Oxyhalide glass for solar blind light detection and imaging and preparation method thereof

Abstract

The invention relates to the technical field of optical functional glass materials, in particular to oxyhalide glass for solar blind optical detection and imaging and a preparation method of the oxyhalide glass. The oxyhalide glass comprises matrix glass and a Tb < 3 + >-containing compound, the Tb < 3 + >-containing compound is doped into the matrix glass in an external doping form, and the Tb < 3 + >-containing compound accounts for 0.1-10.0 mol% of the matrix glass. The prepared oxyhalide glass has high luminous efficiency, the quantum efficiency can reach 90% or above, excellent photoluminescence and photoelectric response are achieved in the solar blind wave band, the amorphous state can be kept all the time, and the light transmittance is 90% or above.

Description

Technical Field

[0001] The invention relates to the technical field of optical functional glass materials, and in particular to an oxyhalide glass for solar-blind light detection and imaging and a preparation method thereof. Background Art

[0002] The mid-ultraviolet radiation in the 180-280 nm band of sunlight cannot reach the earth's surface due to absorption by ozone in the stratosphere, resulting in a blind zone for ultraviolet radiation in sunlight near the surface of the earth. Therefore, this ultraviolet spectrum area is called the "solar blind zone". Solar blind light has the advantages of low noise, anti-interference, and high sensitivity. It has a wide range of application values ​​in military, communication, and civil fields such as flame sensing, ultraviolet communication, ozone detection, and missile attack warning. However, solar blind light cannot be directly perceived by the human eye. It is necessary to develop effective luminescent materials to convert solar blind light into visible light in order to achieve detection and imaging of solar blind light.

[0003] At present, the research on luminescent materials for the detection and imaging of solar-blind light is more focused on powder, liquid and crystal materials, but these three have their own shortcomings. First, for powder materials, their light transmittance is low, which is not conducive to their application in solar-blind light imaging; second, liquid materials have poor reliability when prepared into devices, which is not conducive to their large-scale and widespread application; third, crystal materials grow slowly and have high preparation costs, which is not conducive to their large-scale production and application.

[0004] Compared with the above three materials, glass has the following advantages: 1) Glass is isotropic and has good optical transmittance, and is a high-quality optical medium material; 2) It has excellent resistance to moisture and heat, radiation and mechanical properties, and has high reliability when made into devices; 3) It has low production cost and high processability, and is suitable for large-scale batch production; 4) Glass has the characteristics of softening and drawing, and can be made into optical fiber. When it is made into an optical fiber panel, it can further improve the imaging resolution. These advantages make glass have very important application prospects in the field of solar blind light detection and imaging.

[0005] At present, the research on the detection and imaging of glass in the solar-blind band mainly focuses on the rare earth ion Tb 3+ Glass with luminescent center. 3+ The ion has a strong natural absorption in the solar-blind band of 180-280 nm. When excited in this band, it can produce excellent photoluminescence with a wavelength of 545 nm, which is highly matched with the sensitive wavelength (500-750 nm) of common photodetectors such as CCD. These characteristics make Tb 3+Doped glass has broad application prospects in the field of solar-blind light detection and imaging. At present, Tb³⁺-doped glass mainly relies on crystal precipitation to improve its luminous efficiency. When preparing small pieces of glass, it can maintain a high optical transmittance. However, when preparing large pieces of glass, crystallization is uncontrollable, the glass transmittance is reduced, and the luminous efficiency also drops sharply. This also brings difficulties to the preparation of optical fibers. When drawing optical fibers, crystallization is serious and optical loss is large, which hinders its application in optical fiber arrays.

[0006] Therefore, it is necessary to develop and research new products to address the shortcomings of current glass in the detection and imaging of solar-blind bands. Summary of the invention

[0007] The purpose of the present invention is to solve the shortcomings and problems existing in the current glass used for detection and imaging in the solar-blind band, to provide an oxyhalide glass for solar-blind light detection and imaging, and to provide a corresponding preparation method.

[0008] The oxyhalide glass prepared by the present invention has high photoluminescence efficiency, high stability, high transmittance, always maintains an amorphous state, and has good photoelectric response to solar-blind light at 180-280 nm. At the same time, it can also be made into large pieces of glass, which has potential application value in large-scale solar-blind light imaging and optical fiber array imaging.

[0009] The technical solution adopted by the present invention to solve its technical problem is: A halogenated oxide glass for solar-blind light detection and imaging, the halogenated oxide glass comprising a substrate glass and a Tb-containing 3+ The compound containing Tb 3+ The compound is doped into the matrix glass in the form of an external dopant, and contains Tb 3+ The molar percentage of the compound in the matrix glass is 0.1 to 10.0%.

[0010] Furthermore, the Tb-containing 3+ The compound is any one, two or more of Tb2O3, Tb4O7, and TbF3.

[0011] Furthermore, the molar percentages of the components of the matrix glass are as follows: Glass network body: 50-70%, ZnO: 5.5~15%, MO: 10-15%, Cs2O: 7~10%, NaX:7.5~10%.

[0012] Furthermore, in the matrix glass, the main body of the glass network is one or more of SiO2, GeO2, B2O3, TeO2, and P2O5.

[0013] Furthermore, the MO is any one of MgO, CaO, SrO and BaO.

[0014] Furthermore, the NaX is any one of NaF, NaCl, NaBr and NaI.

[0015] A method for preparing oxyhalide glass, the method comprising the following steps: (1) Prepare the raw materials of matrix glass according to the following ratio: glass network body: 50-70%, ZnO: 5.5-15%, MO: 10-15%, Cs2O: 7-10%, NaX: 7.5-10%; and prepare a Tb-containing catalyst according to a molar percentage of 0.1 to 10.0% of the matrix glass. 3+ Compounds of (2) Weigh high-purity powdered raw materials according to the above components in proportion and mix them thoroughly in an agate mortar; (3) Pour the uniformly mixed materials into the glass, put it into a high-temperature melting furnace at 1100-1240°C for melting for 20-60 minutes, keep it warm for 1-2 hours, then discharge the material and form it into a block glass sample; (4) The glass is immediately placed in an annealing furnace and kept at 500-550°C for 2-3 hours to eliminate some stress and obtain the product oxyhalide glass.

[0016] Compared with the prior art, the present invention has the following beneficial effects: (1) The oxyhalide glass prepared by the method of the present invention has high luminous efficiency, with a quantum efficiency of more than 90%, and has excellent photoluminescence and photoelectric response in the solar-blind band; (2) The oxyhalide glass-ceramics prepared by the present invention can always remain amorphous regardless of any subsequent operation and has a light transmittance of more than 90%; (3) The method of the present invention can be used to prepare large-sized glass, providing excellent matrix materials for large-sized solar-blind imaging and optical fiber array imaging; (4) The present invention proposes a new method for preparing oxyhalide glass for solar-blind light detection and imaging, which provides a good reference for the preparation of glass of more different system types for solar-blind light detection and imaging. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is the photoelectric response diagram of the glass in Example 1 under the excitation of solar-blind light.

[0018] Figure 2 This is the transmission spectrum of the glass in Example 1.

[0019] Figure 3 This is the X-ray diffraction pattern of the glass in Example 1.

[0020] Figure 4 This is a photo of the large-size glass prepared in Example 2. DETAILED DESCRIPTION

[0021] In order to enable those skilled in the art to better understand the solution of the present invention, the technical solution of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0022] The present invention provides an oxyhalide glass for solar-blind light detection and imaging, wherein the oxyhalide glass comprises a substrate glass and a Tb-containing 3+ The compound containing Tb 3+ The compound is doped into the matrix glass in the form of an external dopant, and contains Tb 3+ The molar percentage of the compound in the matrix glass is 0.1 to 10.0%; The Tb-containing 3+ The compound is any one, two or more of Tb2O3, Tb4O7, and TbF3.

[0023] The components of the matrix glass are as follows in terms of molar percentage: glass network body: 50-70%, ZnO: 5.5-15%, MO: 10-15%, Cs2O: 7-10%, NaX: 7.5-10%; in, The main body of the glass network is one or more of SiO2, GeO2, B2O3, TeO2, and P2O5; MO is any one of MgO, CaO, SrO and BaO; NaX is any one of NaF, NaCl, NaBr and NaI.

[0024] The method for preparing the above-mentioned oxyhalide glass comprises the following steps: (1) Prepare the raw materials of matrix glass according to the following ratio: glass network body: 50-70%, ZnO: 5.5-15%, MO: 10-15%, Cs2O: 7-10%, NaX: 7.5-10%; and preparing a compound containing Tb3+ in a molar percentage of 0.1 to 10.0% of the matrix glass; (2) Weigh high-purity powdered raw materials according to the above components in proportion and mix them thoroughly in an agate mortar; (3) Pour the uniformly mixed materials into a glass container, place it into a high-temperature melting furnace at 1100-1240°C for melting for 20-60 minutes, keep it warm for 1-2 hours, then discharge the materials and form them into block glass samples; (4) The glass is immediately placed in an annealing furnace and kept at 500-550°C for 2-3 hours to eliminate some stress and obtain the product oxyhalide glass.

[0025] Embodiment 1: An oxyhalide glass for solar-blind light detection and imaging is prepared by the following steps: (1) The glass adopts the following formula: molar percentage of each component SiO2: 34%, B2O3: 36%, ZnO: 6%, BaO: 8%, NaBr: 8%, Cs2O:8%, Tb2O3: 3.5%; (2) Weigh 50 g of high-purity powdered raw materials according to the component formula and mix them thoroughly in an agate mortar; (3) Pour the mixed material into a 100 ml quartz glass container, cover it, put it into a high-temperature melting furnace, slowly heat it to 1200 °C and keep it warm for 30 min, then put in a stirring rod and stir it slowly (10 rpm) for 30 min, keep it warm for another 1 h, unload it, and form it into a block glass sample; (4) The glass is immediately placed in an annealing furnace and kept at 550°C for 2 h to eliminate some of the stress and obtain the final product, oxyhalide glass.

[0026] The microstructure and luminescence properties of the obtained product oxyhalide glass were characterized.

[0027] Embodiment 2: An oxyhalide glass for solar-blind light detection and imaging is prepared by the following steps: (1) The glass adopts the following formula: molar percentage of components P2O5: 30%, B2O3:40%, ZnO: 6%, SrO:8%, NaBr: 8%, Cs2O:8%, Tb2O3: 3.5%; (2) Weigh 500 g of high-purity powdered raw materials according to the component formula and mix them thoroughly in an agate mortar; (3) Pour the mixed material into a 1000 ml quartz glass container, cover it, put it into a high-temperature melting furnace, slowly heat it to 1200 °C and keep it warm for 30 min, then put in a stirring rod and stir it slowly (10 rpm) for 30 min, keep it warm for another 1 h, unload it, and form it into a block glass sample; (4) The glass is immediately placed in an annealing furnace and kept at 550°C for 2 h to eliminate some of the stress and obtain the final product, oxyhalide glass.

[0028] The microstructure and luminescence properties of the obtained product oxyhalide glass were characterized.

[0029] Characterize the microstructure and luminescence properties of glass.

[0030] Embodiment 3: An oxyhalide glass for solar-blind light detection and imaging is prepared by the following steps: (1) The glass adopts the following formula: molar percentage of each component: SiO2: 30%, B2O3:40%, ZnO: 6%, CaO: 8%, NaCl: 8%, Cs2O:8%, TbF3:6%, (2) Weigh 50 g of high-purity powdered raw materials according to the component formula and mix them thoroughly in an agate mortar; (3) Pour the mixed material into a 100 ml quartz glass container, cover it, put it into a high-temperature melting furnace, slowly heat it to 1200 °C and keep it warm for 30 min, then put in a stirring rod and stir it slowly (10 rpm) for 30 min, keep it warm for another 1 h, unload it, and form it into a block glass sample; (4) The glass is immediately placed in an annealing furnace and kept at 550°C for 2 h to eliminate some of the stress and obtain the final product, oxyhalide glass.

[0031] The microstructure and luminescence properties of the obtained product oxyhalide glass were characterized.

[0032] For test results, please refer to the attached Figure 1 As shown, Figure 1 The glass prepared in Example 1 has good photoelectric response in the solar-blind band. Figure 2 As shown, the glass prepared in Example 2 maintains an optical transmittance of more than 90% and can always remain in an amorphous state (see Figure 3 ).

[0033] Figure 4 This is the finished glass product prepared in Example 1.

[0034] It is obvious to those skilled in the art that the above embodiments are not intended to be exhaustive or limit the embodiments to the specific precise forms disclosed. It is obvious to those skilled in the art that certain modifications, combinations and variations can be made based on the above teachings.

Claims

1. An oxyhalide glass for solar-blind light detection and imaging, characterized in that: The oxyhalide glass comprises a base glass and a Tb-containing 3+ The compound containing Tb 3+ The compound is doped into the matrix glass in the form of an external dopant, and contains Tb 3+ The molar percentage of the compound in the matrix glass is 0.1 to 10.0%.

2. The oxyhalide glass according to claim 1, characterized in that: The Tb-containing 3+ The compound is any one, two or more of Tb2O3, Tb4O7, and TbF3.

3. The oxyhalide glass according to claim 1, characterized in that: The components of the matrix glass are as follows in terms of molar percentage: Glass network body: 50-70%, ZnO: 5.5~15%, MO: 10-15%, Cs2O: 7~10%, NaX:7.5~10%.

4. The oxyhalide glass according to claim 1, characterized in that: In the matrix glass, the main body of the glass network is one or more of SiO2, GeO2, B2O3, TeO2, and P2O5.

5. The oxyhalide glass according to claim 1, characterized in that: The MO is any one of MgO, CaO, SrO and BaO.

6. The oxyhalide glass according to claim 1, characterized in that: The NaX is any one of NaF, NaCl, NaBr and NaI.

7. A method for preparing the oxyhalide glass according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: (1) Prepare the raw materials of matrix glass according to the following ratio: glass network body: 50-70%, ZnO: 5.5-15%, MO: 10-15%, Cs2O: 7-10%, NaX: 7.5-10%; and prepare a Tb-containing catalyst according to a molar percentage of 0.1 to 10.0% of the matrix glass. 3+ Compounds of (2) Weigh high-purity powdered raw materials according to the above components in proportion and mix them thoroughly in an agate mortar; (3) Pour the uniformly mixed materials into the glass, put it into a high-temperature melting furnace at 1100-1240°C for melting for 20-60 minutes, keep it warm for 1-2 hours, then discharge the material and form it into a block glass sample; (4) The glass is immediately placed in an annealing furnace and kept at 500-550°C for 2-3 hours to eliminate some stress and obtain the product oxyhalide glass.

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