction curve of sample prepared by embodiments of the invention 2.
Fig. 6 is the near infrared steady persistence extinction curve of sample prepared by embodiments of the invention 3.
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
According to following composition: GdGa
3o
6: 0.001Cr, 0.001Nd, namely with GdGa
3o
6for matrix, the Nd of Cr and 0.1mol% of doping 0.1mol%; Take gadolinium sesquioxide, gallium oxide, chromic oxide, Neodymium trioxide respectively, take out after 3 hours 1000 DEG C of pre-burnings after being ground, again after grinding, fire 3 hours in 1500 DEG C.
The near-infrared fluorescent spectrum of sample prepared by the present embodiment as shown in Figure 1, under the exciting of 460nm, have issued the luminescence of 1064nm, and this steady persistence is the luminescence of Nd3+.The luminescence of 1064nm correspond to excitation peak as shown in the excitation spectrum of Fig. 1 left side.Fig. 2 show long-afterglow material under sunlight, irradiate 10min after the near infrared steady persistence spectrum of 1 minute, show that this kind of material possesses long afterglow property.Fig. 3 is that sample prepared by the present embodiment irradiates the sunset glow attenuation of monitoring 1064nm after 10 minutes under sunlight, and the material showing the present embodiment possesses the visible steady persistence of certain hour.Fig. 4 is the Visible-to-Near InfaRed steady persistence emmission spectrum of this sample, shows this material and possesses the long-persistence luminous of different-waveband simultaneously.
Embodiment 2
According to following composition: Gd
3ga
5o
12: 0.005Cr, 0.02Nd, namely with Gd
3ga
5o
12for matrix, the Nd of Cr and 2mol% of doping 0.5mol%, takes Gadolinium trinitrate, gallium oxide, chromium fluoride, neodymium fluoride respectively, takes out after being ground 800 DEG C of pre-burnings after 4 hours, again after grinding, fires 4 hours in 1450 DEG C.
Fig. 5 is that sample prepared by the present embodiment irradiates the sunset glow decay spectrum of monitoring 1064nm after 10 minutes under sunlight, and the material showing the present embodiment has the near infrared steady persistence of certain hour.
Embodiment 3
According to following composition: GdGa
7o
12: 0.015Cr, 0.005Nd, namely with GdGa
7o
12matrix, the Nd of Cr and 0.5%mol of doping 1.5%mol; Take gallium nitrate, gallium oxide, chromic oxide, Neodymium trioxide respectively, take out after 5 hours 800 DEG C of pre-burnings after being ground, again after grinding, fire 5 hours in 1500 DEG C.
Fig. 6 is that sample prepared by the present embodiment irradiates the sunset glow decay spectrum of monitoring 1064nm after 10 minutes under sunlight, and the material showing the present embodiment has the near infrared steady persistence of certain hour.
Above-described embodiment is the present invention's preferably embodiment, but embodiments of the present invention are not limited by the examples, as conventional containing gadolinium compound in also can be other containing gadolinium compound; Also can be containing gallium compound that other are conventional containing gallium compound; Also can be containing chromium cpd that other are conventional containing chromium cpd; Compound containing neodymium also can be other conventional compounds containing neodymium; 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 (6)
1. the gallic acid gadolinium near infrared long-afterglow material mixed altogether of chromium, neodymium, it is characterized in that, its general structure is Gd
x-mga
y-no
(1.5x+1.5y): nCr, mNd, wherein, 1≤x≤3,1≤y≤7,0.001≤n≤0.02,0.001≤m≤0.02.
2. the preparation method of gallic acid gadolinium near infrared long-afterglow material that mixes altogether of chromium, neodymium described in claim 1, is characterized in that, comprise the following steps:
(1) material is weighed: choosing containing gadolinium compound, containing gallium compound, containing chromium cpd, containing neodymium compound is respectively raw material, and weighs;
(2) material takes out after 3 ~ 5 hours 800 ~ 1000 DEG C of pre-burnings after being ground, and again after grinding, fires 3 ~ 5 hours in 1300 ~ 1500 DEG C.
3. the preparation method of gallic acid gadolinium near infrared long-afterglow material that mixes altogether of chromium according to claim 2, neodymium, it is characterized in that, described is gadolinium sesquioxide, Gadolinium trinitrate or gadolinium fluoride containing gadolinium compound.
4. the preparation method of gallic acid gadolinium near infrared long-afterglow material that mixes altogether of chromium according to claim 2, neodymium, it is characterized in that, described is gallium oxide, gallium nitrate or gallium fluoride containing gallium compound.
5. the preparation method of gallic acid gadolinium near infrared long-afterglow material that mixes altogether of chromium according to claim 2, neodymium, it is characterized in that, described is chromic oxide or chromium fluoride containing chromium cpd.
6. the preparation method of gallic acid gadolinium near infrared long-afterglow material that mixes altogether of chromium according to claim 2, neodymium, it is characterized in that, the described compound containing neodymium is Neodymium trioxide or neodymium fluoride.
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| CN201410803569.1A CN104673312B (en) | 2014-12-18 | 2014-12-18 | Gallic acid gadolinium near-infrared long-afterglow material that a kind of chromium, neodymium are co-doped with and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111971366A (en) * | 2018-04-23 | 2020-11-20 | 大电株式会社 | Near-infrared light-emitting phosphor, phosphor mixture, light-emitting element, and light-emitting device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120261617A1 (en) * | 2009-09-21 | 2012-10-18 | Unversity Of Georgia Research Foundation, Inc | Near infrared doped phosphors having an alkaline gallate matrix |
| CN103911147A (en) * | 2014-01-13 | 2014-07-09 | 广东工业大学 | Near-infrared long-afterglow fluorescent powder and preparation method thereof |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120261617A1 (en) * | 2009-09-21 | 2012-10-18 | Unversity Of Georgia Research Foundation, Inc | Near infrared doped phosphors having an alkaline gallate matrix |
| CN103911147A (en) * | 2014-01-13 | 2014-07-09 | 广东工业大学 | Near-infrared long-afterglow fluorescent powder and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| M.E.DOROSHENKO等: "Large single crystals of neodymium and chromium co-doped gadolinium gallium garnet for efficient solid state lasers", 《SPIE SOLID STATE LASERS AND NEW LASER MATERIALS》 * |
| 闫武钊: "超长红外长余辉材料研究及其发光机理的探索", 《中国科学技术大学博士学位论文》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111971366A (en) * | 2018-04-23 | 2020-11-20 | 大电株式会社 | Near-infrared light-emitting phosphor, phosphor mixture, light-emitting element, and light-emitting device |
| US11578267B2 (en) | 2018-04-23 | 2023-02-14 | Dyden Corporation | Near-infrared light-emitting phosphor, phosphor mixture, light-emitting element, and light-emitting device |
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| CN104673312B (en) | 2016-10-05 |
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