CN112745840B - Near-infrared silicate germanate long-afterglow luminescent material and preparation method thereof - Google Patents
Near-infrared silicate germanate long-afterglow luminescent material and preparation method thereof Download PDFInfo
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- CN112745840B CN112745840B CN202110277041.5A CN202110277041A CN112745840B CN 112745840 B CN112745840 B CN 112745840B CN 202110277041 A CN202110277041 A CN 202110277041A CN 112745840 B CN112745840 B CN 112745840B
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Abstract
The invention discloses a near-infrared silicate germanate long-afterglow luminescent material and a preparation method thereof, wherein the chemical formula of the luminescent material is BaSi 1.5 Ge 2.5‑x O 9 ：xCr 3+ . Weighing the raw materials according to the stoichiometric ratio of the raw materials in the chemical formula, wherein Ba is introduced through carbonate, oxide or nitrate, and Si, ge and Cr are introduced through respective oxide; mixing the raw materials, adding Li 2 CO 3 Fully mixing and grinding to obtain raw material powder; li in the raw material powder 2 CO 3 Is 3% by mass. Preserving heat in nitrogen atmosphere at a certain temperature, cooling to room temperature along with the furnace, and grinding to obtain the near-infrared germanosilicate long-afterglow luminescent material. The preparation method has the advantages of long afterglow time, high intensity, wide spectrum coverage and the like, is simple and convenient, does not discharge waste water and waste gas, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of near-infrared luminescent materials, and relates to Cr 3+ A doped near-infrared long-afterglow luminescent material and a preparation method thereof.
Background
Long persistence luminescence refers to long-term luminescence in the visible or near infrared region of a material that is excited by a light source (visible, ultraviolet, X-ray, etc.). The duration of this light emission varies from a few microseconds to a few days. It is generally believed that this long persistence phenomenon is due to the slow release of electrons trapped by traps under thermal excitation. This phenomenon has been widely used in the fields of safety indication, instrument display, bio-imaging, night vision investigation, and the like. The early long-afterglow luminescent materials are concentrated in a visible region, and the research and the preparation of the early long-afterglow luminescent materials are basically mature, so that the requirements of practical application can be met. However, in the near-infrared luminescence field, the kind of near-infrared long afterglow materials is rare, and the afterglow performance (afterglow intensity and afterglow time) of most materials is not ideal enough, so that the search for new near-infrared long afterglow materials with excellent performance is of great scientific and practical significance.
Disclosure of Invention
The invention aims to provide a near-infrared germanosilicate long-afterglow luminescent material, which has the luminescent wavelength of 650-1200 nm, the emission peak of 800nm and the afterglow time of more than 8 hours.
The invention also aims to provide a preparation method of the near-infrared germanosilicate long-afterglow luminescent material.
In order to realize the purpose, the technical scheme adopted by the invention is as follows: a near-infrared silicon germanate long-afterglow luminescent material with the chemical expression of BaSi 1.5 Ge 2.5-x O 9 ：xCr 3+ Wherein, 0.002 is less than or equal tox≤0.02。
The invention adopts another technical scheme that: the preparation method of the near-infrared germanosilicate long-afterglow luminescent material specifically comprises the following steps:
1) According to the chemical expression BaSi of the long afterglow luminescent material 1.5 Ge 2.5-x O 9 ：xCr 3+ The stoichiometric ratio of the chemical compositions in the process is respectively taken as the following raw materials:
BaCO 3、 BaO or Ba (NO) 3 ) 2 ；
H 2 SiO 3 Or SiO 2 ；
GeO 2 And Cr 2 O 3 ；
Mixing the above materials, adding Li 2 CO 3 The powder is used as a fluxing agent, and the raw material powder is prepared by fully mixing and grinding the powder;
li in raw material powder 2 CO 3 Is 3 percent.
2) Placing the raw material powder in a closed environment with inert atmosphere, heating to 1000-1100 ℃ at a heating rate of 5 ℃/min, roasting for 4-6 h, and cooling to room temperature to obtain a calcined substance;
the inert atmosphere is pure nitrogen with the purity of 99.8 percent or pure argon with the purity of 99.8 percent.
3) And grinding the calcined substance to obtain the near-infrared germanosilicate long-afterglow luminescent material.
The long afterglow luminescent material is excited by ultraviolet light and has ground state 4 A 2 ) Will transition to the conduction band and some will relax to Cr 3+ And produces near infrared emission, some of which are captured by electron traps through the conduction band. After stopping the ultraviolet irradiation, the trapped electrons will return to Cr through the conduction band 3+ Thereby producing a near-infrared long afterglow emission.
The preparation method of the invention has the following advantages:
1) Using Cr 3+ As activator ion, low temperature calcining to obtain the near infrared long afterglow luminescent material which can emit light with the wavelength of 650-1200 nm after being excited by light with the wavelength of 200-400 nm.
2) The preparation method is simple, pollution-free, low in cost and suitable for large-scale industrial production, and does not discharge waste water and waste gas.
3) The prepared long-afterglow luminescent material has long afterglow time, high intensity and wide spectrum coverage.
Drawings
FIG. 1 shows BaSi obtained in example 1 1.5 Ge 2.49 O 9 ：0.01Cr 3+ XRD spectrum of the material.
FIG. 2 shows BaSi obtained in example 1 1.5 Ge 2.49 O 9 ：0.01Cr 3+ Excitation and emission spectra of the material.
FIG. 3 shows BaSi obtained in example 1 1.5 Ge 2.49 O 9 ：0.01Cr 3+ After the material is irradiated under an ultraviolet lamp for 10min, the light source is closed, and after 30min, an afterglow spectrogram is measured.
FIG. 4 shows BaSi obtained in example 1 1.5 Ge 2.49 O 9 ：0.01Cr 3+ After the material is irradiated under an ultraviolet lamp for 10min, a sample afterglow picture shot by a near-infrared camera capable of monitoring near-infrared luminescence is used.
Detailed Description
The invention is described in detail below with reference to the figures and the specific embodiments.
Example 1
According to BaSi 1.5 Ge 2.49 O 9 ：0.01Cr 3+ In a stoichiometric ratio of the formula, 0.23444g of BaCO was weighed 3 0.30956g of GeO 2 0.13917g of H 2 SiO 3 0.00090g of Cr 2 O 3 After mixing, 0.02116g of Li is added 2 CO 3 Fully mixing and grinding the powder to obtain raw material powder, transferring the raw material powder to an alumina crucible, heating the raw material powder to 1050 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, preserving the heat for 4 hours, cooling the raw material powder to room temperature along with a furnace to obtain a calcined substance, and grinding the calcined substance to obtain the near-infrared long afterglow luminescent material BaSi 1.5 Ge 2.49 O 9 ：0.01Cr 3+ 。
FIG. 1 is an X-ray diffraction (XRD) pattern of the material obtained in example 1, which confirmed that the material was BaSi 1.5 Ge 2.5 O 9 Single phase samples. FIG. 2 is a graph showing the excitation spectrum and the emission spectrum of the material obtained in example 1, and it can be seen that the material obtained has an emission wavelength ranging from 650nm to 1200nm and an emission peak at about 810 nm, which is attributed to Cr 3+ Indicating that the material is capable of emitting light in the near infrared region upon excitation by a suitable light source. Fig. 3 is a graph of the afterglow spectrum of the material prepared in example 1 after the ultraviolet lamp is turned off for 10min and the light source is turned off for 30s, which shows that the afterglow spectrum of the prepared material is partially different from the peak position and shape of the emission spectrum due to different electron transport processes of photoluminescence and long afterglow. The afterglow wavelength range is 650 nm-910 nm, the emission peak is about 690nm and 780nm respectively, which shows that the prepared material has near-infrared long afterglow luminescence property. FIG. 4 is a afterglow luminescence image of the sample obtained from the material obtained in example 1, which is taken by a near-infrared camera capable of observing near-infrared luminescence after the material is irradiated by an ultraviolet lamp for 10min, and it can be seen that the prepared sample still has luminescence phenomenon within 8h after the excitation is stopped, which indicates that the near-infrared afterglow time of the sample is above 8 h.
Example 2
According to BaSi 1.5 Ge 2.498 O 9 ：0.002Cr 3+ In a stoichiometric ratio of the formula, 0.23444g of BaCO was weighed 3 、0.31053g GeO 2 、0.13917g H 2 SiO 3 And 0.00018g of Cr 2 O 3 After mixing, 0.02116g of Li is added 2 CO 3 Fully mixing and grinding the powder to obtain raw material powder; transferring to an alumina crucible, heating to 1000 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, preserving heat for 5h, cooling to room temperature along with the furnace to obtain a calcined substance, grinding to obtain the near-infrared long afterglow luminescent material BaSi 1.5 Ge 2.498 O 9 ：0.002Cr 3+ 。
The long afterglow luminescent material prepared in the embodiment 2 has the luminescent wavelength range of 650 nm-1200 nm, the emission peak is about 810 nm, and the afterglow time is more than 8 h.
Example 3
According to BaSi 1.5 Ge 2.494 O 9 ：0.006Cr 3+ In a stoichiometric ratio of the formula, 0.23444g of BaCO was weighed 3 0.31003g of GeO 2 0.13917g of H 2 SiO 3 And 0.00054g of Cr 2 O 3 After mixing, 0.02116g of Li is added 2 CO 3 Fully mixing and grinding the powder to obtain raw material powder; transferring to an alumina crucible, heating to 1100 deg.C at a heating rate of 5 deg.C/min in argon atmosphere, holding for 6h, cooling to room temperature with the furnace to obtain calcined substance, grinding to obtain near-infrared long afterglow luminescent material BaSi 1.5 Ge 2.494 O 9 ：0.006Cr 3+ 。
The long-afterglow luminescent material prepared in the embodiment 3 has the luminescent wavelength range of 650nm to 1200nm, the emission peak is about 810 nm, and the afterglow time is more than 8 h.
Example 4
According to BaSi 1.5 Ge 2.485 O 9 ：0.015Cr 3+ In a stoichiometric ratio of the formula, 0.23444g of BaCO was weighed 3 0.30891g of GeO 2 0.13917g of H 2 SiO 3 And 0.00135g of Cr 2 O 3 After mixing, 0.02116g of Li is added 2 CO 3 Fully mixing and grinding the powder to obtain raw material powder; transferring to an alumina crucible, and heating to 105 deg.C at a temperature rise rate of 5 deg.C/min in nitrogen atmosphereKeeping the temperature at 0 ℃ for 4h, cooling to room temperature along with the furnace, grinding the calcined product to obtain the near-infrared long-afterglow luminescent material BaSi 1.5 Ge 2.485 O 9 ：0.015Cr 3+ 。
The long-afterglow luminescent material prepared in the embodiment 4 has the luminescent wavelength range of 650nm to 1200nm, the emission peak is about 810 nm, and the afterglow time is more than 8 h.
Example 5
According to BaSi 1.5 Ge 2.48 O 9 ：0.02Cr 3+ In a stoichiometric ratio of the formula, 0.23444g of BaCO was weighed 3 0.30829g of GeO 2 0.13917g of H 2 SiO 3 And 0.00181g of Cr 2 O 3 After mixing, 0.02116g of Li is added 2 CO 3 Fully mixing and grinding the powder to obtain raw material powder; transferring to an alumina crucible, heating to 1050 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, keeping the temperature for 4 hours, cooling to room temperature along with the furnace to obtain a calcined substance, and grinding to obtain the near-infrared long afterglow luminescent material BaSi 1.5 Ge 2.48 O 9 ：0.02Cr 3+ 。
The long-afterglow luminescent material prepared in the embodiment 5 has the luminescent wavelength range of 650nm to 1200nm, the emission peak is about 810 nm, and the afterglow time is more than 8 h.
Claims (4)
1. The near infrared silicon germanate long afterglow luminescent material is characterized in that the chemical formula of the long afterglow luminescent material is BaSi 1.5 Ge 2.5-x O 9 ：xCr 3+ Wherein 0.002 is less than or equal tox≤0.02。
2. A method for preparing the near-infrared germanosilicate long-afterglow luminescent material of claim 1, comprising the following steps:
1) According to the chemical formula BaSi 1.5 Ge 2.5-x O 9 ：xCr 3+ The stoichiometric ratio of the raw materials in the process is that the raw materials are weighed respectively, and the following raw materials are taken respectively:
BaCO 3、 BaO or Ba (NO) 3 ) 2 ；
H 2 SiO 3 Or SiO 2 ；
GeO 2 And Cr 2 O 3 ；
2) Mixing the above raw materials, and adding Li 2 CO 3 Fully mixing and grinding to obtain raw material powder; placing the mixture in an environment with inert atmosphere, heating to 1000-1100 ℃, roasting for 4-6 hours, cooling to room temperature along with the furnace, and grinding to obtain the near-infrared germanosilicate long-afterglow luminescent material.
3. The method for preparing the near-infrared germanosilicate long-afterglow luminescent material as claimed in claim 2, wherein in the step 2), the inert atmosphere is pure nitrogen or pure argon.
4. The method for preparing a near infrared germanosilicate long-afterglow luminescent material as claimed in claim 2, wherein in the step 2), the temperature is raised to 1000 to 1100 ℃ at a temperature raising rate of 5 ℃/min.
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| CN110003893A (en) * | 2019-04-08 | 2019-07-12 | 北京科技大学 | A kind of yellow-orange long after glow luminous material of SiGe hydrochlorate and preparation method |
| CN110257064A (en) * | 2019-07-15 | 2019-09-20 | 兰州大学 | Chromium ion-doped germanium silicate near-infrared long after glow luminous material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110003893A (en) * | 2019-04-08 | 2019-07-12 | 北京科技大学 | A kind of yellow-orange long after glow luminous material of SiGe hydrochlorate and preparation method |
| CN110257064A (en) * | 2019-07-15 | 2019-09-20 | 兰州大学 | Chromium ion-doped germanium silicate near-infrared long after glow luminous material and preparation method thereof |
Non-Patent Citations (2)
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| A High Efficiency Trivalent Chromium-Doped Near-Infrared-Emitting Phosphor and Its NIR Spectroscopy Application;Zhou Yunpeng;《ACS Sustainable Chemistry&Engineering》;20210214;全文 * |
| Spectroscopic and structural properties of Cr3+ ions in lead niobium germanosilicate glasses;T. Narendrudu;《Journal of Luminescence》;20161110;全文 * |
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