CN110713830A - Fluorescent material - Google Patents

Abstract

The invention relates to a fluorescent material, which is represented by a chemical formula of Ca₃Ga₂Ge_3‑xSn_xO₁₂: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

fluorescent material

technical field

The present invention relates to a fluorescent material, in particular to a near-infrared light fluorescent material.

Background technique

Near-infrared light generally refers to electromagnetic waves with wavelengths ranging from 780nm to 1400nm. Due to the advantages of fast, accurate, online or long-distance detection, high penetration, high sensitivity to heat sources, and non-destructive detection, near-infrared light has been widely used in the detection of agricultural, fishery, and animal husbandry products in recent years. In addition, it is also used in industrial fields such as petrochemical industry, environmental protection industry, biomedicine, semiconductor industry and so on.

Because halogen lamps are readily available and inexpensive, and can provide high-intensity continuous emission of near-infrared light, they are most often used with infrared filters to provide near-infrared light sources. However, when the halogen lamp is used to generate a near-infrared light source, a large amount of heat is generated, and the wavelength of the continuously emitted near-infrared light also varies with time. In addition, a certain proportion of the wavelength of the emitted light provided by the halogen lamp falls outside the near-infrared light region, thus causing energy loss.

In view of this, a brand-new near-infrared fluorescent material is urgently needed to solve the above-mentioned problems of using a halogen lamp to generate a near-infrared light source.

SUMMARY OF THE INVENTION

The purpose of the present invention is to overcome the problems faced by the existing halogen lamps to generate near-infrared light sources, that is, in the process of using the halogen lamps to generate near-infrared light sources, a large amount of heat will be generated, and the wavelength of the continuously emitted near-infrared light will will also change over time. In addition, a certain proportion of the wavelength of the emitted light provided by the halogen lamp falls outside the near-infrared region, thus causing energy loss. Therefore, the present invention proposes a near-infrared light fluorescent material, and the near-infrared light fluorescent material of the present invention has a broad band emission spectrum, which is more suitable for practical use.

The purpose of the present invention and the solution to its technical problems are achieved by adopting the following technical solutions.

The fluorescent material proposed according to the present invention is represented by the chemical formula Ca ₃ Ga ₂ Ge _3-x Sn _x O ₁₂ :yCr ³⁺ , wherein x is a value from 0.01 to 0.5, and y is a value from 0.001 to 0.5.

The purpose of the present invention and the solution to its technical problems can be further achieved by adopting the following technical measures.

The aforementioned fluorescent material, wherein x is greater than or equal to 0.1, but less than or equal to 0.3.

The aforementioned fluorescent material, wherein x is equal to 0.1.

The aforementioned fluorescent material, wherein x is equal to 0.2.

The aforementioned fluorescent material, wherein x is equal to 0.3.

The aforementioned fluorescent material, wherein y is greater than or equal to 0.005, but less than or equal to 0.02.

The aforementioned fluorescent material, wherein the excitation wavelength of the fluorescent material ranges from about 400 nm to about 530 nm.

The aforementioned fluorescent material, wherein the excitation wavelength range of the fluorescent material has a peak value of about 465 nm.

The aforementioned fluorescent material, wherein the first emission wavelength range of the fluorescent material is about 650 nm to about 850 nm, and the first emission wavelength range has a peak value of about 755 nm.

The aforementioned fluorescent material, wherein the second emission wavelength of the fluorescent material ranges from about 850 nm to about 1150 nm.

The aforementioned fluorescent material, wherein the fluorescent material is a near-infrared light fluorescent material.

Compared with the prior art, the present invention has obvious advantages and beneficial effects. By means of the above technical solutions, the fluorescent material of the present invention can achieve considerable technical progress and practicability, and has extensive industrial value, and at least has the following advantages:

1. The fluorescent material of the present invention provides a near-infrared light fluorescent material with a broad band emission spectrum, and with the increase of Sn doping ratio in the fluorescent material of the present invention, the emission ratio of near-infrared light can be increased.

2. The fluorescent material of the present invention has the characteristics of simple manufacture, convenient use and low cost, and has a wide range of application fields.

The above description is only an overview of the technical solutions of the present invention, in order to be able to understand the technical means of the present invention more clearly, it can be implemented according to the content of the description, and in order to make the above and other purposes, features and advantages of the present invention more obvious and easy to understand , the following specific preferred embodiments, and in conjunction with the accompanying drawings, are described in detail as follows.

【Characteristic chemical formula】

Ca ₃ Ga ₂ Ge _3-x Sn _x O ₁₂ :yCr ³⁺

Among them, x=0.01-0.5, y=0.001-0.5

Description of drawings

1A, FIG. 2A and FIG. 3A are X-ray diffraction patterns of the fluorescent material of the present invention, which are used to illustrate the crystal structure and crystal phase purity of the embodiment of the present invention;

1B, FIG. 2B and FIG. 3B are fluorescence excitation spectrum diagrams with a fixed emission wavelength of 755 nm of the fluorescent material of the present invention, which are used to illustrate the excitation light wavelength and intensity of the embodiment of the present invention;

1C, FIG. 2C and FIG. 3C are fluorescence emission spectrum diagrams of the fluorescent material of the present invention, which are used to illustrate the wavelength and intensity of the emitted light in the embodiment of the present invention; and

4 is a fluorescence emission spectrum diagram of the three embodiments of the fluorescent material of the present invention shown in FIGS. 1C , 2C and 3C , for comparing the wavelength and intensity of the emitted light of the three embodiments of the present invention.

Detailed ways

The present invention provides a fluorescent material, which can be represented by the chemical formula Ca ₃ Ga ₂ Ge _3-x Sn _x O ₁₂ :yCr ³⁺ , wherein x is a value of 0.01 to 0.5, preferably a value of 0.03 to 0.3, more preferably A value of 0.05 to 0.1; and y is a value of 0.001 to 0.5, preferably a value of 0.01 to 0.3, more preferably a value of 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 properties, which are mainly affected by the Sn content in the fluorescent material, so that the fluorescent material of the present invention has an excitation wavelength range of about 400 nm to about 530 nm, wherein the peak of the excitation wavelength is about 465 nm. In addition, the fluorescent material of the present invention can be excited by the excitation light with a light wavelength of 465 nm, so that the fluorescent material of the present invention can emit an emission spectrum with a wavelength greater than about 650 nm and a wavelength in the red light and near-infrared light range. More specifically, the emission light wavelength may range from about 650 nm to about 1150 nm, wherein in the emission wavelength range of about 650 nm to about 850 nm, the near-infrared light having a peak value of about 755 nm, that is, the wavelength of about 755 nm, has the highest intensity of near-infrared light. Strong, indicating that the fluorescent material of the present invention is a near-infrared light fluorescent material.

The present invention will be described in further detail below in conjunction with the embodiments.

Example 1 of the fluorescent material of the present invention: Synthesis of a Ca ₃ Ga ₂ Ge _2.9 Sn _0.1 O ₁₂ :0.01Cr ³⁺ fluorescent material.

Put calcium carbonate, germanium oxide, gallium oxide, tin dioxide and chromium trioxide into a ball mill according to the ratio of the above chemical formula, and add an appropriate amount of ethanol as a medium to assist mixing. Then, the mixture is ground and mixed with a planetary ball mill for about 8 to 10 hours, and the obtained mixed slurry is dried to obtain a precursor powder. Then, the above-mentioned precursor powder was placed in a high-temperature furnace, and calcined at a temperature of about 1000° C. for about 3 hours. The ambient gas during calcination was air, and the fluorescent material Ca ₃ Ga ₂ Ge of Example 1 was prepared. _2.9 Sn _0.1 O ₁₂ : 0.01Cr ³⁺ .

Please refer to FIG. 1A , which is an X-ray diffraction pattern of the fluorescent material of Embodiment 1 of the present invention. When the molar ratio of Sn is 0.1, the diffraction peak of the fluorescent material is consistent with the standard X-ray diffraction pattern of the known crystal structure (Ca ₃ Ga ₂ Ge ₃ O ₁₂ ) (ICSD Code: 1123) , it can be confirmed that the synthesized fluorescent material is pure phase, and it also shows that Sn with a similar atomic radius to Ge can effectively replace Ge in the process of synthesizing fluorescent materials, and smoothly enter the lattice of Ca ₃ Ga ₂ Ge ₃ O ₁₂ to form It is a solid solution, and there is no secondary phase and impurity phase in the X-ray diffraction pattern.

Please refer to FIG. 1B , which is an excitation spectrum diagram of the fluorescent material of Example 1 of the fluorescent material of the present invention, wherein the ordinate is the intensity of the emission light with the emission peak wavelength of 755 nm, and the abscissa is the wavelength of the excitation light. As shown in FIG. 1B , the Ca ₃ Ga ₂ Ge _2.9 Sn _0.1 O ₁₂ :0.01Cr ³⁺ fluorescent material can be excited to emit excitation light with a wavelength of 755 nm in a wavelength range of about 400 nm to about 530 nm, with a peak wavelength of about 465 nm. That is to say, the fluorescent material of Example 1 of the present invention can be excited by violet light, blue light, cyan light or green light, and emits emission light with a wavelength of 755 nm, wherein the fluorescent material of Example 1 is excited by blue light with a wavelength of 465 nm , the intensity of the emitted light at the wavelength of 755nm is the highest.

Please refer to FIG. 1C , which is an emission spectrum of the fluorescent material of the present invention obtained by exciting the fluorescent material of Example 1 of the present invention with blue light with a wavelength of 465 nm. As shown in FIG. 1C, the wavelength of the emitted light may range from about 650 nm to about 850 nm, with a peak wavelength of about 755 nm. That is to say, the fluorescent material of Example 1 of the present invention, after being excited by blue light with a wavelength of 465 nm, can emit a radiation spectrum with a wavelength in the red light and near-infrared light range, wherein the near-infrared light with a wavelength of about 755 nm is used. The light intensity is the strongest, indicating that the fluorescent material of Example 1 of the present invention is a near-infrared fluorescent material.

Example 2 of the fluorescent material of the present invention: Synthesis of Ca ₃ Ga ₂ Ge _2.8 Sn _0.2 O ₁₂ : 0.01Cr ³⁺ fluorescent material.

Put calcium carbonate, germanium oxide, gallium oxide, tin dioxide and chromium trioxide into a ball mill according to the ratio of the above chemical formula, and add an appropriate amount of ethanol as a medium to assist mixing. Then, the mixture is ground and mixed with a planetary ball mill for about 8 to 10 hours, and the obtained mixed slurry is dried to obtain a precursor powder. Then, the above-mentioned precursor powder was placed in a high-temperature furnace, and calcined at a temperature of about 1000° C. for about 3 hours. The ambient gas during calcination was air, and the fluorescent material Ca ₃ Ga ₂ Ge of Example 2 was prepared. _2.8 Sn _0.2 O ₁₂ : 0.01Cr ³⁺ .

Please refer to FIG. 2A for the X-ray diffraction pattern of the fluorescent material according to Embodiment 2 of the fluorescent material of the present invention. When the molar ratio of Sn is 0.2, the diffraction peak of the fluorescent material is consistent with the standard X-ray diffraction pattern of the known crystal structure (Ca ₃ Ga ₂ Ge ₃ O ₁₂ ) (ICSD Code: 1123). It is confirmed that the synthesized fluorescent material is pure phase, and it also shows that Sn with a similar atomic radius to Ge can effectively replace Ge in the process of synthesizing fluorescent materials, and smoothly enter the lattice of Ca ₃ Ga ₂ Ge ₃ O ₁₂ to form a solid solution. And there is no secondary phase and impurity phase in the X-ray diffraction pattern.

Please refer to FIG. 2B , which is an excitation spectrum diagram of the fluorescent material according to Embodiment 2 of the fluorescent material of the present invention, wherein the ordinate is the emission light intensity with the emission peak wavelength of 755 nm, and the abscissa is the wavelength of the excitation light. As shown in FIG. 2B , the Ca ₃ Ga ₂ Ge _2.8 Sn _0.2 O ₁₂ :0.01Cr ³⁺ fluorescent material can be excited to emit excitation light with a wavelength of 755 nm in a wavelength range of about 400 nm to about 530 nm, wherein the peak wavelength is about 465 nm. That is to say, the fluorescent material of Example 2 of the present invention can be excited by violet light, blue light, cyan light or green light, and emits emission light with a wavelength of 755 nm, wherein the fluorescent material of Example 2 is excited by blue light with a wavelength of 465 nm , the intensity of the emitted light at the wavelength of 755nm is the highest.

Please refer to FIG. 2C , which is an 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 with a wavelength of 465 nm. As shown in FIG. 2C, the wavelength of the emitted light may range from about 650 nm to about 850 nm, with a peak wavelength of about 755 nm. That is to say, the fluorescent material of Example 2 of the present invention, after being excited by blue light irradiation with a wavelength of 465 nm, can emit a radiation spectrum with a wavelength in the red light and near-infrared light regions, wherein the near-infrared light with a wavelength of about 755 nm is used. The light intensity is the strongest, indicating that the fluorescent material of Example 2 of the present invention is a near-infrared fluorescent material.

Embodiment 3 of the fluorescent material of the present invention: synthesis of Ca ₃ Ga ₂ Ge _2.7 Sn _0.3 O ₁₂ : 0.01Cr ³⁺ fluorescent material.

Put calcium carbonate, germanium oxide, gallium oxide, tin dioxide and chromium trioxide into a ball mill according to the ratio of the above chemical formula, and add an appropriate amount of ethanol as a medium to assist mixing. Then, the mixture is ground and mixed with a planetary ball mill for about 8 to 10 hours, and the obtained mixed slurry is dried to obtain a precursor powder. Then, the above-mentioned precursor powder was placed in a high-temperature furnace, and calcined at a temperature of about 1000° C. for about 3 hours. The ambient gas during calcination was air, and the fluorescent material Ca ₃ Ga ₂ Ge of Example 3 was prepared. _2.7 Sn _0.3 O ₁₂ : 0.01Cr ³⁺ .

Please refer to FIG. 3A for the X-ray diffraction pattern of the fluorescent material according to Embodiment 3 of the fluorescent material of the present invention. When the molar ratio of Sn is 0.3, the diffraction peak of the fluorescent material is consistent with the standard X-ray diffraction pattern of the known crystal structure (Ca ₃ Ga ₂ Ge ₃ O ₁₂ ) (ICSD Code: 1123). It is confirmed that the synthesized fluorescent material is pure phase, and it also shows that Sn with a similar atomic radius to Ge can effectively replace Ge in the process of synthesizing fluorescent materials, and smoothly enter the lattice of Ca ₃ Ga ₂ Ge ₃ O ₁₂ to form a solid solution. And there is no secondary phase and impurity phase in the X-ray diffraction pattern.

Please refer to FIG. 3B , which is an excitation spectrum diagram of the fluorescent material according to Embodiment 3 of the fluorescent material of the present invention, wherein the ordinate is the radiation intensity of the emission peak wavelength of 755 nm, and the abscissa is the wavelength of the excitation light. As shown in FIG. 3B , the Ca ₃ Ga ₂ Ge _2.7 Sn _0.3 O ₁₂ :0.01Cr ³⁺ fluorescent material can be excited to emit excitation light with a wavelength of 755 nm in a wavelength range of about 400 nm to about 530 nm, wherein the peak wavelength is about 465 nm. That is to say, the fluorescent material of Example 3 of the present invention can be excited by violet light, blue light, cyan light or green light, and emits emission light with a wavelength of 755 nm, wherein the fluorescent material of Example 3 is excited by blue light with a wavelength of 465 nm , the intensity of the emitted light at the wavelength of 755nm is the highest.

Please refer to FIG. 3C , which is an emission spectrum of the fluorescent material of the present invention obtained by exciting the fluorescent material of Example 3 of the present invention with blue light with a wavelength of 465 nm. As shown in FIG. 3C, the wavelength of the emitted light may range from about 650 nm to about 850 nm, with a peak wavelength of about 755 nm. That is to say, the fluorescent material of Example 3 of the present invention, after being excited by the blue light with a wavelength of 465 nm, can emit a radiation spectrum with a wavelength in the red light and near-infrared light regions, wherein the near-infrared light with a wavelength of about 755 nm can emit a radiation spectrum. The light intensity is the strongest, indicating that the fluorescent material in Example 3 of the present invention is a near-infrared fluorescent material.

Please refer to FIG. 4 for the fluorescence emission spectrum diagrams of the three embodiments of the fluorescent material of the present invention shown in FIGS. 1C , 2C and 3C for comparing the wavelength and intensity of the emitted light of the three embodiments of the present invention. It should be particularly emphasized that the Ca ₃ Ga ₂ Ge _2.9 Sn _0.1 O ₁₂ : 0.01Cr ³⁺ in Example 1 of the present invention, Ca ₃ Ga ₂ Ge _2.8 Sn _0.2 O ₁₂ : 0.01Cr ³⁺ in Example 2 of the present invention, and The Ca ₃ Ga ₂ Ge _2.7 Sn _0.3 O ₁₂ :0.01Cr ³⁺ in Example 3 of the present invention was measured for the fluorescence emission spectrum in the same environment. As the Sn doping ratio increases (from the molar ratio of 0.01 in Example 1 of the present invention to 0.03 in Example 3 of the present invention), the peaks of the wavelengths of the emitted light obtained by exciting the fluorescent material with excitation light with a wavelength of 465 nm are all It is about 755 nm, however, it can be observed that the full width at half maximum of the emission spectrum gradually becomes wider in the long wavelength direction as the Sn doping ratio increases. It is worth noting that all three examples show that the intensity of the emission spectrum continues to increase after the line shape of the emission spectrum is higher than about 850 nm. Specifically, according to the analysis of the existing spectrum, the emission wavelength range should not only be limited from about 650 nm to about 850 nm, but widen to 1150 nm, wherein the emission wavelength range also includes about 850 nm to about 1150 nm. That is to say, by increasing the Sn doping ratio in the fluorescent material, the wavelength range of the emission light spectrum can be expanded, and a broad band near-infrared light fluorescent material can be obtained.

The technical innovation of the present invention constituted by the above-mentioned structure has many merits for those skilled in the same industry today, and is indeed technologically advanced.

Within the technical field of the present invention, as long as one has the most basic knowledge, other operable embodiments of the present invention can be improved. In the present invention, a patent protection request is made for the substantive technical solution, and the protection scope shall include all the variations with the above-mentioned technical features.

Claims (11)

1. A fluorescent material characterized in that Ca is represented by the chemical formula₃Ga₂Ge_3-xSn_xO₁₂: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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