Ge-Sb-Se-In chalcogenide glass as well as preparation method and application thereof

Abstract

The invention discloses Ge-Sb-Se-In chalcogenide glass as well as a preparation method and application thereof, and the Ge-Sb-Se-In chalcogenide glass comprises the following element components: 20-30 at% of Ge, 20-30 at% of Se, 20-30 at% of Sb, 20-30 at% of In, 20-30 at% of Sb, 10- 10 to 20 at% of Sb; se: 60 at%; and 1 to 10 at% of In. The preparation method of the Ge-Sb-Se-In chalcogenide glass comprises the following steps: mixing the elementary substance Ge, the elementary substance Sb, the elementary substance Se and the elementary substance In, and sequentially carrying out vacuum packaging, heating melting, cooling, quenching, heat preservation and annealing to obtain the Ge-Sb-Se-In chalcogenide glass. According to the Ge-Sb-Se-In chalcogenide glass disclosed by the invention, through cooperation of In, Ge, Sb and Se, the infrared transmission range is remarkably widened, the short wave cutoff wavelength is 750nm, the long wave cutoff wavelength is 16 microns, and the hardness is improved and can reach 176kgf / mm < 2 >. The material can be used as an infrared window material or an infrared lens, and the imaging effect and the detection precision are improved.

Description

Technical Field

[0001] The present invention relates to a Ge-Sb-Se-In chalcogenide glass, a preparation method thereof and uses thereof, belonging to the technical field of chalcogenide glasses. Background Art

[0002] Chalcogenide glasses refer to a kind of amorphous materials mainly composed of S, Se, Te in Group VIA of the periodic table of elements and introducing a certain amount of metal or metalloid elements. It has a series of excellent optical properties such as low phonon energy, wide infrared transmission range, high linear and nonlinear refractive indices. Chalcogenide glasses can be directly processed into infrared optical lenses through precision molding. Its preparation and processing costs are lower than those of single crystal germanium, and the size is not limited. Therefore, a series of problems such as complex preparation process, long processing cycle and low qualification rate of traditional infrared system lenses can be solved. Therefore, this material has gradually attracted attention and is regarded as the core material of a new generation of temperature adaptive infrared optical systems.

[0003] In order to broaden the infrared transmission range of Se-based chalcogenide glasses, improve the transmittance, and at the same time improve the hardness of Se-based chalcogenide glasses, the present invention provides a Ge-Sb-Se-In chalcogenide glass, a preparation method thereof and uses thereof. Summary of the Invention

[0004] The present invention provides a Ge-Sb-Se-In chalcogenide glass, a preparation method thereof and uses thereof. The short-wave cut-off wavelength of the Ge-Sb-Se-In chalcogenide glass of the present invention is 750 nm, the long-wave cut-off wavelength is 16 μm, and the hardness reaches 176 kgf / mm 2 , thereby improving the imaging effect and detection accuracy.

[0005] To solve the above technical problems, the technical solutions adopted by the present invention are as follows:

[0006] A Ge-Sb-Se-In chalcogenide glass comprises the following elemental components: Ge: 20-30 at%; Sb: 10-20 at%; Se: 60 at%; In: 1-10 at%.

[0007] The Ge-Sb-Se-In chalcogenide glass of the present application is in a glassy state. Ceramic phase and glassy state are two different states of matter in materials science. They have significant differences in structure, properties, etc. and have their own unique uses in different fields.

[0008] To further broaden the infrared transmission range, preferably, the above Ge-Sb-Se-In chalcogenide glass comprises the following elemental components: Ge: 20-28 at%; Sb: 10-15 at%; Se: 60 at%; In: 5-10 at%.

[0009] The preparation method of the above Ge-Sb-Se-In chalcogenide glass: After mixing elemental Ge, elemental Sb, elemental Se and elemental In, vacuum encapsulation, heating and melting, cooling, quenching, heat preservation and annealing are carried out in sequence to obtain Ge-Sb-Se-In chalcogenide glass.

[0010] In the above preparation method, the temperature of heating and melting is 200-950 °C, preferably 700-900 °C, and the heat preservation time is 30-38 h, preferably 35-38 h.

[0011] In order to better ensure the optical properties of the obtained Ge-Sb-Se-In chalcogenide glass, in the above preparation method, the final temperature of cooling is 550-650 °C, preferably 600-650 °C.

[0012] In the above preparation method, quenching is to blow cold the quartz ampoule bottle from bottom to top with compressed air, and stop blowing after the melt in the bottle solidifies.

[0013] In order to ensure the comprehensive properties of the obtained Ge-Sb-Se-In chalcogenide glass, in the above preparation method, the temperature of heat preservation is 230-280 °C, and the heat preservation time is 20-24 h.

[0014] In order to further improve the quality of the obtained Ge-Sb-Se-In chalcogenide glass, in the above preparation method, the annealing temperature is 230-280 °C, and the annealing rate is -3 °C / h.

[0015] In the above preparation method, the purities of elemental Ge, elemental Sb, elemental Se and elemental In are all not less than 5N.

[0016] The Ge-Sb-Se-In chalcogenide glass prepared in this application can be used as an infrared window material or an infrared lens.

[0017] For technologies not mentioned in the present invention, refer to the prior art.

[0018] The Ge-Sb-Se-In chalcogenide glass of the present invention significantly broadens the infrared transmission range through the synergy of In, Ge, Sb and Se. The short-wave cut-off wavelength is 750 nm, and the long-wave cut-off wavelength is 16 μm, and the hardness is increased to 176 kgf / mm 2 . It can be used as an infrared window material or an infrared lens to improve the imaging effect and detection accuracy. Description of the Drawings

[0019] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required to be used in the embodiments. The drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0020] Figure 1 This is the transmittance curve of the Ge-Sb-Se-In chalcogenide glass prepared in Example 1 of the present invention. Detailed implementation manners

[0021] The present invention provides a Ge-Sb-Se-In chalcogenide glass, which comprises the following elemental components: Ge: 20-30 at%, Sb: 10-20 at%, Se: 60 at%, In: 1-10%.

[0022] The multi-component chalcogenide glass provided by the present invention comprises the element Ge: 20-30 at%. Preferably, it is 20-28 at%.

[0023] The multi-component chalcogenide glass provided by the present invention comprises the element Sb: 10-20 at%. Preferably, it is 10-15 at%.

[0024] The multi-component chalcogenide glass provided by the present invention comprises the element Se: 60 at%.

[0025] The multi-component chalcogenide glass provided by the present invention comprises the element In: 1-10 at%, preferably 5-10 at%.

[0026] For the preparation method of the above Ge-Sb-Se-In chalcogenide glass, after weighing and mixing elemental Ge, elemental Sb, elemental Se and elemental In, vacuum encapsulation, heating and melting, cooling, quenching, heat preservation and annealing are carried out in sequence to obtain the Ge-Sb-Se-In chalcogenide glass.

[0027] In this application, each elemental raw material is loaded into a quartz ampoule bottle for subsequent steps.

[0028] In the present invention, the purity of the elemental Ge, elemental Sb, elemental Se and elemental In is preferably not less than 5N, and more preferably 5N;

[0029] In the present invention, the raw material weighing is carried out on an electronic balance with an accuracy of 0.001. Elemental Ge, elemental Sb, elemental Se and elemental In are weighed in sequence and put into a quartz ampoule bottle. This operation is carried out in a vacuum glove box.

[0030] In the present invention, the vacuum encapsulation is preferably: sealing the connecting pipe nozzle of the quartz ampoule bottle with a vacuum degree of 4.0*10 -4 Pa; the sealing is carried out by using a hydrogen-oxygen flame.

[0031] In the present invention, the temperature of the heating and melting is preferably 200 - 900 °C, more preferably 700 - 900 °C, still more preferably 850 - 900 °C, and the heat preservation time is preferably 35 - 38 h; the equipment for the heating and melting is preferably a rocking heating furnace; in the present invention, the raw materials in the quartz ampoule are heated and melted to obtain a melt.

[0032] In the present invention, the final temperature of the cooling is preferably 550 - 650 °C, more preferably 600 - 650 °C.

[0033] In the present invention, the quenching is preferably as follows: after cooling, the quartz ampoule containing the melt is taken out of the rocking heating furnace and quickly fixed on a fixture, and compressed air generated by an air compressor is blown from the bottom to the top of the quartz ampoule. The blowing is stopped after the melt in the bottle solidifies.

[0034] In the present invention, the heat preservation temperature is 280 °C, the heat preservation time is 24 h, the annealing temperature is 280 °C, and the annealing rate is -3 °C / h.

[0035] To further illustrate the present invention, the solutions of the present invention will be described in detail below in conjunction with the drawings and embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0036] Example 1

[0037] This example provides a preparation method of Ge-Sb-Se-In chalcogenide glass, including the following steps: 300 g of element Ge, element Sb, element Se and element In with a purity of 5N (the mass sum of each element is 300 g, and the following examples have similar expressions with similar meanings) are weighed in a glove box filled with inert gas and are successively loaded into a quartz ampoule to obtain an element mixture;

[0038] The raw materials are proportioned according to the following atomic percentages:

[0039] Ge: 20 at%

[0040] Sb: 11 at%

[0041] Se: 60 at%

[0042] In: 9 at%

[0043] The quartz ampoule containing the element mixture is taken out of the glove box, evacuated, and the vacuum degree is evacuated to 4.0×10 -4 Pa, then the evacuation is stopped, and the mouth of the quartz ampoule is sealed with a hydrogen-oxygen flame;

[0044] Put the encapsulated purification tube into a heating rocking furnace for high-temperature melting and full reaction. The heating temperature is 900 °C, the heating time is 38 h. After the heating and melting are completed, stop rocking, set the temperature reduction for the encapsulated quartz ampoule bottle, and take out the quartz ampoule bottle when the temperature drops to 600 °C;

[0045] Take out the quartz ampoule containing the melt after temperature reduction from the rocking heating furnace and quickly fix it on the fixture. Use the compressed air generated by an air compressor to blow air from the bottom to the top of the quartz ampoule bottle.

[0046] Put the quenched quartz ampoule bottle into an annealing furnace for heat preservation and annealing. The heat preservation temperature is 280 °C, and the heat preservation time is 24 h. The annealing temperature is 280 °C, and the annealing rate is -3 °C / h.

[0047] Experimental results:

[0048] The hardness of the Ge-Sb-Se-In chalcogenide glass obtained in this example is 176 kgf / mm 2 , the transmission range is 0.75 - 16 μm, and the transmittance of the Ge-Sb-Se-In chalcogenide glass obtained in this example is 61% (as Figure 1 shown).

[0049] Example 2

[0050] This example provides a preparation method of Ge-Sb-Se-In chalcogenide glass, including the following steps: Weigh 300 g of elemental Ge, elemental Sb, elemental Se, and elemental In with a purity of 5N in a glove box filled with inert gas and sequentially load them into a quartz ampoule bottle to obtain an elemental mixture;

[0051] The raw materials are proportioned according to the following atomic percentage contents:

[0052] Ge: 20 at%

[0053] Sb: 15 at%

[0054] Se: 60 at%

[0055] In: 5 at%

[0056] Take out the quartz ampoule containing the elemental mixture from the glove box, evacuate it, and stop evacuating when the vacuum degree reaches 4.0 * 10 -4 Pa, and then seal the mouth of the quartz ampoule bottle with a hydrogen-oxygen flame;

[0057] Put the encapsulated purification tube into a heating rocking furnace for high-temperature melting and full reaction. The heating temperature is 900 °C, the heating time is 38 h. After the heating and melting are completed, stop rocking, set the temperature reduction for the encapsulated quartz ampoule bottle, and take out the quartz ampoule bottle when the temperature drops to 600 °C;

[0058] Take out the quartz ampoule filled with the melt after cooling from the rocking heating furnace and quickly fix it on the fixture, and blow air from the bottom to the top of the quartz ampoule using compressed air generated by an air compressor.

[0059] Put the quenched quartz ampoule into an annealing furnace for heat preservation and annealing. The heat preservation temperature is 280 °C, and the heat preservation time is 24 h. The annealing temperature is 280 °C, and the annealing rate is -3 °C / h.

[0060] Experimental results:

[0061] The hardness of the Ge-Sb-Se-In chalcogenide glass obtained in this example is 156 kgf / mm 2 , the transmittance range is 0.80 - 16 μm, and the transmittance of the multi-component chalcogenide glass obtained in this example is 61%.

[0062] Example 3

[0063] This example provides a preparation method of Ge-Sb-Se-In chalcogenide glass, including the following steps: Weigh 300 g of elemental Ge, elemental Sb, elemental Se, and elemental In with a purity of 5N in a glove box filled with inert gas and sequentially load them into a quartz ampoule to obtain an elemental mixture;

[0064] The raw materials are proportioned according to the following atomic percentages:

[0065] Ge: 20 at%

[0066] Sb: 17 at%

[0067] Se: 60 at%

[0068] In: 3 at%

[0069] Take out the quartz ampoule filled with the elemental mixture from the glove box, evacuate it, and stop evacuating after the vacuum degree reaches 4.0 * 10 -4 Pa, and then seal the mouth of the quartz ampoule with a hydrogen-oxygen flame;

[0070] Put the encapsulated purification tube into a heating rocking furnace for high-temperature melting, fully react. The heating temperature is 900 °C, and the heating time is 38 h. After the heating and melting are completed, stop rocking, set the temperature of the encapsulated quartz ampoule to decrease, and take out the quartz ampoule when the temperature drops to 600 °C;

[0071] Take out the quartz ampoule filled with the melt after cooling from the rocking heating furnace and quickly fix it on the fixture, and blow air from the bottom to the top of the quartz ampoule using compressed air generated by an air compressor.

[0072] The quenched quartz ampoule is placed in an annealing furnace for heat preservation and annealing. The heat preservation temperature is 280 °C, and the heat preservation time is 24 h. The annealing temperature is 280 °C, and the annealing rate is -3 °C / h.

[0073] Experimental results:

[0074] The hardness of the Ge-Sb-Se-In chalcogenide glass obtained in this example is 140 kgf / mm 2 , and the transmittance range is 0.85 - 16 μm. The transmittance of the Ge-Sb-Se-In chalcogenide glass obtained in this example is 60%.

[0075] Comparative Example 1

[0076] The difference from Example 1 is that the element contents are replaced with: Ge: 20 at%, Sb: 20 at%, Se: 60 at%, that is, In is omitted, and the rest refer to Example 1.

[0077] Experimental results:

[0078] The hardness of the Ge-Sb-Se chalcogenide glass obtained in this example is 117.5 kgf / mm 2 , and the transmittance range is 0.9 - 16 μm, and the transmittance is 59%.

[0079] Although the above embodiments have described the present invention in detail, they are only a part of the embodiments of the present invention, rather than all embodiments. Other embodiments can be obtained according to this example without creative efforts, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A Ge-Sb-Se-In chalcogenide glass, characterized in that: Contains the following element components: Ge: 20-30at%; Sb: 10-20at%; Se: 60at%; In: 1-10at%.

2. The Ge-Sb-Se-In chalcogenide glass according to claim 1, characterized in that: It contains the following element components: Ge: 20-28 at%; Sb: 10-15 at%; Se: 60 at%; In: 5-10 at%.

3. The method for preparing the Ge-Sb-Se-In chalcogenide glass according to claim 1 or 2, characterized in that: After mixing single elements Ge, single elements Sb, single elements Se and single elements In, vacuum packaging, heating and melting, cooling, quenching, heat preservation and annealing are carried out in sequence to obtain Ge-Sb-Se-In chalcogenide glass.

4. The preparation method according to claim 3, characterized in that: The heating melting temperature is 200-950°C and the holding time is 30-38h.

5. The preparation method according to claim 3 or 4, characterized in that: The final temperature of the cooling is 550-650°C.

6. The preparation method according to claim 3 or 4, characterized in that: The quenching process is carried out by blowing compressed air from bottom to top, and the blowing is stopped after the melt solidifies.

7. The preparation method according to claim 3 or 4, characterized in that: The insulation temperature is 230-280°C and the insulation time is 20-24h.

8. The preparation method according to claim 3 or 4, characterized in that: The annealing temperature is 230-280°C, and the annealing rate is -3°C / h.

9. The preparation method according to claim 3 or 4, characterized in that: The purity of single element Ge, single element Sb, single element Se and single element In is not less than 5N.

10. Use of the Ge-Sb-Se-In chalcogenide glass according to claim 1 or 2, characterized in that: Used as infrared window material or as infrared lens.

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