A Ge-Sb-Se-Ga chalcogenide glass and preparation method thereof

Abstract

The present disclosure relates to the technical field of chalcogenide glasses, and in particular to a Ge-Sb-Se-Ga chalcogenide glass and a preparation method thereof. The Ge-Sb-Se-Ga chalcogenide glass comprises the following components: Ge: 20-40 at%; Ga: 1-10 at%; Sb: 5-20 at%; and Se: 40-60 at%. The present application also provides a preparation method for the Ge-Sb-Se-Ga chalcogenide glass according to the above technical solution, comprising the following steps: (1) removing impurities and purifying a raw material to obtain a purified product; and (2) sequentially melting, quenching, and annealing the purified product obtained in step (1) to obtain the Ge-Sb-Se-Ga chalcogenide glass.

Description

Technical Field

[0001] The present disclosure relates to the technical field of chalcogenide glass, and in particular to a Ge-Sb-Se-Ga chalcogenide glass and a preparation method thereof. Background Art

[0002] For over half a century, chalcogenide glass has been considered an infrared optical material due to its numerous advantages, including excellent infrared transmittance, tunable composition, thermochemical stability, high refractive index, and nonlinear refractive index coefficient. Chalcogenide glass, which began to be developed and applied as an infrared material in the 1950s, boasts low phonon energy, high refractive index, and high infrared transmittance. It has been widely used in military and civilian applications, and has played a significant role in responding to the pandemic.

[0003] However, the hardness of the common chalcogenide glass on the market does not exceed 300 kg / mm 2 The surface is easily scratched or even broken. The hardness of the most widely used commercial glass As2Se3 is only 157 kg / mm 2 Therefore, it is urgent to develop a high-hardness chalcogenide glass. Summary of the Invention

[0004] In view of the shortcomings and problems of the prior art, the present disclosure provides a Ge-Sb-Se-Ga chalcogenide glass to alleviate the defect of the relatively weak hardness of the chalcogenide glass on the market.

[0005] The technical solution adopted by the present disclosure to solve the above technical problems is: a Ge-Sb-Se-Ga chalcogenide glass, including the following components: Ge: 20-40 at%; Ga: 1-10 at%; Sb: 5-20 at%; Se: 40-60 at%.

[0006] As a preferred embodiment, the Ge-Sb-Se-Ga chalcogenide glass comprises the following components: Ge: 25-35 at%; Ga: 3-9 at%; Sb: 8-17 at%; and Se: 43-57 at%.

[0007] The Vickers hardness of the Ge-Sb-Se-Ga chalcogenide glass is 250-400 kg / mm 2 .

[0008] As a preferred embodiment, the Vickers hardness of the Ge-Sb-Se-Ga chalcogenide glass is 300-400 kg / mm 2 .

[0009] The present application also provides a method for preparing the Ge-Sb-Se-Ga chalcogenide glass described in the above technical solution, comprising the following steps:

[0010] step:

[0011] (1) removing impurities and purifying the raw materials to obtain a purified product;

[0012] (2) The purified material obtained in step (1) is melted, quenched and annealed in sequence to obtain Ge-Sb-Se-Ga chalcogenide glass.

[0013] As a preferred embodiment, the purification method in step (1) is any one of vacuum distillation, deoxidizer method and vacuum distillation combined with deoxidizer method.

[0014] As a preferred embodiment, the raw materials in step (1) include Ge, Ga, Sb and Se elements, and the raw materials are placed in a quartz reactor, which is then evacuated and sealed.

[0015] As a preferred embodiment, the purification method in step (1) is vacuum distillation combined with a deoxidizer method.

[0016] As a preferred embodiment, the deoxidizer used in the vacuum distillation combined with deoxidizer method is elemental Mg or elemental Al.

[0017] As a preferred embodiment, the melting temperature in step (2) is 800-950° C., and the melting time is 30-35 hours.

[0018] As a preferred embodiment, the quenching temperature in step (2) is 400-500°C, and the quenching method is air-cooling quenching.

[0019] As a preferred embodiment, the annealing temperature in step (2) is 300-400°C, and the cooling rate of the annealing is 2-10°C / h.

[0020] The Ge-Sb-Se-Ga chalcogenide glass provided in the present application is obtained by doping Ga element on the basis of Ge-Sb-Se glass and obtaining nanocrystals by annealing to increase the hardness of the glass itself, and adjusting the annealing time and doping the Ga element glass to obtain a chalcogenide glass with both high hardness and high transmittance. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The present application will be further described in detail below with reference to the accompanying drawings and preferred embodiments. However, those skilled in the art will appreciate that these drawings are drawn only for the purpose of explaining the preferred embodiments and therefore should not be construed as limiting the scope of the present application. In addition, unless otherwise specified, the drawings are merely schematic representations of the composition or structure of the described objects and may contain exaggerated representations. The drawings are not necessarily drawn to scale.

[0022] Figure 1This is the infrared window transmission curve of the Ge-Sb-Se-Ga chalcogenide glass prepared in Example 1. DETAILED DESCRIPTION

[0023] In order to enable those skilled in the art to better understand the technical solutions of the present disclosure, the present disclosure is described in detail, clearly, and completely in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present disclosure and are not intended to limit the present disclosure.

[0024] The present application provides a Ge-Sb-Se-Ga chalcogenide glass, comprising the following components: Ge: 20-40 at%; Ga: 1-10 at%; Sb: 5-20 at%; and Se: 40-60 at%.

[0025] Preferably, the Ge-Sb-Se-Ga chalcogenide glass provided herein comprises the following components, expressed in atomic percentage: Ge: 25-35 at%; Ga: 3-9 at%; Sb: 8-17 at%; and Se: 43-57 at%. Ge has a high coordination number and, when added to the chalcogenide glass, can increase the hardness of the glass. By controlling the germanium content within the aforementioned range, the chalcogenide glass can be ensured to have a high hardness. Ga is introduced to react with Ge and Se elements after heat treatment to form Ga2Se3, Ga4Se8, and GeSe grains, thereby increasing the hardness of the glass after heat treatment. Sb can improve the clarification effect of the glass, reduce the interference of bubbles, and improve the stability of the glass. Se can form GeSe grains with Ge after heat treatment, thereby increasing the hardness of the glass after heat treatment.

[0026] Furthermore, the Ge-Sb-Se-Ga chalcogenide glass provided in the present application includes the following components, in terms of atomic percentage: Ge: 26-31 at%; Ga: 5-7 at%; Sb: 11-16 at%; and Se: 46-51 at%.

[0027] The Vickers hardness of the Ge-Sb-Se-Ga chalcogenide glass is 250-400 kg / mm 2 This chalcogenide glass has higher hardness than the existing commercial infrared chalcogenide glass materials on the market.

[0028] Preferably, the Vickers hardness of the Ge-Sb-Se-Ga chalcogenide glass is 300-400 kg / mm 2 .

[0029] The present application increases the hardness of the glass itself by doping Ga element on the basis of Ge-Sb-Se glass and obtaining nanocrystals through annealing, and adjusts the annealing time and Ga element doped glass to obtain chalcogenide glass with both high hardness and high transmittance.

[0030] The present application also provides a method for preparing the Ge-Sb-Se-Ga chalcogenide glass described in the above technical solution, comprising the following steps:

[0031] step:

[0032] (1) removing impurities and purifying the raw materials to obtain a purified product: the raw materials include Ge, Ga, Sb and Se elements, placing the raw materials in a quartz reactor, evacuating the reactor and sealing the reactor, and removing impurities and purifying the raw materials to obtain a purified product;

[0033] (2) The purified material obtained in step (1) is melted, quenched and annealed in sequence to obtain Ge-Sb-Se-Ga chalcogenide glass.

[0034] In the present application, the Ge is preferably high-purity Ge; the Ga is preferably high-purity Ga; the Sb is preferably high-purity Sb; and the Se is preferably high-purity Se. The purity of each of Ge, Ga, Sb, and Se is preferably independently ≥ 5N. By selecting high-purity single elements as raw materials, the present invention can reduce the content of impurities and oxides in the raw materials, thereby further improving the purity of the glass.

[0035] In the present application, the purification is preferably performed in a quartz reactor, preferably an H-shaped double-barreled quartz ampoule. In the present application, the H-shaped double-barreled quartz ampoule comprises a raw material tube, a purification tube, and a connecting tube connecting the raw material tube and the purification tube. One end of the raw material tube is provided with an opening, or both one end of the raw material tube and one end of the purification tube are provided with openings. The present application utilizes the above-described device to facilitate sealing the opening of the raw material tube during purification, thereby providing a vacuum environment for the mixture and deoxidizer placed in the H-shaped double-barreled quartz ampoule, preventing oxidation of the raw materials and the introduction of impurities, thereby reducing the extrinsic absorption of the chalcogenide glass in the infrared region.

[0036] In the present application, the quartz reactor is preferably pretreated with dehydroxylation; the dehydroxylation pretreatment process preferably includes: sequentially cleaning the quartz reactor with hydrofluoric acid, deionized water, and anhydrous ethanol, and finally placing it in a dry oven for complete drying. By pretreating the quartz reactor with dehydroxylation, the present application can prevent the quartz reactor from introducing impurity oxygen into the reaction.

[0037] In this application, the quartz reactor is preferably preheated and vacuumed before purification; the preheating and vacuuming are preferably performed simultaneously. In this application, the preheating temperature is preferably 50-100°C; the vacuum degree of the vacuuming is preferably ≥5×10 -5 Pa, more preferably 5×10 -5 ~1×10 -3The vacuuming time is preferably ≥3h. The present application can avoid the influence of oxygen in the air by performing purification in a vacuum atmosphere; the vacuum degree of the quartz reactor can meet the requirements through the above process.

[0038] In the present application, when one end of the raw material tube is provided with an opening, the vacuuming method is preferably: adding the raw material into the raw material tube through the opening on the raw material tube of the quartz reactor, then vacuuming, and finally sealing the opening on the raw material tube; when one end of the raw material tube and one end of the purification tube are both provided with openings, the vacuuming method is preferably: adding the raw material into the raw material tube through the opening on the raw material tube of the quartz reactor, sealing the opening on the raw material tube, then vacuuming through the opening on the purification tube, and finally sealing the opening on the purification tube. In the present invention, an oxyhydrogen flame or an oxyacetylene flame is preferably used for the sealing. By adopting the above-mentioned method for sealing, the present application can reduce the impurity oxygen introduced into the reaction during the sealing process.

[0039] In the present application, the purification method is preferably any one of vacuum distillation, a deoxidizer method, and a vacuum distillation combined with a deoxidizer method, with vacuum distillation combined with a deoxidizer method being more preferred. Purifying the raw materials in the present application can eliminate [-OH] and [HOH] impurities in the chalcogenide glass, thereby reducing the impact of extrinsic absorption losses in the chalcogenide glass on its infrared properties.

[0040] In the present application, the vacuum distillation combined with deoxidizer method preferably comprises the following steps:

[0041] 1) Ge, Ga, Sb and Se are mixed to obtain a mixture, and then a scavenger is added to the mixture to obtain a mixture to be purified;

[0042] 2) adding the mixture to be purified obtained in step (1) into a quartz reactor, and then placing the quartz reactor into a dual-temperature zone distillation furnace for purification to obtain a purified mixture.

[0043] In the present application, the oxygen scavenger is preferably elemental Mg or elemental Al. The amount of the oxygen scavenger used in the present application is preferably 0.03-0.1 wt % of the mixture, more preferably 0.05-0.08 wt %. The present application uses the above substances as oxygen scavengers. Elemental Mg or elemental Al are both active elements that preferentially form bonds with oxygen, thereby eliminating XO bonds present in chalcogenide glass and causing a series of harmful absorptions in the near, mid, and far infrared regions. Furthermore, the oxides generated by the oxygen scavengers have a low vapor pressure and can volatilize without remaining in the chalcogenide glass, thereby not affecting the composition of the chalcogenide glass. By controlling the amount of oxygen scavenger used, it is possible to avoid the problem of insufficient oxygen impurities in the chalcogenide glass due to insufficient use, and to avoid the problem of glass crystallization and devitrification during glass drawing due to excessive use of the oxygen scavenger.

[0044] After obtaining the material to be purified, the present application preferably adds the material to be purified into a quartz reactor, and then places the quartz reactor into a dual-temperature zone distillation furnace for purification to obtain a purified material.

[0045] In the present application, the cold end temperature of the dual-zone distillation furnace is preferably 300-500° C., more preferably 350-450° C.; the hot end temperature of the dual-zone distillation furnace is preferably 800-950° C., more preferably 850-900° C. The present invention purifies the raw material in a dual-zone distillation furnace, utilizing the large difference in vapor pressure between the elemental substance and its oxide at a certain temperature to perform a distillation treatment to remove oxygen and other non-volatile impurities, thereby achieving a deoxygenation effect.

[0046] After obtaining the purified material, the present application sequentially melts, quenches and anneals the purified material to obtain nanocrystalline high-hardness chalcogenide glass.

[0047] In the present application, the melting temperature is preferably 800-950°C, and the melting time is preferably 30-35 hours. By controlling the melting parameters, the present application can completely melt and mix the raw materials together to form a glass liquid state, thereby forming a chalcogenide glass with short-range order and long-range disorder.

[0048] After the melting is completed, the present application preferably cools the molten product naturally to a quenching temperature for quenching. The present application does not specifically limit the method of natural cooling, which can be determined according to the technical common sense of those skilled in the art.

[0049] In the present application, the quenching temperature is preferably 400-500°C, and the quenching method is preferably air-cooled quenching. There is no specific limitation on the quenching time; quenching to room temperature is sufficient. Through quenching, the glass structure is characterized by short-range order and long-range disorder, resulting in excellent performance.

[0050] In the present application, the annealing temperature is preferably 300-400°C, and the cooling rate is preferably 2-10°C / h. The present invention reduces or eliminates the uneven permanent thermal stress formed in the chalcogenide glass during the quenching process by annealing the chalcogenide glass, thereby improving the mechanical strength and thermal stability of the chalcogenide glass.

[0051] The present application purifies the raw materials to remove excess impurities in the raw materials, and then sequentially performs melting, quenching and annealing. The components are evenly mixed by melting, and a short-range ordered and long-range disordered glass is formed by quenching. The mechanical and physical properties of the glass are further improved by annealing, thereby obtaining a high-hardness chalcogenide glass. The preparation method is simple and convenient for large-scale industrial production.

[0052] The present application provides the application of the nanocrystalline high-hardness chalcogenide glass described in the above technical solution or the nanocrystalline high-hardness chalcogenide glass prepared by the preparation method described in the above technical solution in infrared optics.

[0053] This application does not specifically limit the specific manner of the application, which can be determined based on the technical common sense of those skilled in the art.

[0054] The following will be combined with the embodiments of this application to clearly and completely describe the technical solutions in this application. Obviously, the embodiments described are only some of the embodiments of this application, not all of them. Based on the embodiments of this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0055] Example 1

[0056] A nanocrystalline high-hardness chalcogenide glass composed of the following components: Ge: 26 at; Ga: 5 at; Sb: 12 at; Se: 57 at;

[0057] The method for preparing the nanocrystalline high-hardness chalcogenide glass comprises the following steps:

[0058] (1) mixing the high-purity Ge, high-purity Ga, high-purity Sb and high-purity Se and purifying them by vacuum distillation combined with a deoxidizer method to obtain a purified mixture;

[0059] (2) Melting the purified mixture obtained in step (1), then naturally cooling it to a quenching temperature for quenching, and finally heating it to an annealing temperature for annealing to obtain high-hardness Ge-Ga-Sb-Se; the melting temperature is 950°C, and the melting time is 35h; the quenching temperature is 450°C, and the quenching method is air-cooled quenching; the annealing temperature is 370°C, and the annealing cooling rate is 10°C / h;

[0060] The vacuum distillation combined with deoxidizer method consists of the following steps:

[0061] 1) Ge source, Ga source, Sb source and Se source are mixed to obtain a mixture, and a deoxidizer is added to the mixture to obtain a mixture to be purified; the purity of the high-purity Ge, high-purity Ga, high-purity Sb and high-purity Se is 5N; the deoxidizer is elemental Mg, and the amount of the deoxidizer is 0.1wt% of the mixture;

[0062] 2) adding the mixture to be purified obtained in step 1) into the raw material tube through the opening on the raw material tube of the H-shaped double-tube quartz ampoule, then evacuating and preheating simultaneously, finally sealing the opening on the raw material tube, and then placing the quartz reactor in a dual-temperature zone distillation furnace for purification; the quartz reactor undergoes dehydroxylation pretreatment, and the dehydroxylation pretreatment process comprises sequentially cleaning the quartz reactor with hydrofluoric acid, deionized water, and anhydrous ethanol, and finally placing the quartz reactor in a dry oven for complete drying; the preheating temperature is 90° C.; the vacuum degree of the evacuation is 1×10 -3 Pa, the vacuuming time is 3h; the cold end temperature of the dual-temperature zone distillation furnace is 400°C, and the hot end temperature of the dual-temperature zone distillation furnace is 950°C.

[0063] The performance of the high hardness Ge-Ga-Sb-Se prepared in Example 1 was tested, and the results are as follows: Figure 1 shown.

[0064] Figure 1 This is the transmittance of the high-hardness Ge-Ga-Sb-Se infrared window prepared in Example 1.

[0065] The high-hardness Ge-Ga-Sb-Se prepared by the present invention has an infrared window transmittance of 55%. The high-hardness chalcogenide glass of the nanocrystalline was tested and the glass transition temperature was 281 degrees Celsius and the hardness was 343.5 kg / mm 2 , which is 2.5 times that of As2Se3 glass.

[0066] Example 2

[0067] A nanocrystalline high-hardness chalcogenide glass composed of the following components: Ge: 26 at; Ga: 7 at; Sb: 11 at; Se: 56 at;

[0068] The method for preparing the nanocrystalline high-hardness chalcogenide glass comprises the following steps:

[0069] (2) mixing the high-purity Ge, high-purity Ga, high-purity Sb and high-purity Se and purifying them by vacuum distillation combined with a deoxidizer method to obtain a purified mixture;

[0070] (2) Melting the purified mixture obtained in step (1), then naturally cooling it to a quenching temperature for quenching, and finally heating it to an annealing temperature for annealing to obtain high-hardness Ge-Ga-Sb-Se; the melting temperature is 950°C, and the melting time is 30h; the quenching temperature is 450°C, and the quenching method is air-cooled quenching; the annealing temperature is 360°C, and the annealing cooling rate is 10°C / h;

[0071] The vacuum distillation combined with deoxidizer method consists of the following steps:

[0072] 1) Ge source, Ga source, Sb source and Se source are mixed to obtain a mixture, and a deoxidizer is added to the mixture to obtain a mixture to be purified; the purity of the high-purity Ge, high-purity Ga, high-purity Sb and high-purity Se is 5N; the deoxidizer is elemental Mg, and the amount of the deoxidizer is 0.1wt% of the mixture;

[0073] 2) adding the mixture to be purified obtained in step 1) into the raw material tube through the opening on the raw material tube of the H-shaped double-tube quartz ampoule, then evacuating and preheating simultaneously, finally sealing the opening on the raw material tube, and then placing the quartz reactor in a dual-temperature zone distillation furnace for purification; the quartz reactor undergoes dehydroxylation pretreatment, and the dehydroxylation pretreatment process comprises sequentially cleaning the quartz reactor with hydrofluoric acid, deionized water, and anhydrous ethanol, and finally placing the quartz reactor in a dry oven for complete drying; the preheating temperature is 90° C.; the vacuum degree of the evacuation is 1×10 -3 Pa, the vacuuming time is 3h; the cold end temperature of the dual-temperature zone distillation furnace is 400°C, and the hot end temperature of the dual-temperature zone distillation furnace is 950°C.

[0074] The high hardness chalcogenide glass of the nano-crystal was tested and its glass transition temperature was 310 degrees Celsius and its hardness was 331.2 kg / mm 2 .

[0075] Example 3

[0076] A nanocrystalline high-hardness chalcogenide glass composed of the following components: Ge: 25 at%; Ga: 9 at%; Sb: 11 at%; Se: 55 at%;

[0077] The method for preparing the nanocrystalline high-hardness chalcogenide glass comprises the following steps:

[0078] (3) mixing the high-purity Ge, high-purity Ga, high-purity Sb and high-purity Se, and purifying the mixture by vacuum distillation combined with a deoxidizer method to obtain a purified mixture;

[0079] (2) Melting the purified mixture obtained in step (1), then naturally cooling it to a quenching temperature for quenching, and finally heating it to an annealing temperature for annealing to obtain high-hardness Ge-Ga-Sb-Se; the melting temperature is 950°C, and the melting time is 30h; the quenching temperature is 450°C, and the quenching method is air-cooled quenching; the annealing temperature is 340°C, and the annealing cooling rate is 10°C / h;

[0080] The vacuum distillation combined with deoxidizer method consists of the following steps:

[0081] 1) Ge source, Ga source, Sb source and Se source are mixed to obtain a mixture, and a deoxidizer is added to the mixture to obtain a mixture to be purified; the purity of the high-purity Ge, high-purity Ga, high-purity Sb and high-purity Se is 5N; the deoxidizer is elemental Mg, and the amount of the deoxidizer is 0.1wt% of the mixture;

[0082] 2) adding the mixture to be purified obtained in step 1) into the raw material tube through the opening on the raw material tube of the H-shaped double-tube quartz ampoule, then evacuating and preheating simultaneously, finally sealing the opening on the raw material tube, and then placing the quartz reactor in a dual-temperature zone distillation furnace for purification; the quartz reactor undergoes dehydroxylation pretreatment, and the dehydroxylation pretreatment process comprises sequentially cleaning the quartz reactor with hydrofluoric acid, deionized water, and anhydrous ethanol, and finally placing the quartz reactor in a dry oven for complete drying; the preheating temperature is 90° C.; the vacuum degree of the evacuation is 1×10 -3 Pa, the vacuuming time is 3h; the cold end temperature of the dual-temperature zone distillation furnace is 400°C, and the hot end temperature of the dual-temperature zone distillation furnace is 950°C.

[0083] The high hardness chalcogenide glass of the nano-crystal was tested and its glass transition temperature was 287 degrees Celsius and its hardness was 322.2 kg / mm 2 .

[0084] Comparative Example 1

[0085] A nanocrystalline high-hardness chalcogenide glass composed of the following components: Ge: 10 at%; Sb: 30 at%; Se: 60 at%;

[0086] The method for preparing the nanocrystalline high-hardness chalcogenide glass comprises the following steps:

[0087] (4) mixing the high-purity Ge, high-purity Sb, and high-purity Se, and purifying the mixture by vacuum distillation combined with a deoxidizer method to obtain a purified mixture;

[0088] (2) Melting the purified mixture obtained in step (1), then naturally cooling it to a quenching temperature for quenching, and finally heating it to an annealing temperature for annealing to obtain Ge-Sb-Se glass; the melting temperature is 900°C, and the melting time is 30 hours; the quenching temperature is 500°C, and the quenching method is air-cooled quenching; the annealing temperature is 200°C, and the annealing cooling rate is 5°C / h;

[0089] The vacuum distillation combined with deoxidizer method consists of the following steps:

[0090] 1) A Ge source, an Sb source, and a Se source are mixed to obtain a mixture, and a deoxidizer is added to the mixture to obtain a mixture to be purified; the purity of the high-purity Ge, high-purity Sb, and high-purity Se is 5N; the deoxidizer is elemental Mg, and the amount of the deoxidizer is 0.1wt% of the mixture;

[0091] 2) adding the mixture to be purified obtained in step 1) into the raw material tube through the opening on the raw material tube of the H-shaped double-tube quartz ampoule, then evacuating and preheating simultaneously, finally sealing the opening on the raw material tube, and then placing the quartz reactor in a dual-temperature zone distillation furnace for purification; the quartz reactor undergoes dehydroxylation pretreatment, and the dehydroxylation pretreatment process comprises sequentially cleaning the quartz reactor with hydrofluoric acid, deionized water, and anhydrous ethanol, and finally placing the quartz reactor in a dry oven for complete drying; the preheating temperature is 90° C.; the vacuum degree of the evacuation is 1×10 -3 Pa, the vacuuming time is 3h; the cold end temperature of the dual-temperature zone distillation furnace is 400°C, and the hot end temperature of the dual-temperature zone distillation furnace is 950°C.

[0092] The hardness of the nanocrystalline high-hardness chalcogenide glass was tested, and the result was 176.1 kg / mm 2 .

[0093] Comparative Example 2

[0094] A nanocrystalline high-hardness chalcogenide glass composed of the following components: Ge: 28 at; Sb: 12 at; Se: 60 at;

[0095] The method for preparing the nanocrystalline high-hardness chalcogenide glass comprises the following steps:

[0096] (5) mixing the high-purity Ge, high-purity Sb, and high-purity Se, and purifying the mixture by vacuum distillation combined with a deoxidizer method to obtain a purified mixture;

[0097] (2) Melting the purified mixture obtained in step (1), then naturally cooling it to a quenching temperature for quenching, and finally heating it to an annealing temperature for annealing to obtain Ge-Sb-Se glass; the melting temperature is 900°C, and the melting time is 30 hours; the quenching temperature is 500°C, and the quenching method is air cooling quenching; the annealing temperature is 270°C, and the annealing cooling rate is 5°C / h;

[0098] The vacuum distillation combined with deoxidizer method consists of the following steps:

[0099] 1) A Ge source, an Sb source, and a Se source are mixed to obtain a mixture, and a deoxidizer is added to the mixture to obtain a mixture to be purified; the purity of the high-purity Ge, high-purity Sb, and high-purity Se is 5N; the deoxidizer is elemental Mg, and the amount of the deoxidizer is 0.1wt% of the mixture;

[0100] 2) adding the mixture to be purified obtained in step 1) into the raw material tube through the opening on the raw material tube of the H-shaped double-tube quartz ampoule, then evacuating and preheating simultaneously, finally sealing the opening on the raw material tube, and then placing the quartz reactor in a dual-temperature zone distillation furnace for purification; the quartz reactor undergoes dehydroxylation pretreatment, and the dehydroxylation pretreatment process comprises sequentially cleaning the quartz reactor with hydrofluoric acid, deionized water, and anhydrous ethanol, and finally placing the quartz reactor in a dry oven for complete drying; the preheating temperature is 90° C.; the vacuum degree of the evacuation is 1×10 -3 Pa, the vacuuming time is 3h; the cold end temperature of the dual-temperature zone distillation furnace is 400°C, and the hot end temperature of the dual-temperature zone distillation furnace is 950°C.

[0101] The hardness of the nanocrystalline high-hardness chalcogenide glass was tested, and the result was 222.7 kg / mm 2 .

[0102] By comparing Examples 1 to 3 with Comparative Examples 1 and 2, it can be seen that the hardness of the nanocrystalline glass obtained after Ga doping and heat treatment far exceeds that of the glass obtained by conventional annealing, and is 2.5 times that of the common glass As2Se3.

[0103] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

[0104] The present application has been described in detail above. Specific examples have been used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is intended only to facilitate understanding of the present application and its core concepts. It should be noted that, without departing from the principles of the present application, a number of improvements and modifications may be made to the present application by a person skilled in the art, and such improvements and modifications shall fall within the scope of protection of the claims of the present application.

Claims

1. A method for preparing Ge-Sb-Se-Ga chalcogenide glass, characterized in that: The following steps are involved: (1) removing impurities and purifying the raw materials to obtain a purified product; (2) melting, quenching and annealing the purified product obtained in step (1) to obtain Ge-Sb-Se-Ga chalcogenide glass; The raw materials are placed in a quartz reactor; the quartz reactor is pretreated by dehydroxylation; the quartz reactor is preheated and vacuumed; the preheating and vacuuming are performed simultaneously; The chalcogenide glass comprises the following components: Ge: 20-40 at%; Ga: 3~9 at%; Sb: 5~20 at%; Se: 40~60at%; The melting temperature in step (2) is 800-950°C and the melting time is 30-35h; The quenching temperature in step (2) is 400-500°C, and the quenching method is air-cooling quenching; The annealing temperature in step (2) is 300-400°C, and the cooling rate of the annealing is 2-10°C / h.

2. The method for preparing Ge-Sb-Se-Ga chalcogenide glass according to claim 1, wherein: It includes the following components: Ge: 25~35 at%; Sb: 8~17 at%; Se: 43~57 at%.

3. The method for preparing Ge-Sb-Se-Ga chalcogenide glass according to claim 1, wherein: The Vickers hardness of the Ge-Sb-Se-Ga chalcogenide glass is 250-400 kg / mm 2 .

4. The method for preparing Ge-Sb-Se-Ga chalcogenide glass according to claim 1, wherein: The purification method in step (1) is any one of vacuum distillation, deoxidizer method and vacuum distillation combined with deoxidizer method.

5. The method for preparing Ge-Sb-Se-Ga chalcogenide glass according to claim 4, characterized in that: The deoxidizer used in the vacuum distillation combined with deoxidizer method is elemental Mg or elemental Al.

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