Large-size Ge-In-Ag-Te quaternary chalcogenide glass as well as preparation method and application thereof

Abstract

The invention discloses large-size Ge-In-Ag-Te quaternary chalcogenide glass as well as a preparation method and application thereof, and the Ge-In-Ag-Te quaternary chalcogenide glass comprises the following components: 10-20 at% of Ge, 10-20 at% of Ag, 10-20 at% of Te, 10-20 at% of Te, 10-20 at% of Te, 10-20 70 to 80 at% of Te; 1 to 10 at% of In; and 5 to 10 at% of Ag. The preparation method comprises the following steps: mixing elementary substance Ge, elementary substance Te, elementary substance In and elementary substance Ag, and sequentially carrying out vacuum packaging, heating melting, cooling, quenching, heat preservation and annealing to obtain the large-size Ge-In-Ag-Te quaternary chalcogenide glass. The large-size Ge-In-Ag-Te quaternary chalcogenide glass provided by the invention is mainly composed of a Te element and has high atomic mass and polarizability, the prepared chalcogenide glass has a high linear refractive index, the refractive index of the chalcogenide glass is greater than 3.53 and higher than that of the existing chalcogenide glass at 25 DEG C and a wavelength of 10 [mu] m, the glass-transition temperature of the chalcogenide glass is 160-175 DEG C, and the transmittance of the chalcogenide glass in an infrared window reaches 54-60%. The transmission range can be expanded to 20 microns or above, and the preparation method is simple, easy to operate and easy to control; and effective bars with the diameter larger than or equal to 90 mm can be obtained.

Description

Technical Field

[0001] The present invention relates to a large-sized Ge-In-Ag-Te quaternary chalcogenide glass, a preparation method thereof and an application thereof, belonging to the technical field of optical materials. Background Art

[0002] Chalcogenide glass refers to an amorphous material mainly formed by 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.

[0003] Chalcogenide glass can be directly processed into infrared optical lenses by 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.

[0004] The existing chalcogenide glass is generally a rod with a diameter less than 30 mm, and it is difficult to obtain a large-sized effective rod. With the development of science and technology and people's pursuit of higher-quality products, the present invention provides a large-sized Ge-In-Ag-Te quaternary chalcogenide glass to improve the infrared optical properties of chalcogenide glass and obtain a large-sized effective chalcogenide glass. Summary of the Invention

[0005] The present invention provides a large-sized Ge-In-Ag-Te quaternary chalcogenide glass, a preparation method thereof and an application thereof. The refractive index of the large-sized Ge-In-Ag-Te quaternary chalcogenide glass of the present invention at a wavelength of 10 μm is greater than 3.6, the transmission range can be extended to more than 25 μm, and it has good heat resistance and can be used for the preparation of high-quality products; and the present invention can melt an effective rod with a diameter ≥ 90 mm to meet the requirements of different occasions.

[0006] To solve the above technical problems, the technical solutions adopted by the present invention are as follows:

[0007] A large-sized Ge-In-Ag-Te quaternary chalcogenide glass, comprising: Ge: 10-20 at%; Te: 70-80 at%; In: 1-10 at%; Ag: 5-10 at%; the sum of the contents of Ge, Te, In and Ag is 100 at%.

[0008] Further preferably, in the large-sized Ge-In-Ag-Te quaternary chalcogenide glass, Ge: 10-15 at%, Te: 70-76 at%, In: 4-8 at%, Ag: 7-10 at%. In the large-sized Ge-In-Ag-Te quaternary chalcogenide glass, the sum of the contents of the four elements is 100 at%.

[0009] For the large-sized Ge-In-Ag-Te quaternary chalcogenide glass of the present application, at 25 °C, the refractive index at a wavelength of 10 μm is ≥ 3.53.

[0010] The effects of different elements on chalcogenide glasses are different. The inventors found through experiments that the addition of indium In synergizes with Ge, Te, and Ag, significantly improving the compactness of the glass network structure, significantly enhancing the refractive index and transmittance, and having advantages such as reducing the element size and improving the imaging quality.

[0011] The glass transition temperature of the large-sized Ge-In-Ag-Te quaternary chalcogenide glass of the present application is 160-175 °C.

[0012] The preparation method of the above-mentioned large-sized Ge-In-Ag-Te quaternary chalcogenide glass is as follows: After mixing elemental Ge, elemental Te, elemental In, and elemental Ag, vacuum encapsulation, heating and melting, cooling, quenching, heat preservation, and annealing are carried out in sequence to obtain the large-sized Ge-In-Ag-Te quaternary chalcogenide glass.

[0013] In the present application, each elemental raw material is loaded into a quartz ampoule bottle for subsequent steps.

[0014] The control of the temperature in the above steps will affect the formation and quality of the glass. The temperature of the above heating and melting is 200-950 °C, preferably 700-900 °C, and the heat preservation time is 30-38 h.

[0015] In order to ensure the optical quality of the obtained Ge-In-Ag-Te quaternary chalcogenide glass, the final temperature of cooling is 400-430 °C.

[0016] The above-mentioned quenching is to blow with compressed air from bottom to top and stop blowing after the melt solidifies.

[0017] In order to further improve the optical quality of the obtained large-sized Ge-In-Ag-Te quaternary chalcogenide glass, the temperature of the above heat preservation is 120-150 °C, the heat preservation time is 18-24 h; the annealing temperature is 120-150 °C, and the annealing rate is -3 °C / h.

[0018] The present application can obtain an effective (the structure is consistent at different positions, and the performance such as infrared transmittance is uniform) rod with a diameter ≥ 90 mm.

[0019] The purities of the above-mentioned elemental Ge, elemental Te, elemental In, and elemental Ag are all not less than 5N.

[0020] The above-mentioned large-sized Ge-In-Ag-Te quaternary chalcogenide glass can be used as an infrared optical material. It has the advantages of high refractive index, wide infrared transmission window, and wide application range, etc., improving the economic benefits of the application of chalcogenide glass.

[0021] For technologies not mentioned in the present invention, reference is made to the prior art.

[0022] The large-sized Ge-In-Ag-Te quaternary chalcogenide glass of the present invention is mainly composed of Te element. Its atomic mass and polarizability are relatively high. The prepared chalcogenide glass has a high linear refractive index. At 25°C, the refractive index at a wavelength of 10μm is greater than 3.53, higher than that of the existing chalcogenide glass. Its glass transition temperature is 160 - 175°C, and the transmittance in the infrared window reaches 54 - 61%, and the transmission range can be extended to more than 20μm. The preparation method is simple, easy to operate and control; and an effective rod with a diameter ≥90mm can be obtained. Description of the Drawings

[0023] 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, other drawings can be obtained based on these drawings without creative efforts.

[0024] Figure 1 It is the refractive index curve graph of the Te-containing multi-component chalcogenide glass prepared in Example 1 of the present invention;

[0025] Figure 2 It is the transmittance curve graph of the Te-containing multi-component chalcogenide glass prepared in Example 1 of the present invention. Detailed Embodiments

[0026] The present invention provides a large-sized Ge-In-Ag-Te quaternary chalcogenide glass, including the following elemental components:

[0027] Ge: 10 - 20 at%; Te: 70 - 80 at%; In: 1 - 10 at%; Ag: 5 - 10 at%; the sum of the contents of Ge, Te, In, and Ag is 100 at%. Element Ge is preferably 10 - 15 at%.

[0028] The present invention also provides a preparation method of the above-mentioned large-sized Ge-In-Ag-Te quaternary chalcogenide glass. After weighing and mixing elemental Ge, elemental Te, elemental In, and elemental Ag, vacuum packaging, heating and melting, cooling, quenching, heat preservation, and annealing are carried out in sequence to obtain the large-sized Ge-In-Ag-Te quaternary chalcogenide glass.

[0029] In the present invention, the purity of the elemental Ge, elemental In, elemental Te, and elemental Ag is preferably not less than 5N, and more preferably 5N.

[0030] In the present invention, the raw materials are weighed on an electronic scale with a precision of 0.001. The elemental Ge, elemental In, elemental Te, and elemental Ag are weighed in sequence and placed into a quartz ampoule bottle. This operation is carried out in a vacuum glove box.

[0031] In the present invention, the vacuum encapsulation is preferably as follows: the connecting pipe nozzle of the quartz ampoule bottle with a vacuum degree of 4.0*10 -4 Pa is sealed by melting; the melting seal is carried out using a hydrogen-oxygen flame.

[0032] In the present invention, the temperature of the heating and melting is preferably 200 - 900 °C, more preferably 700 - 900 °C, and further preferably 850 - 900 °C. 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 bottle are heated and melted to obtain a melt.

[0033] In the present invention, the final temperature of the cooling is preferably 380 - 430 °C, and more preferably 420 - 430 °C.

[0034] In the present invention, the quenching is preferably as follows: the quartz ampoule containing the melt after cooling is taken out from 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 bottle. The blowing is stopped after the melt in the bottle solidifies.

[0035] In the present invention, the heat preservation temperature is 150 °C, and the heat preservation time is 24 h. The annealing temperature is 150 °C, and the annealing rate is -3 °C / h.

[0036] The present invention also provides the application of the multi-component chalcogenide glass described in the above scheme or the multi-component chalcogenide glass obtained by the preparation method described in the above scheme as an infrared optical material.

[0037] The present invention has no special requirements for the specific manner of using the multi-component chalcogenide glass as an infrared optical material. The multi-component chalcogenide glass can be processed into the required shape.

[0038] In order to further illustrate the present invention, the following describes the scheme of the present invention in detail with reference to the accompanying drawings and embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0039] Example 1

[0040] This example provides a preparation method of a multi-component chalcogenide glass containing Te with a high refractive index, including the following steps:

[0041] Weigh 300 g of elemental Ge, elemental In, elemental Te, and elemental Ag with a purity of 5N (the sum of the masses of elemental Ge, elemental In, elemental Te, and elemental Ag is 300 g, and the following similar expressions have the same meaning) in a glove box filled with inert gas and sequentially load them into a quartz ampoule bottle to obtain a mixture of elements;

[0042] The raw materials are proportioned according to the following atomic percentages:

[0043] Ge: 12 at%

[0044] Te: 70 at%

[0045] In: 8 at%

[0046] Ag: 10 at%

[0047] Take out the quartz ampoule containing the elemental mixture from the glove box, evacuate it, and evacuate the vacuum to 4.0 * 10 -4 Pa, then stop evacuating, and seal the mouth of the quartz ampoule bottle with a hydrogen-oxygen flame;

[0048] Put the encapsulated purification tube into a heating and rocking furnace for high-temperature melting, fully react, the melting temperature is 900 °C, the melting time is 38 h, stop rocking after the heating and melting is completed, set the temperature of the encapsulated quartz ampoule bottle to decrease, and take out the quartz ampoule bottle when the temperature drops to 430 °C;

[0049] Take out the quartz ampoule containing 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 bottle with the compressed air generated by an air compressor. Stop blowing air after the melt in the bottle solidifies.

[0050] Put the quenched quartz ampoule bottle into an annealing furnace for heat preservation and annealing, the heat preservation temperature is 150 °C, heat preservation for 24 h, the annealing temperature is 150 °C, and the annealing rate is -3 °C / h to obtain an effective rod with a diameter of 90 mm and uniform infrared transmission.

[0051] Experimental results:

[0052] The refractive index of the Te-based multi-component chalcogenide glass obtained in this example at a wavelength of 10 μm is 3.53 (as Figure 1 shown), which is much higher than the common As-Se chalcogenide glass on the market. The transmittance of the multi-component chalcogenide glass obtained in this example is 61% (as Figure 2 shown), and the glass transition temperature is 168 °C.

[0053] Example 2

[0054] This embodiment provides a method for preparing a Te-containing multi-component chalcogenide glass with a high refractive index, comprising the following steps:

[0055] Weigh 300 g of elemental Ge, elemental In, elemental Te, and elemental Ag with a purity of 5N in a glove box filled with inert gas and sequentially load them into a quartz ampoule to obtain a mixture of elemental substances;

[0056] The raw materials are proportioned according to the following atomic percentages:

[0057] Ge: 15 at%

[0058] Te: 70 at%

[0059] In: 5 at%

[0060] Ag: 10 at%

[0061] Take out the quartz ampoule containing the mixture of elemental substances from the glove box, evacuate it, and evacuate the vacuum to 4.0*10 -4 Pa, then stop evacuating, and use a hydrogen-oxygen flame to seal the mouth of the quartz ampoule;

[0062] Put the sealed 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 of the sealed quartz ampoule to decrease. When the temperature drops to 420 °C, take out the quartz ampoule;

[0063] Take out the quartz ampoule containing the melt after cooling from the rocking heating furnace and quickly fix it on a fixture, and blow air from the bottom to the top of the quartz ampoule with compressed air generated by an air compressor.

[0064] Put the quenched quartz ampoule into an annealing furnace for heat preservation and annealing. The heat preservation temperature is 145 °C, the heat preservation time is 24 h, the annealing temperature is 145 °C, and the annealing rate is -3 °C / h to obtain an effective rod with a diameter of 90 mm and uniform infrared transmission.

[0065] Experimental results:

[0066] The refractive index of the Te-based multi-component chalcogenide glass obtained in this embodiment at a wavelength of 10 μm is 3.54, which is much higher than that of the common As-Se chalcogenide glass on the market. The transmittance of the multi-component chalcogenide glass obtained in this embodiment is 61%, and the transition temperature is 170 °C.

[0067] Example 3

[0068] This embodiment provides a method for preparing a Te-containing multi-component chalcogenide glass with a high refractive index, comprising the following steps:

[0069] Weigh 300 g of elemental Ge, elemental In, elemental Te, and elemental Ag with a purity of 5N in a glove box filled with inert gas and sequentially load them into quartz ampoules to obtain a mixture of elemental substances;

[0070] The raw materials are proportioned according to the following atomic percentages:

[0071] Ge: 13 at%

[0072] Te: 76 at%

[0073] In: 4 at%

[0074] Ag: 7 at%

[0075] Take out the quartz ampoule containing the mixture of elemental substances from the glove box, evacuate it, and evacuate the vacuum degree to 4.0 * 10 -4 Pa, then stop evacuating, and seal the mouth of the quartz ampoule with a hydrogen-oxygen flame;

[0076] Put the sealed purification tube into a heating and 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 sealed quartz ampoule, and take out the quartz ampoule when the temperature drops to 420 °C;

[0077] Take out the quartz ampoule containing the melt after temperature reduction 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 with compressed air generated by an air compressor.

[0078] Put the quenched quartz ampoule into an annealing furnace for heat preservation and annealing. The heat preservation temperature is 145 °C, and the heat preservation time is 24 h. The annealing temperature is 145 °C, and the annealing rate is -3 °C / h to obtain an effective rod with a diameter of 90 mm and uniform infrared transmittance.

[0079] Experimental results:

[0080] The refractive index of the Te-based multi-component chalcogenide glass obtained in this example at a wavelength of 10 μm is 3.58, which is much higher than that of the common As-Se chalcogenide glass on the market. The transmittance of the multi-component chalcogenide glass obtained in this example is 56%, and the transition temperature is 160 °C.

[0081] Comparative Example 1

[0082] The difference from Example 1 is that In is replaced by Ga, and the rest are referred to Example 1.

[0083] The refractive index of the Te-based multi-component chalcogenide glass obtained in this example at a wavelength of 10 μm is 3.45. The transmittance of the multi-component chalcogenide glass obtained in this example is 54%, and the transition temperature is 160 °C.

[0084] Comparative Example 2

[0085] The difference from Example 1 is that the element contents are replaced with: Ge: 12 at%, Te: 78 at%, Ag: 10 at%, that is, In is omitted, and the rest refers to Example 1.

[0086] The maximum diameter of the Te-based multi-component chalcogenide glass obtained in this example is 20 mm, and larger sizes will crystallize and lose the infrared transmission effect.

[0087] Comparative Example 3

[0088] The difference from Example 1 is that the element contents are replaced with: Ge: 12 at%, Te: 66 at%, In: 12 at% Ag: 10 at%, that is, excessive use of In will cause crystallization and loss of infrared transmission performance, and the rest refers to Example 1.

[0089] 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 embodiment without creative efforts, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A large-sized Ge-In-Ag-Te quaternary chalcogenide glass, characterized in that: Including: Ge: 10 - 20 at%; Te: 70 - 80 at%; In: 1 - 10 at%; Ag: 5 - 10 at%.

2. The large-sized Ge-In-Ag-Te quaternary chalcogenide glass according to claim 1, wherein: At 25 °C, its refractive index at a wavelength of 10 μm is ≥ 3.

53.

3. The large-sized Ge-In-Ag-Te quaternary chalcogenide glass according to claim 1 or 2, characterized in that: Its glass transition temperature is 160 - 175 °C.

4. A method for preparing the large-size Ge-In-Ag-Te quaternary chalcogenide glass according to any one of claims 1-3, characterized in that: After mixing elemental Ge, elemental Te, elemental In, and elemental Ag, vacuum encapsulation, heating and melting, cooling, quenching, heat preservation, and annealing are carried out in sequence to obtain large - sized Ge - In - Ag - Te quaternary chalcogenide glass.

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

6. The preparation method according to claim 4 or 5, characterized in that: The final temperature of cooling is 400 - 430 °C.

7. The preparation method according to claim 4 or 5, characterized in that: Quenching is carried out by blowing compressed air from bottom to top and stopping blowing after the melt solidifies.

8. The preparation method according to claim 4 or 5, characterized in that: The heat preservation temperature is 120 - 150 °C, and the heat preservation time is 18 - 24 h; the annealing temperature is 120 - 150 °C, and the annealing rate is - 3 °C / h; large - sized Ge - In - Ag - Te quaternary chalcogenide glass rods with a diameter ≥ 90 mm can be obtained.

9. The preparation method according to claim 4 or 5, characterized in that: The purities of elemental Ge, elemental Te, elemental In, and elemental Ag are all not less than 5N.

10. Application of the large-size Ge-In-Ag-Te quaternary chalcogenide glass according to any one of claims 1-3, characterized in that: As an infrared optical material.

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