Ge-as-se-cscl glass-ceramics and method for producing the same

Abstract

The application provides a Ge-As-Se-CsCl glass ceramic and a preparation method thereof, which comprises a base and CsCl crystals uniformly dispersed in the base; the base is a Ge-As-Se chalcogenide glass; the CsCl crystals are uniformly dispersed in the base in a nano form; the molar composition of the Ge-As-Se-CsCl glass ceramic is represented by a chemical formula as follows: (1-y)Ge 0.2 As x Se (0.8‑x) -yCsCl, the range of x is 0.1-0.7, and the range of y is 0.05-0.2. Compared with the prior art, the Ge-As-Se-CsCl glass ceramic prepared by two-stage heat treatment crystallization disclosed by the application can ensure that the Ge-As-Se-CsCl glass ceramic has good infrared transmittance, can greatly improve the hardness of the Ge-As-Se-CsCl glass ceramic, and widens the application range of the chalcogenide glass ceramic.

Description

Technical Field

[0001] The present invention belongs to the field of semiconductor materials, and in particular relates to a Ge-As-Se-CsCl glass ceramic and a preparation method thereof. Background Art

[0002] The booming development of infrared thermal imaging in various fields has garnered significant attention from researchers. It can reveal the temperature field of an object's surface, extending the human eye's perception beyond visible light to the invisible infrared. This technology is crucial for defense, military, environmental monitoring, medical imaging, and space exploration. Current mid- and far-infrared optical devices are primarily made of materials such as silicon, germanium, zinc selenide, fluoride glass, and chalcogenide glass. Compared to visible light, the range of materials available for infrared is much narrower. These materials exhibit excellent light transmittance in the mid-infrared band, with a refractive index ranging from approximately 1.38 to 4.

[0003] Due to the mature micro- and nano-fabrication processes for silicon and germanium, the fabrication of infrared lenses based on these materials has developed rapidly, finding widespread application in the near- and mid-infrared. However, silicon's absorption increases dramatically in the far-infrared beyond 8μm, severely impacting transmittance. Germanium's high raw material cost, low processing efficiency, and significant thermal effects significantly limit its civilian application. Chalcogenide glass, a glass material containing at least one of the Group VI elements S, Se, and Te, can meet application requirements such as a wide operating band, a wide refractive index range, low thermal expansion, a low temperature coefficient of refractive index, and a high dielectric constant. It also offers the advantage of adjustable composition. Chalcogenide glass boasts the widest transmittance and highest refractive index of all infrared glass materials, and the processes for preparing chalcogenide thin films and etching structures are relatively mature.

[0004] While chalcogenide glass offers numerous advantages in infrared imaging, its weak chemical bonding results in poor mechanical properties. Its hardness is only about one-seventh that of a single crystal of germanium, significantly limiting its practical applications. Therefore, improving the mechanical strength of chalcogenide glass is a key research direction for applications. Currently, two main methods are commonly used to enhance the mechanical properties of chalcogenide glass-ceramics. One approach is to enhance the strength of covalent bonds within chalcogenide glass by adjusting its composition. For example, increasing the Ge content causes Se and Te to preferentially bond with it, resulting in a large number of strong Ge-Se and Ge-Te bonds within the glass network and a significant reduction in weaker bonds such as Se-Se, Te-Te, and Se-Te. This significantly improves the glass network strength of the chalcogenide film. However, this method is limited to the glass-forming region. The other approach is to precipitate crystals through heat treatment to form glass-ceramics. Crystals possess significantly greater mechanical strength than amorphous glass. Introducing an appropriate amount of crystals into the glass matrix can significantly enhance the mechanical strength of glass-ceramics without compromising transmittance or refractive index. However, it is difficult to control the size and distribution of crystals precipitated by heat treatment. Summary of the Invention

[0005] In order to solve the above-mentioned technical problems, the present invention provides a Ge-As-Se-CsCl glass ceramic with high hardness and controllable crystal precipitation and a preparation method thereof.

[0006] The present invention provides a Ge-As-Se-CsCl glass ceramic, which includes a matrix and CsCl crystals uniformly dispersed in the matrix. The matrix is ​​Ge-As-Se chalcogenide glass, and the CsCl crystals are uniformly dispersed in the matrix in nanometer form. The molar composition of the Ge-As-Se-CsCl glass ceramic is expressed as follows according to the chemical formula: (1-y)Ge 0.2 As x Se (0.8-x) -yCsCl, where x ranges from 0.1 to 0.7 and y ranges from 0.05 to 0.2.

[0007] In some embodiments, the grain size of the CsCl crystals is 5-30 nm.

[0008] A second object of the present invention is to provide a method for preparing the above-mentioned Ge-As-Se-CsCl glass-ceramic, the preparation method specifically comprising the following steps:

[0009] S1, according to the chemical formula (1-y)Ge 0.2 As x Se (0.8-x)- yCsCl, respectively, Ge element, As element, Se element, CsCl compound are weighed as raw materials, the weighed raw materials are mixed uniformly and then placed in a quartz ampoule, the quartz ampoule is vacuumized to a vacuum degree less than 10 -3 Pa, and then the quartz ampoule is sealed by an acetylene-oxygen flame;

[0010] S2, the quartz ampoule in step S1 is placed in a swing heating furnace for glass melting treatment, then the quartz ampoule is taken out and sequentially subjected to quenching treatment and annealing treatment, and then is cooled to below 50 DEG C in the furnace and taken out, so that a base glass is obtained in the quartz ampoule;

[0011] S3, the quartz ampoule in step S2 is placed in a crystallization furnace, two-stage crystallization heat treatment is performed on the base glass, and then the quartz ampoule is taken out after being cooled to below 50 DEG C in the furnace, so that a Ge-As-Se-CsCl glass ceramic is obtained.

[0012] In some embodiments, in the step S2, the specific steps of the glass melting treatment are as follows: the temperature is raised to a glass melting temperature of 830-950 DEG C at a temperature raising rate of 80-100 DEG C / h, and the temperature is kept at the glass melting temperature for 8-18 hours.

[0013] In some embodiments, in the step S2, the specific steps of the quenching treatment are as follows: the quartz ampoule is quenched in ice water for 3-10 s, or is quenched by compressed air for 3-10 s.

[0014] In some embodiments, in the step S2, the specific steps of the annealing treatment are as follows: the quartz ampoule is placed in an annealing furnace at 180-205 DEG C for 2-5 h.

[0015] In some embodiments, in the step S3, the specific steps of the two-stage crystallization heat treatment are as follows: the temperature is raised to a first-stage crystallization heat treatment temperature for crystallization heat treatment for 5-10 min, CsCl nanocrystals are precipitated in the base glass, and then the temperature is rapidly lowered to a second-stage crystallization heat treatment temperature for crystallization heat treatment for 10-100 h.

[0016] Compared with the prior art, the Ge-As-Se-CsCl glass ceramic prepared by the two-stage heat treatment crystallization disclosed in the application is firstly treated at a high temperature for a short time to form a large number of crystal nuclei, and then is rapidly lowered to a low temperature for a long time crystallization, so that the precipitated crystal grains are small and uniformly distributed in the base glass, which not only ensures that the Ge-As-Se-CsCl glass ceramic has good infrared transmittance, but also greatly improves the hardness of the Ge-As-Se-CsCl glass ceramic, and further widens the application range of the chalcogenide glass ceramic.

[0017] In some embodiments, the temperature of the first crystallization heat treatment is 80-100° C. higher than the glass transition temperature of the base glass, and the temperature of the second crystallization heat treatment is 10-20° C. higher than the glass transition temperature of the base glass.

[0018] Compared with the prior art, the preparation method of the high-hardness, two-stage heat-treated crystallized Ge-As-Se glass-ceramics disclosed in the present invention can achieve effective control of the grain size and grain distribution of the precipitated grains. The grain size of the precipitated CsCl crystals is controlled within the range of 5-30nm and is evenly distributed in the Ge-As-Se glass matrix. The preparation method of the present invention is simple to operate, the process is controllable, and has good stability. The prepared Ge-As-Se-CsCl glass-ceramics have both good infrared transmittance and high hardness.

[0019] In some embodiments, the first stage of crystallization heat treatment temperature is 300-350°C, and the second stage of crystallization heat treatment temperature is 230-240°C. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl glass ceramic indentation test diagram. DETAILED DESCRIPTION

[0021] To make the above-mentioned objects, features, and advantages of the present invention more clearly understood, specific embodiments of the present invention are described in detail below. It should be noted that the following embodiments are only intended to illustrate the implementation methods and typical parameters of the present invention, and are not intended to limit the parameter ranges described in the present invention. Reasonable variations derived therefrom are still within the scope of protection of the claims of the present invention.

[0022] It should be noted that the endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be considered to be specifically disclosed herein.

[0023] Unless otherwise defined, all terms, symbols and other scientific terms used herein are intended to have the same meaning as commonly understood by those skilled in the art to which the present invention belongs. In some cases, terms with conventional meanings are defined herein for the purpose of clarification or ease of reference, and such definitions herein should not be construed as indicating significant differences from conventional understandings in the art. The technical methods described or cited herein are generally well understood by those skilled in the art and are adopted by conventional methods. Unless otherwise stated, the use of commercially available kits, reagents and instruments was carried out in accordance with the protocols and parameters given by the manufacturers.

[0024] The technical effects of the present invention are described below with reference to specific embodiments.

[0025] Example 1

[0026] This embodiment provides a glass ceramic. The chemical formula of the glass ceramic in this embodiment is 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl.

[0027] In this embodiment, 0.92Ge 0.2 As 0.2 Se 0.6 The preparation method of -0.08CsCl glass ceramics includes the following two steps:

[0028] Step 1: Preparation of base glass: Weigh Ge, As, Se and CsCl as raw materials respectively, and the ratio is based on the chemical formula 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl; Mix the weighed raw materials evenly and place them in a quartz ampoule, evacuate the quartz ampoule to a vacuum degree of less than 10 -3 Pa, and then sealing the quartz ampoule with an acetylene-oxygen flame; placing the quartz ampoule in a swing heating furnace for glass melting treatment, heating the temperature at a heating rate of 100°C / h to a glass melting temperature of 900°C, and keeping it at the glass melting temperature for 15 hours, then taking out the quartz ampoule and quenching it in ice water or quenching it with compressed air for 5 seconds, and then quickly placing it in an annealing furnace at 200°C for 3 hours, cooling it to below 50°C with the furnace and taking it out of the furnace, thus obtaining the basic glass in the quartz ampoule;

[0029] Step 2, Preparation of Ge-As-Se-CsCl Glass-Ceramics: Place a quartz ampoule in a crystallization furnace and perform a two-stage crystallization heat treatment on the base glass. The first stage of the crystallization heat treatment is at a temperature of 330°C. The crystallization heat treatment is performed at this temperature for 10 minutes to precipitate CsCl nanocrystals inside the base glass. Then, the second stage of the crystallization temperature is rapidly lowered to 240°C. The crystallization heat treatment is performed at this temperature for 50 hours. Finally, the base glass is cooled to below 50°C and removed from the furnace. The quartz ampoule is removed to obtain a Ge-As-Se-CsCl nanocrystalline composite chalcogenide glass-ceramic material.

[0030] Example 2

[0031] This embodiment provides a glass ceramic. The chemical formula of the glass ceramic in this embodiment is 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl.

[0032] The preparation method of the glass ceramics in this embodiment is different from that in embodiment 1 only in that the temperature of the first stage of crystallization heat treatment in step 2 is 340° C. The rest is the same as in embodiment 1 and will not be described again here.

[0033] Example 3

[0034] This embodiment provides a glass ceramic. The chemical formula of the glass ceramic in this embodiment is 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl.

[0035] The preparation method of the glass ceramics in this embodiment is different from that in embodiment 1 only in that the temperature of the first stage of crystallization heat treatment in step 2 is 350° C. The rest is the same as in embodiment 1 and will not be described again here.

[0036] Example 4

[0037] This embodiment provides a glass ceramic. The chemical formula of the glass ceramic in this embodiment is 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl.

[0038] In this embodiment, 0.92Ge 0.2 As 0.2 Se 0.6 The preparation method of -0.08CsCl glass ceramics includes the following two steps:

[0039] Step 1: Preparation of base glass: Weigh Ge, As, Se and CsCl as raw materials respectively, and the ratio is based on the chemical formula 0.92Ge 0.2 As0.2 Se 0.6 -0.08CsCl; the weighed raw materials were mixed uniformly and then placed in a quartz ampoule, the quartz ampoule was vacuumized to a vacuum degree less than 10 -3 Pa, and then the quartz ampoule was sealed by an acetylene-oxygen flame; the quartz ampoule was placed in a rocking furnace for glass melting treatment, and was heated to a glass melting temperature of 900℃ at a heating rate of 100℃ / h, and was kept at the glass melting temperature for 15 hours, after which the quartz ampoule was taken out, quenched in ice water or quenched by compressed air for 5 seconds, and then quickly placed in an annealing furnace at 200℃ for treatment for 3 hours, and was cooled in the furnace to below 50℃ and taken out, so that the base glass was obtained in the quartz ampoule;

[0040] Step two, preparation of the Ge-As-Se-CsCl glass ceramic: the quartz ampoule was placed in a crystallization furnace, and the base glass was subjected to two-stage crystallization heat treatment, the first-stage crystallization heat treatment temperature was 350℃, the first-stage crystallization heat treatment time was 5 minutes, CsCl nanocrystals were precipitated in the base glass, then the second-stage crystallization temperature was quickly lowered to 240℃, and the base glass was subjected to crystallization heat treatment at this temperature for 50 hours, and finally the base glass was cooled in the furnace to below 50℃ and taken out, and the quartz ampoule was removed, so that the Ge-As-Se-CsCl nanocrystal composite chalcogenide glass ceramic material was obtained.

[0041] Example 5

[0042] This example provides a glass ceramic, and the chemical formula of the glass ceramic in this example is 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl.

[0043] The preparation method of the glass ceramic in this example is different from that in Example 4 only in that the first-stage crystallization heat treatment time in Step two is 8 minutes, and the other steps are the same as those in Example 4, which will not be repeated here.

[0044] Example 6

[0045] This example provides a glass ceramic, and the chemical formula of the glass ceramic in this example is 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl.

[0046] The preparation method of the 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl glass ceramic in this example includes the following two steps:

[0047] Step 1: Preparation of base glass: Weigh Ge, As, Se and CsCl as raw materials respectively, and the ratio is based on the chemical formula 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl; Mix the weighed raw materials evenly and place them in a quartz ampoule, evacuate the quartz ampoule to a vacuum degree of less than 10 -3 Pa, and then sealing the quartz ampoule with an acetylene-oxygen flame; placing the quartz ampoule in a swing heating furnace for glass melting treatment, heating the temperature at a heating rate of 100°C / h to a glass melting temperature of 900°C, and keeping it at the glass melting temperature for 15 hours, then taking out the quartz ampoule and quenching it in ice water or quenching it with compressed air for 5 seconds, and then quickly placing it in an annealing furnace at 200°C for 3 hours, cooling it to below 50°C with the furnace and taking it out of the furnace, thus obtaining the basic glass in the quartz ampoule;

[0048] Step 2, Preparation of Ge-As-Se-CsCl Glass-Ceramics: Place a quartz ampoule in a crystallization furnace and perform a two-stage crystallization heat treatment on the base glass. The first stage of the crystallization heat treatment is at a temperature of 350°C. The crystallization heat treatment is performed at this temperature for 10 minutes to precipitate CsCl nanocrystals inside the base glass. The second stage of the crystallization heat treatment is at a temperature of 230°C. The crystallization heat treatment is performed at this temperature for 50 hours. Finally, the base glass is cooled to below 50°C and removed from the furnace. The quartz ampoule is removed to obtain a Ge-As-Se-CsCl nanocrystalline composite chalcogenide glass-ceramic material.

[0049] Example 7

[0050] This embodiment provides a glass ceramic. The chemical formula of the glass ceramic in this embodiment is 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl.

[0051] The preparation method of the glass ceramics in this embodiment differs from that in embodiment 6 only in that the second stage crystallization temperature in step 2 is 235° C. The rest is the same as in embodiment 6 and will not be described again here.

[0052] Example 8

[0053] This embodiment provides a glass ceramic. The chemical formula of the glass ceramic in this embodiment is 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl.

[0054] In this embodiment, 0.92Ge 0.2 As 0.2 Se 0.6 The preparation method of -0.08CsCl glass ceramics includes the following two steps:

[0055] Step 1: Preparation of base glass: Weigh Ge, As, Se and CsCl as raw materials respectively, and the ratio is based on the chemical formula 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl; Mix the weighed raw materials evenly and place them in a quartz ampoule, evacuate the quartz ampoule to a vacuum degree of less than 10 -3 Pa, and then sealing the quartz ampoule with an acetylene-oxygen flame; placing the quartz ampoule in a swing heating furnace for glass melting treatment, heating the temperature at a heating rate of 100°C / h to a glass melting temperature of 900°C, and keeping it at the glass melting temperature for 15 hours, then taking out the quartz ampoule and quenching it in ice water or quenching it with compressed air for 5 seconds, and then quickly placing it in an annealing furnace at 200°C for 3 hours, cooling it to below 50°C with the furnace and taking it out of the furnace, thus obtaining the basic glass in the quartz ampoule;

[0056] Step 2, Preparation of Ge-As-Se-CsCl Glass-Ceramics: Place a quartz ampoule in a crystallization furnace and perform a two-stage crystallization heat treatment on the base glass. The first stage of the crystallization heat treatment is performed at a temperature of 350°C for 10 minutes to precipitate CsCl nanocrystals inside the base glass. Then, the second stage of the crystallization heat treatment is rapidly lowered to 240°C for 30 hours. Finally, the glass is cooled to below 50°C and removed from the furnace. The quartz ampoule is removed to obtain a Ge-As-Se-CsCl nanocrystalline composite chalcogenide glass-ceramic material.

[0057] Example 9

[0058] This embodiment provides a glass ceramic. The chemical formula of the glass ceramic in this embodiment is 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl.

[0059] The preparation method of the glass ceramics in this embodiment differs from that in Example 8 only in that the second stage of crystallization heat treatment in step 2 is performed for 80 hours. The rest is the same as in Example 8 and will not be described again here.

[0060] Example 10

[0061] This embodiment provides a glass ceramic. The chemical formula of the glass ceramic in this embodiment is 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl.

[0062] In this embodiment, 0.92Ge 0.2 As 0.2 Se 0.6The preparation method of -0.08CsCl glass ceramics includes the following two steps:

[0063] Step 1: Preparation of base glass: Weigh Ge, As, Se and CsCl as raw materials respectively, and the ratio is based on the chemical formula 0.92Ge 0.2 As 0.2 Se 0.6 -0.08CsCl; Mix the weighed raw materials evenly and place them in a quartz ampoule, evacuate the quartz ampoule to a vacuum degree of less than 10 -3 Pa, and then sealing the quartz ampoule with an acetylene-oxygen flame; placing the quartz ampoule in a swing heating furnace for glass melting treatment, heating the temperature at a heating rate of 100°C / h to a glass melting temperature of 900°C, and keeping it at the glass melting temperature for 15 hours, then taking out the quartz ampoule and quenching it in ice water or quenching it with compressed air for 5 seconds, and then quickly placing it in an annealing furnace at 200°C for 3 hours, cooling it to below 50°C with the furnace and taking it out of the furnace, thus obtaining the basic glass in the quartz ampoule;

[0064] Step 2, Preparation of Ge-As-Se-CsCl Glass-Ceramics: A quartz ampoule is placed in a crystallization furnace. As a comparative example, Example 10 is subjected to a one-step crystallization heat treatment on the base glass at a crystallization heat treatment temperature of 300°C for 50 hours. Finally, the glass is cooled to below 50°C and removed from the furnace. The quartz ampoule is removed to obtain a Ge-As-Se-CsCl nanocrystalline composite chalcogenide glass-ceramic material.

[0065] Example 11

[0066] This embodiment provides a glass ceramic. The chemical formula of the glass ceramic in this embodiment is 0.92Ge 0.2 As 0.3 Se 0.5 -0.08CsCl.

[0067] The preparation method of the glass ceramic in this embodiment includes the following two steps:

[0068] Step 1: Preparation of base glass: Weigh Ge, As, Se and CsCl as raw materials respectively, and prepare the glass according to the chemical formula 0.92Ge 0.2 As 0.3 Se 0.5 -0.08CsCl; Mix the weighed raw materials evenly and place them in a quartz ampoule, evacuate the quartz ampoule to a vacuum degree of less than 10 -3Pa, and then the quartz ampoule is placed in a rocking furnace for glass melting treatment, and the temperature is increased to a glass melting temperature of 900 °C at a temperature increasing rate of 100 °C / h, and the temperature is kept at the glass melting temperature for 15 hours, after which the quartz ampoule is taken out and quenched in ice water or quenched with compressed air for 5 seconds, and then quickly placed in an annealing furnace at 200 °C for treatment for 3 hours, and the furnace is cooled to below 50 °C, and the quartz ampoule is taken out, to obtain the base glass in the quartz ampoule.

[0069] Step two, preparation of the Ge-As-Se-CsCl glass ceramic: the quartz ampoule is placed in a crystallization furnace, and the base glass is subjected to two-stage crystallization heat treatment, the first stage of crystallization heat treatment temperature is 350 °C, and the temperature is kept at this temperature for 10 minutes, and CsCl nanocrystals are precipitated in the base glass, and then the second stage of crystallization temperature is quickly reduced to 240 °C, and the temperature is kept at this temperature for 50 hours, and finally the furnace is cooled to below 50 °C, and the quartz ampoule is taken out, to obtain the Ge-As-Se-CsCl nanocrystal composite chalcogenide glass ceramic material.

[0070] Example 12

[0071] The present embodiment provides a glass ceramic, and the chemical formula of the glass ceramic in the present embodiment is 0.9Ge 0.2 As 0.2 Se 0.6 -0.1CsCl.

[0072] The preparation method of the glass ceramic in the present embodiment includes the following two steps:

[0073] Step one, preparation of the base glass: Ge, As, Se, and CsCl compound are weighed as raw materials according to the chemical formula 0.9Ge 0.2 As 0.2 Se 0.6 -0.1CsCl; the weighed raw materials are mixed uniformly and then placed in a quartz ampoule, the quartz ampoule is vacuumized to a vacuum degree less than 10 -3 Pa, and then the quartz ampoule is placed in a rocking furnace for glass melting treatment, and the temperature is increased to a glass melting temperature of 900 °C at a temperature increasing rate of 100 °C / h, and the temperature is kept at the glass melting temperature for 15 hours, after which the quartz ampoule is taken out and quenched in ice water or quenched with compressed air for 5 seconds, and then quickly placed in an annealing furnace at 200 °C for treatment for 3 hours, and the furnace is cooled to below 50 °C, and the quartz ampoule is taken out, to obtain the base glass in the quartz ampoule.

[0074] Step 2, Preparation of Ge-As-Se-CsCl Glass-Ceramics: Place a quartz ampoule in a crystallization furnace and perform a two-stage crystallization heat treatment on the base glass. The first stage of the crystallization heat treatment is at a temperature of 350°C. The crystallization heat treatment is performed at this temperature for 10 minutes to precipitate CsCl nanocrystals inside the base glass. Then, the second stage of the crystallization temperature is rapidly lowered to 240°C. The crystallization heat treatment is performed at this temperature for 50 hours. Finally, the base glass is cooled to below 50°C and removed from the furnace. The quartz ampoule is removed to obtain a Ge-As-Se-CsCl nanocrystalline composite chalcogenide glass-ceramic material.

[0075] The main preparation parameters and properties of Ge-As-Se-CsCl glass-ceramics in Examples 1-12 are shown in Table 1:

[0076] Table 1: Main preparation parameters and properties of Ge-As-Se-CsCl glass-ceramics in Examples 1-12

[0077]

[0078]

[0079] The above results indicate that the method for preparing the high-hardness, two-stage heat-treated crystallized Ge-As-Se glass-ceramics disclosed herein can achieve effective control over the grain size and distribution of the precipitated grains. The grain size of the precipitated CsCl crystals is controlled within the range of 5-30 nm and is uniformly distributed in the Ge-As-Se glass matrix. The preparation method of the present invention is simple to operate, has a controllable process, and exhibits good stability. The prepared Ge-As-Se-CsCl glass-ceramics exhibit both good infrared transmittance and high hardness.

[0080] Although the present disclosure is disclosed as above, the protection scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and these changes and modifications will fall within the protection scope of the present invention.

Claims

1. A method for preparing Ge-As-Se-CsCl glass ceramics, characterized in that: The preparation method specifically comprises the following steps: S1, according to the chemical formula (1-y)Ge 0.2 As x Se (0.8-x) -yCsCl, Ge, As, Se and CsCl compounds were weighed as raw materials respectively, and the weighed raw materials were mixed evenly and placed in a quartz ampoule, and the quartz ampoule was evacuated to a vacuum degree of less than 10 -3 Pa, and then seal the quartz ampoule with an acetylene-oxygen flame; S2, placing the quartz ampoule of step S1 into a swing heating furnace for glass melting treatment, then taking out the quartz ampoule and sequentially performing quenching treatment and annealing treatment, cooling it to below 50° C. and taking it out of the furnace to obtain the basic glass in the quartz ampoule; S3, placing the quartz ampoule from step S2 in a crystallization furnace, performing a two-stage crystallization heat treatment on the base glass, then cooling it to below 50° C. and removing the quartz ampoule to obtain Ge-As-Se-CsCl glass ceramics; In step S3, the specific steps of the two-stage crystallization heat treatment are: raising the temperature to the first stage crystallization heat treatment temperature for crystallization heat treatment for 5-10 minutes to precipitate CsCl nanocrystals inside the base glass, and then rapidly lowering the temperature to the second stage crystallization heat treatment temperature for crystallization heat treatment for 10-100 hours; The temperature of the first stage of crystallization heat treatment is 80-100°C higher than the glass transition temperature of the base glass, and the temperature of the second stage of crystallization heat treatment is 10-20°C higher than the glass transition temperature of the base glass; The Ge-As-Se-CsCl glass ceramic comprises a matrix and CsCl crystals uniformly dispersed in the matrix, wherein the matrix is ​​Ge-As-Se chalcogenide glass, and the CsCl crystals are uniformly dispersed in the matrix in nanometer form. The molar composition of the Ge-As-Se-CsCl glass ceramic is expressed as follows according to the chemical formula: (1-y)Ge 0.2 As x Se (0.8-x) -yCsCl, where x ranges from 0.1 to 0.7 and y ranges from 0.05 to 0.

2.

2. The method for preparing Ge-As-Se-CsCl glass ceramics according to claim 1, wherein: In step S2, the specific steps of the glass melting treatment are as follows: heating the glass to a glass melting temperature of 830-950°C at a heating rate of 80-100°C / h, and keeping the glass at the glass melting temperature for 8-18 hours.

3. The method for preparing Ge-As-Se-CsCl glass ceramics according to claim 1, wherein: In step S2, the specific steps of the quenching treatment are: quenching in ice water for 3-10 seconds, or quenching with compressed air for 3-10 seconds.

4. The method for preparing Ge-As-Se-CsCl glass ceramics according to claim 1, wherein: In step S2, the specific steps of annealing are: placing in an annealing furnace at 180-205° C. for 2-5 hours.

5. A Ge-As-Se-CsCl glass ceramic prepared by the preparation method according to any one of claims 1 to 4, characterized in that: The grain size of the CsCl crystal is 5-30 nm.

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