CN110713830A - Fluorescent material - Google Patents
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- CN110713830A CN110713830A CN201810763730.5A CN201810763730A CN110713830A CN 110713830 A CN110713830 A CN 110713830A CN 201810763730 A CN201810763730 A CN 201810763730A CN 110713830 A CN110713830 A CN 110713830A
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
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- C09K11/684—Chalcogenides with alkaline earth metals
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Abstract
The invention relates to a fluorescent material, which is represented by a chemical formula of Ca3Ga2Ge3‑xSnxO12:yCr3+Wherein x is a number from 0.01 to 0.5 and y is a number from 0.001 to 0.5. By using the fluorescent material of the invention, an infrared emission spectrum with a broadband can be obtained.
Description
Technical Field
The invention relates to a fluorescent material, in particular to a near-infrared fluorescent material.
Background
Near infrared light generally refers to electromagnetic waves having wavelengths between 780nm and 1400 nm. Near infrared light has the advantages of rapidness, accuracy, on-line or remote detection, high penetrating power, high sensitivity to heat sources, non-destructive property and the like, and is widely used for detecting agricultural, fishery and pastoral products in recent years. In addition, it is also applied to industrial fields such as petrochemical industry, environmental protection industry, biomedicine, semiconductor industry, and the like.
Halogen lamps are most commonly used in conjunction with infrared filters to provide near infrared light sources because they are readily available and inexpensive and they provide high intensity, continuous emission of near infrared light. However, the halogen lamp generates a large amount of heat when used for generating the near-infrared light source, and the wavelength of the continuously emitted near-infrared light also varies with time. In addition, the halogen lamp also provides a certain proportion of the wavelength of the emitted light that falls outside the near infrared region, thereby causing a loss of energy.
In view of the above, there is a need for a new near-infrared fluorescent material to solve the above-mentioned problems of using halogen lamps to generate near-infrared light sources.
Disclosure of Invention
The invention aims to overcome the problems of the prior halogen lamp generating a near-infrared light source, namely, a large amount of heat is generated in the process of generating the near-infrared light source by the halogen lamp, and the wavelength of the continuously emitted near-infrared light also changes along with time. In addition, the halogen lamp provides emitted light with a certain proportion of its wavelength outside the near infrared region, thus causing a loss of energy. Therefore, the invention provides a near-infrared fluorescent material which has a broadband (broadband) emission spectrum and is more suitable for practical use.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme.
The fluorescent material provided by the invention has a chemical formula of Ca3Ga2Ge3-xSnxO12:yCr3+Wherein x is a number from 0.01 to 0.5 and y is a number from 0.001 to 0.5.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
The fluorescent material described above, wherein x is greater than or equal to 0.1, but less than or equal to 0.3.
The fluorescent material described above, wherein x is equal to 0.1.
The fluorescent material described above, wherein x is equal to 0.2.
The fluorescent material described above, wherein x is equal to 0.3.
The fluorescent material described above, wherein y is greater than or equal to 0.005 but less than or equal to 0.02.
The fluorescent material described above, wherein the excitation wavelength of the fluorescent material ranges from about 400nm to about 530 nm.
The foregoing fluorescent material, wherein the excitation wavelength range of the fluorescent material has a peak value of about 465 nm.
The fluorescent material, wherein the first emission wavelength range of the fluorescent material is about 650nm to about 850nm, and the first emission wavelength range has a peak value of about 755 nm.
The fluorescent material, wherein the second emission wavelength of the fluorescent material is in a range of about 850nm to about 1150 nm.
The fluorescent material is a near-infrared fluorescent material.
Compared with the prior art, the invention has obvious advantages and beneficial effects. By means of the technical scheme, the fluorescent material can achieve considerable technical progress and practicability, has wide industrial utilization value, and at least has the following advantages:
1. the fluorescent material provided by the invention has a broadband (broadband) emission spectrum, and can improve the emission proportion of near infrared light along with the increase of the doping proportion of Sn in the fluorescent material.
2. The fluorescent material has the characteristics of simple manufacture, convenient use and low cost, and has wide application field.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following preferred embodiments are described in detail with reference to the accompanying drawings.
[ CHEMICAL SPECIFIC CHEMICAL FORMULA ]
Ca3Ga2Ge3-xSnxO12:yCr3+
Wherein x is 0.01-0.5, y is 0.001-0.5
Drawings
FIGS. 1A, 2A and 3A are X-ray diffraction patterns of the fluorescent material of the present invention, illustrating the crystal structure and the purity of the crystal phase of the embodiment of the present invention;
FIGS. 1B, 2B and 3B are fluorescence excitation spectra of the fluorescent material of the present invention with a fixed emission wavelength of 755nm, illustrating the wavelength and intensity of the excitation light according to the embodiment of the present invention;
FIGS. 1C, 2C and 3C are fluorescence emission spectra of the fluorescent material of the present invention, illustrating the wavelength and intensity of the emitted light according to the embodiment of the present invention; and
FIG. 4 is a graph of the fluorescence emission spectra of three examples of the fluorescent material of the present invention of FIGS. 1C, 2C and 3C, comparing the wavelength and intensity of the emitted light of the three examples of the present invention.
Detailed Description
The present invention provides a fluorescent material represented by the chemical formula Ca3Ga2Ge3-xSnxO12:yCr3+Wherein x is a number from 0.01 to 0.5, preferably from 0.03 to 0.3, more preferably from 0.05 to 0.1; and y is a number from 0.001 to 0.5, preferably from 0.01 to 0.3, more preferably from 0.05 to 0.1. In some embodiments, x is greater than or equal to 0.1, but less than or equal to 0.3. In some embodiments, x is equal to 0.1. In some embodiments, x is equal to 0.2. In some embodiments, x is equal to 0.3. In some embodiments, y is greater than or equal to 0.005, but less than or equal to 0.02. The fluorescent material of the present invention has special optical characteristics, which are mainly influenced by the content of Sn in the fluorescent material, such that the fluorescent material of the present invention has an excitation wavelength range of about 400nm to about 530nm, wherein the peak value of the excitation wavelength is about 465 nm. In addition, the excitation of the fluorescent material of the present invention with the excitation light having a wavelength of 465nm is fixed, so that the fluorescent material of the present invention can emit an emission spectrum having a wavelength of more than about 650nm and a wavelength falling in the red and near infrared regions. More specifically, the emission wavelength range may be about 650nm to about 1150nm, wherein in the emission wavelength range of about 650nm to about 850nm, the near infrared light intensity having a peak value of about 755nm, i.e., a wavelength of about 755nm, is the strongest, indicating that the fluorescent material of the present invention is a near infrared fluorescent material.
The present invention will be described in further detail with reference to examples.
Fluorescent material example 1 of the present invention: synthesis of Ca3Ga2Ge2.9Sn0.1O12:0.01Cr3+A fluorescent material.
Calcium carbonate, germanium oxide, gallium oxide, tin dioxide and chromium oxide according to the above chemical formulaProportionally placing into a ball milling tank, and adding a proper amount of ethanol as a medium to assist in mixing. Then, the mixture was ground and mixed by a planetary ball mill for about 8 to 10 hours, and the resulting mixed slurry was dried to obtain a precursor powder. Then, the precursor powder was put into a high-temperature furnace and calcined at a holding temperature of about 1000 ℃ for about 3 hours, and the atmosphere during calcination was air, whereby the phosphor Ca of example 1 was obtained3Ga2Ge2.9Sn0.1O12:0.01Cr3+。
Please refer to fig. 1A, which shows an X-ray diffraction pattern of the fluorescent material of example 1 of the fluorescent material of the present invention. When the molar ratio of Sn is 0.1, the diffraction peak and the known crystal structure (Ca) of the fluorescent material3Ga2Ge3O12) The comparison of standard X-ray diffraction patterns is consistent (ICSD Code:1123), which can confirm that the synthesized fluorescent material is pure phase, and also indicate Sn with the approximate radius of Ge atom, and can effectively replace Ge and smoothly enter Ca in the process of synthesizing the fluorescent material3Ga2Ge3O12Form a solid solution in the crystal lattice and no secondary phase and hetero-phase are generated in the X-ray diffraction spectrum.
FIG. 1B is a graph of the excitation spectrum of the fluorescent material of example 1 of the fluorescent material of the present invention, in which the ordinate is the intensity of the emitted light with an emission peak wavelength of 755nm, and the abscissa is the wavelength of the excitation light. As shown in FIG. 1B, Ca can be excited3Ga2Ge2.9Sn0.1O12:0.01Cr3+The fluorescent material emits excitation light having a wavelength of 755nm in a wavelength range of about 400nm to about 530nm, with a peak wavelength of about 465 nm. That is, the fluorescent material of example 1 of the present invention can be excited by violet light, blue light, cyan light or green light and emit radiation light with a wavelength of 755nm, wherein the intensity of the radiation light with the wavelength of 465nm is the highest when the fluorescent material of example 1 is excited by the blue light with the wavelength of 755 nm.
FIG. 1C is a graph showing the emission spectrum of the fluorescent material of the present invention obtained by exciting the fluorescent material of example 1 with blue light having a wavelength of 465 nm. As shown in fig. 1C, the emitted light may range in wavelength from about 650nm to about 850nm, with a peak wavelength of about 755 nm. That is, the fluorescent material of embodiment 1 of the present invention can emit an emission spectrum having wavelengths in the red and near infrared regions after being excited by blue light with a wavelength of 465nm, wherein the intensity of near infrared light with a wavelength of about 755nm is the strongest, which indicates that the fluorescent material of embodiment 1 of the present invention is a near infrared fluorescent material.
Fluorescent material example 2 of the present invention: synthesis of Ca3Ga2Ge2.8Sn0.2O12:0.01Cr3+A fluorescent material.
Putting calcium carbonate, germanium oxide, gallium oxide, tin dioxide and chromium oxide into a ball milling tank according to the proportion of the chemical formula, and adding a proper amount of ethanol as a medium to assist in mixing. Then, the mixture was ground and mixed by a planetary ball mill for about 8 to 10 hours, and the resulting mixed slurry was dried to obtain a precursor powder. Then, the precursor powder was put into a high-temperature furnace and calcined at a holding temperature of about 1000 ℃ for about 3 hours, and the atmosphere during calcination was air, whereby the phosphor Ca of example 2 was obtained3Ga2Ge2.8Sn0.2O12:0.01Cr3+。
FIG. 2A shows the X-ray diffraction pattern of the phosphor according to example 2 of the present invention. When the molar ratio of Sn is 0.2, the diffraction peak and the known crystal structure (Ca) of the fluorescent material3Ga2Ge3O12) The comparison of standard X-ray diffraction patterns is consistent (ICSD Code:1123), which can confirm that the synthesized fluorescent material is pure phase, and also indicate Sn with the approximate radius of Ge atom, and can effectively replace Ge and smoothly enter Ca in the process of synthesizing the fluorescent material3Ga2Ge3O12Form a solid solution in the crystal lattice and no secondary phase and hetero-phase are generated in the X-ray diffraction spectrum.
FIG. 2B is a graph of the excitation spectrum of the fluorescent material according to example 2 of the present invention, wherein the ordinate is the intensity of the emitted light with an emission peak wavelength of 755nm, and the abscissa is the wavelength of the excitation light. As shown in FIG. 2B, Ca can be excited3Ga2Ge2.8Sn0.2O12:0.01Cr3+The fluorescent material emits excitation light having a wavelength of 755nm in a wavelength range of about 400nm to about 530nm, with a peak wavelength of about 465 nm. That is, the fluorescent material of example 2 of the present invention can be excited by violet light, blue light, cyan light or green light and emit radiation light with a wavelength of 755nm, wherein the intensity of the radiation light with the wavelength of 465nm that excites the fluorescent material of example 2 is highest at the wavelength of 755 nm.
FIG. 2C is a graph showing the emission spectrum of the fluorescent material of the present invention obtained by exciting the fluorescent material of example 2 of the present invention with blue light having a wavelength of 465 nm. As shown in fig. 2C, the emitted light may range in wavelength from about 650nm to about 850nm, with a peak wavelength of about 755 nm. That is, the fluorescent material of embodiment 2 of the present invention can emit an emission spectrum with wavelengths in the red and near infrared regions after being excited by blue light with a wavelength of 465nm, wherein the intensity of near infrared light with a wavelength of about 755nm is the strongest, which indicates that the fluorescent material of embodiment 2 of the present invention is a near infrared fluorescent material.
Fluorescent material example 3 of the present invention: synthesis of Ca3Ga2Ge2.7Sn0.3O12:0.01Cr3+A fluorescent material.
Putting calcium carbonate, germanium oxide, gallium oxide, tin dioxide and chromium oxide into a ball milling tank according to the proportion of the chemical formula, and adding a proper amount of ethanol as a medium to assist in mixing. Then, the mixture was ground and mixed by a planetary ball mill for about 8 to 10 hours, and the resulting mixed slurry was dried to obtain a precursor powder. Then, the precursor powder was put into a high-temperature furnace and calcined at a holding temperature of about 1000 ℃ for about 3 hours, and the atmosphere during calcination was air, whereby the phosphor Ca of example 3 was obtained3Ga2Ge2.7Sn0.3O12:0.01Cr3+。
FIG. 3A is an X-ray diffraction pattern of the fluorescent material of example 3 of the fluorescent material of the present invention. When the molar ratio of Sn is 0.3, the diffraction peak and the known crystal structure (Ca) of the fluorescent material3Ga2Ge3O12) Standard X-ray diffraction pattern ratio ofIn accordance with (ICSD Code:1123), it was confirmed that the synthesized fluorescent material was pure phase, and Sn having a radius close to that of Ge atom was also described, which can effectively replace Ge and smoothly enter Ca during the synthesis of fluorescent material3Ga2Ge3O12Form a solid solution in the crystal lattice and no secondary phase and hetero-phase are generated in the X-ray diffraction spectrum.
FIG. 3B is a graph of the excitation spectrum of the fluorescent material of example 3 of the fluorescent material of the present invention, in which the ordinate represents the intensity of the emitted light with an emission peak wavelength of 755nm, and the abscissa represents the wavelength of the excitation light. As shown in FIG. 3B, Ca can be excited3Ga2Ge2.7Sn0.3O12:0.01Cr3+The fluorescent material emits excitation light having a wavelength of 755nm in a wavelength range of about 400nm to about 530nm, with a peak wavelength of about 465 nm. That is, the fluorescent material according to embodiment 3 of the present invention can be excited by violet light, blue light, cyan light, or green light, and emit radiation light having a wavelength of 755nm, wherein the intensity of the radiation light having a wavelength of 755nm is highest when the fluorescent material according to embodiment 3 is excited by blue light having a wavelength of 465 nm.
FIG. 3C is a graph of the emission spectrum of the fluorescent material of the present invention obtained by exciting the fluorescent material of example 3 with blue light having a wavelength of 465 nm. As shown in fig. 3C, the emitted light may range in wavelength from about 650nm to about 850nm, with a peak wavelength of about 755 nm. That is, the fluorescent material of embodiment 3 of the present invention can emit an emission spectrum with wavelengths in the red and near infrared regions after being excited by blue light with a wavelength of 465nm, wherein the intensity of near infrared light with a wavelength of about 755nm is the strongest, which indicates that the fluorescent material of embodiment 3 of the present invention is a near infrared fluorescent material.
FIG. 4 is a fluorescence emission spectrum of three embodiments of the fluorescent material of the present invention shown in FIG. 1C, FIG. 2C and FIG. 3C, for comparing the wavelength and intensity of the emitted light. It should be particularly emphasized that Ca of example 1 of the present invention3Ga2Ge2.9Sn0.1O12:0.01Cr3+Ca of example 2 of the present invention3Ga2Ge2.8Sn0.2O12:0.01Cr3+And Ca of example 3 of the present invention3Ga2Ge2.7Sn0.3O12:0.01Cr3+The fluorescence emission spectrum is measured under the same environment. As the ratio of Sn doping increases (from 0.01 mol ratio of example 1 to 0.03 mol ratio of example 3), the peak values of the emission wavelengths obtained by exciting the fluorescent material with excitation light having a wavelength of 465nm are all about 755nm, but the full width at half maximum of the emission spectrum gradually widens toward the longer wavelength as the ratio of Sn doping increases. It is noted that in all three examples, the emission spectra show a linear profile above about 850nm, with the intensity of the emission spectra continuing to increase again. Specifically, the emission wavelength range should not only be limited to from about 650nm to about 850nm, but also be broadened to 1150nm according to the analysis of the existing spectrum, wherein the emission wavelength range also includes from about 850nm to about 1150 nm. That is, the ratio of Sn doping in the fluorescent material is increased, so that the wavelength range of the emission spectrum can be expanded, and a broadband (broadband band) near-infrared fluorescent material can be obtained.
The technical innovation of the invention constituted by the above structure has many advantages and indeed has technical progress for the technicians in the same industry nowadays.
Other operable embodiments of the present invention may be modified within the technical field of the present invention as long as they have the most basic knowledge. In the present invention, a patent is claimed for the essential technical solution, and the protection scope of the patent should include all the changes with the technical characteristics.
Claims (11)
1. A fluorescent material characterized in that Ca is represented by the chemical formula3Ga2Ge3-xSnxO12:yCr3+Wherein x is a number from 0.01 to 0.5 and y is a number from 0.001 to 0.5.
2. The phosphor of claim 1, wherein x is greater than or equal to 0.1 and less than or equal to 0.3.
3. A luminescent material as claimed in claim 1, wherein x is equal to 0.1.
4. A luminescent material as claimed in claim 1, wherein x is equal to 0.2.
5. A luminescent material as claimed in claim 1, wherein x is equal to 0.3.
6. The phosphor of claim 2, wherein y is greater than or equal to 0.005 and less than or equal to 0.02.
7. The fluorescent material according to claim 1, wherein the excitation wavelength of the fluorescent material is in the range of 400nm to 530 nm.
8. The fluorescent material of claim 7, wherein the excitation wavelength range has a peak at 465 nm.
9. The fluorescent material of claim 1, wherein the fluorescent material has a first emission wavelength range of 650nm to 850nm, and the first emission wavelength range has a peak value of 755 nm.
10. The phosphor of claim 1, wherein the second emission wavelength range of the phosphor is 850nm to 1150 nm.
11. The phosphor of claim 1, wherein the phosphor is a near infrared phosphor.
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| CN201810763730.5A CN110713830A (en) | 2018-07-12 | 2018-07-12 | Fluorescent material |
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| CN201810763730.5A CN110713830A (en) | 2018-07-12 | 2018-07-12 | Fluorescent material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112552912A (en) * | 2020-12-16 | 2021-03-26 | 江西理工大学 | Novel Cr3+Doped broadband near-infrared fluorescent powder, preparation and application |
| CN115746842A (en) * | 2022-11-01 | 2023-03-07 | 五邑大学 | Fluorescent powder and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104560041A (en) * | 2014-12-18 | 2015-04-29 | 华南理工大学 | Near-infrared long persistence/down-conversion fluorescence bimodal biological imaging material and preparation method thereof |
| CN108231979A (en) * | 2017-01-24 | 2018-06-29 | 江苏博睿光电有限公司 | Infrared L ED light source |
-
2018
- 2018-07-12 CN CN201810763730.5A patent/CN110713830A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104560041A (en) * | 2014-12-18 | 2015-04-29 | 华南理工大学 | Near-infrared long persistence/down-conversion fluorescence bimodal biological imaging material and preparation method thereof |
| CN108231979A (en) * | 2017-01-24 | 2018-06-29 | 江苏博睿光电有限公司 | Infrared L ED light source |
Non-Patent Citations (2)
| Title |
|---|
| HUIHONG LIN ET AL.,: ""Site Occupancy and Near-Infrared Luminescence in Ca3Ga2Ge3O12: Cr3+ Persistent Phosphor"", 《ADV. OPTICAL MATER.》 * |
| TING SONG ET AL.,: ""Enhanced near infrared persistent luminescence of Zn2Ga2.98Ge0.75O8:Cr0.023+ nanoparticles by partial substitution of Ge4+ by Sn4+"", 《RSC ADV.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112552912A (en) * | 2020-12-16 | 2021-03-26 | 江西理工大学 | Novel Cr3+Doped broadband near-infrared fluorescent powder, preparation and application |
| CN115746842A (en) * | 2022-11-01 | 2023-03-07 | 五邑大学 | Fluorescent powder and preparation method and application thereof |
| CN115746842B (en) * | 2022-11-01 | 2023-10-03 | 五邑大学 | Fluorescent powder and preparation method and application thereof |
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Application publication date: 20200121 |