Ge-As-Se-CsCl glass ceramic and preparation method thereof

Abstract

The present invention provides a Ge-As-Se-CsCl glass ceramic and a preparation method thereof, the Ge-As-Se-CsCl glass ceramic comprises a matrix and CsCl crystals uniformly dispersed in the matrix, the matrix is Ge-As-Se chalcogenide glass, the CsCl crystals are uniformly dispersed in the matrix in a nanometer form, the molar composition of the Ge-As-Se-CsCl glass ceramic is represented by a chemical formula: (1-y) Ge0. 2AsxSe (0.8-x)-yCsCl, x is in a range of 0.1-0.7, y is in a range of 0.05-0.2, y is in a range of 0-0.2, and y is in a range of 0-0.2. Compared with the prior art, the Ge-As-Se-CsCl glass ceramic prepared by two-stage heat treatment crystallization disclosed by the invention has the advantages that on one hand, the Ge-As-Se-CsCl glass ceramic has good infrared permeability, the hardness of the Ge-As-Se-CsCl glass ceramic can be greatly improved, and the application range of chalcogenide glass ceramic is widened.

Description

Technical Field

[0001] The 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 attracted great attention from researchers. It can reflect the temperature field on the surface of an object, expanding the perception range of the human eye from visible light to invisible infrared light, and is crucial in national defense, military, environmental monitoring, medical imaging, space exploration, etc. The current mid-infrared and far-infrared optical devices are mainly made of silicon, germanium, zinc selenide, fluoride glass, chalcogenide glass and other materials. Compared with visible light, the range of materials used for infrared light is much smaller. These materials have good light transmittance in the mid-infrared band, and the refractive index is approximately between 1.38 and 4.

[0003] Due to the mature micro-nano processing technology of silicon and germanium, the preparation of infrared lenses based on them has developed rapidly and is widely used in the near / mid-infrared. However, the absorption of silicon in the far-infrared band after 8μm increases sharply, which seriously affects the transmittance. The high cost of raw materials, low processing efficiency, and large thermal effect of germanium have greatly limited its application in the civilian field. Sulfur-based glass refers to a glass material containing at least one of the VI main group elements S, Se, and Te. It can meet the application requirements of wide working band, wide refractive index range, low thermal expansion, low refractive index temperature coefficient, high dielectric constant, etc., and also has the advantage of adjustable components; among them, sulfide glass is the infrared glass material with the widest transmittance range and the highest refractive index among all infrared glasses, and the preparation and structural etching processes of sulfide thin films are also relatively mature.

[0004] Although chalcogenide glass has many advantages in the field of infrared imaging, its mechanical properties are poor due to its weak chemical bonding. The hardness of chalcogenide glass is only about 1 / 7 of that of germanium single crystal, which greatly limits the practical application of chalcogenide glass. Therefore, improving the mechanical strength of chalcogenide glass is one of the important research directions for the application end. At present, there are two main methods commonly used to improve chalcogenide glass-ceramics: one is to improve the strength of covalent bonds in chalcogenide glass by controlling the components. For example, increasing the content of Ge elements will make Se and Te elements preferentially bond with them, that is, forming a large number of Ge-Se and Ge-Te strong bonds in the glass network structure, and greatly reducing Se-Se, Te-Te, Se-Te and other weak bonds, which can significantly improve the glass network strength of sulfur film. However, this method is limited to the glass formation area; the second is to precipitate crystals through heat treatment to form glass ceramics. The mechanical strength of crystals is much higher than that of amorphous glass. Introducing an appropriate amount of crystals into the glass matrix can greatly improve the mechanical strength of glass ceramics without affecting the transmittance and 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, wherein 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, and the molar composition of the Ge-As-Se-CsCl glass ceramic is expressed as follows according to a chemical formula: (1-y)Ge 0.2 As x Se (0.8-x) -yCsCl, where x ranges from 0.1-0.7 and y ranges from 0.05-0.2.

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

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

[0009] S1, according to the chemical formula (1-y)Ge 0.2 As x Se (0.8-x)-yCsCl, weigh Ge, As, Se and CsCl as raw materials respectively, mix the weighed raw materials evenly and put them in a quartz ampoule, evacuate the quartz ampoule to a vacuum degree of less than 10 -3 Pa, and then seal the quartz ampoule with acetylene-oxygen flame;

[0010] 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 basic glass in the quartz ampoule;

[0011] S3, placing the quartz ampoule of step S2 in a crystallization furnace, performing a two-stage crystallization heat treatment on the base glass, and then cooling it to below 50° C. and taking it out of the furnace, removing the quartz ampoule, and obtaining Ge-As-Se-CsCl glass ceramics.

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

[0013] In some embodiments, in step S2, the specific steps of quenching treatment are: quenching in ice water for 3-10 seconds, or quenching with compressed air for 3-10 seconds.

[0014] In some embodiments, in step S2, the specific steps of annealing treatment are: placing in an annealing furnace at 180-205° C. for 2-5 hours.

[0015] In some embodiments, in step S3, the specific steps of the two-stage crystallization heat treatment are: heating 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 rapidly reducing the temperature to the second stage crystallization heat treatment temperature for crystallization heat treatment for 10-100 hours.

[0016] Compared with the prior art, the Ge-As-Se-CsCl glass-ceramics prepared by the two-stage heat treatment crystallization disclosed in the present invention is first treated at a high temperature for a short time to form a large number of crystal nuclei, and then quickly cooled to a lower temperature for a long time to crystallize, which can control the precipitated grains to be fine and evenly distributed in the matrix glass. This ensures that the Ge-As-Se-CsCl glass-ceramics has good infrared transmittance, and at the same time can greatly improve the hardness of the Ge-As-Se-CsCl glass-ceramics, further broadening the application range of chalcogenide glass-ceramics.

[0017] In some embodiments, the first stage crystallization heat treatment temperature is 80-100° C. higher than the glass transition temperature of the base glass, and the second stage crystallization heat treatment temperature 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 Ge-As-Se glass-ceramics with high hardness and two-stage heat treatment crystallization disclosed in the present invention can achieve effective control of the grain size and grain distribution of the precipitated grains, and 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 has 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 picture. DETAILED DESCRIPTION

[0021] In order to make the above-mentioned purposes, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below. It should be noted that the following embodiments are only used to illustrate the implementation method and typical parameters of the present invention, and are not used to limit the parameter range described in the present invention. Reasonable changes derived therefrom are still within the scope of protection of the claims of the present invention.

[0022] It should be noted that the endpoints and any values ​​of the ranges disclosed in this article 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 endpoint values ​​of each range, the endpoint values ​​of each range and the 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 regarded as specifically disclosed in this article.

[0023] Unless otherwise defined, all terms, symbols and other scientific terms used herein are intended to have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. In some cases, terms with conventionally understood 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 is carried out in accordance with the protocols and parameters given by the manufacturer.

[0024] The technical effects of the present invention are described below in conjunction with 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 basic glass: Weigh Ge, As, Se and CsCl as raw materials respectively, and the ratio is in accordance with 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, and evacuate the quartz ampoule to a vacuum degree of less than 10 -3 Pa, and then seal the quartz ampoule with acetylene-oxygen flame; put the quartz ampoule into a swing heating furnace for glass melting treatment, heat it to the glass melting temperature of 900°C at a heating rate of 100°C / h, and keep it at the glass melting temperature for 15 hours, then take out the quartz ampoule and put it into ice water for quenching or quench it with compressed air for 5 seconds, and then quickly put it in an annealing furnace at 200°C for 3 hours, cool it to below 50°C with the furnace and take it out of the furnace, that is, the basic glass is obtained in the quartz ampoule;

[0029] Step 2, preparation of Ge-As-Se-CsCl glass-ceramics: placing a quartz ampoule in a crystallization furnace, performing a two-stage crystallization heat treatment on the base glass, wherein the first stage crystallization heat treatment temperature is 330°C, and the crystallization heat treatment is performed at this temperature for 10 minutes, and CsCl nanocrystals are precipitated inside the base glass, and then the second stage crystallization temperature is rapidly reduced to 240°C, and the crystallization heat treatment is performed at this temperature for 50 hours, and finally the glass is cooled to below 50°C and taken out of the furnace, and 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 first stage of crystallization heat treatment temperature in step 2 is 340° C. The rest is the same as in Embodiment 1 and will not be described again.

[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 first stage of crystallization heat treatment temperature in step 2 is 350° C. The rest is the same as in Embodiment 1 and will not be described again.

[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 basic glass: Weigh Ge, As, Se and CsCl as raw materials respectively, and the ratio is in accordance with the chemical formula 0.92Ge 0.2 As0.2 Se 0.6 -0.08CsCl; mix the weighed raw materials evenly and place them in a quartz ampoule, and evacuate the quartz ampoule to a vacuum degree of less than 10 -3 Pa, and then seal the quartz ampoule with acetylene-oxygen flame; put the quartz ampoule into a swing heating furnace for glass melting treatment, heat it to the glass melting temperature of 900°C at a heating rate of 100°C / h, and keep it at the glass melting temperature for 15 hours, then take out the quartz ampoule and put it into ice water for quenching or quench it with compressed air for 5 seconds, and then quickly put it in an annealing furnace at 200°C for 3 hours, cool it to below 50°C with the furnace and take it out of the furnace, that is, the basic glass is obtained in the quartz ampoule;

[0040] Step 2, preparation of Ge-As-Se-CsCl glass-ceramics: placing a quartz ampoule in a crystallization furnace, performing a two-stage crystallization heat treatment on the base glass, the first stage of the crystallization heat treatment temperature is 350°C, the first stage of the crystallization heat treatment time is 5 minutes, CsCl nanocrystals are precipitated inside the base glass, and then the second stage of the crystallization temperature is rapidly reduced to 240°C, and the crystallization heat treatment is performed at this temperature for 50 hours, and finally the furnace is cooled to below 50°C and taken out of the furnace, and the quartz ampoule is removed to obtain a Ge-As-Se-CsCl nanocrystalline composite chalcogenide glass-ceramic material.

[0041] Example 5

[0042] 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.

[0043] The preparation method of the glass ceramics in this embodiment is different from that in Embodiment 4 only in that the first stage of crystallization heat treatment in step 2 is performed for 8 minutes, and the rest is the same as in Embodiment 4 and will not be described again.

[0044] Example 6

[0045] 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.

[0046] 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:

[0047] Step 1: Preparation of basic glass: Weigh Ge, As, Se and CsCl as raw materials respectively, and the ratio is in accordance with 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, and evacuate the quartz ampoule to a vacuum degree of less than 10 -3 Pa, and then seal the quartz ampoule with acetylene-oxygen flame; put the quartz ampoule into a swing heating furnace for glass melting treatment, heat it to the glass melting temperature of 900°C at a heating rate of 100°C / h, and keep it at the glass melting temperature for 15 hours, then take out the quartz ampoule and put it into ice water for quenching or quench it with compressed air for 5 seconds, and then quickly put it in an annealing furnace at 200°C for 3 hours, cool it to below 50°C with the furnace and take it out of the furnace, that is, the basic glass is obtained in the quartz ampoule;

[0048] Step 2, preparation of Ge-As-Se-CsCl glass-ceramics: placing a quartz ampoule in a crystallization furnace, and performing a two-stage crystallization heat treatment on the base glass. The first stage of the crystallization heat treatment temperature is 350°C, and 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 temperature is 230°C, and the crystallization heat treatment is performed at this temperature for 50 hours. Finally, the furnace is cooled to below 50°C and the furnace is removed, and 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 is different 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.

[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 basic glass: Weigh Ge, As, Se and CsCl as raw materials respectively, and the ratio is in accordance with 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, and evacuate the quartz ampoule to a vacuum degree of less than 10 -3 Pa, and then seal the quartz ampoule with acetylene-oxygen flame; put the quartz ampoule into a swing heating furnace for glass melting treatment, heat it to the glass melting temperature of 900°C at a heating rate of 100°C / h, and keep it at the glass melting temperature for 15 hours, then take out the quartz ampoule and put it into ice water for quenching or quench it with compressed air for 5 seconds, and then quickly put it in an annealing furnace at 200°C for 3 hours, cool it to below 50°C with the furnace and take it out of the furnace, that is, the basic glass is obtained in the quartz ampoule;

[0056] Step 2, preparation of Ge-As-Se-CsCl glass-ceramics: placing a quartz ampoule in a crystallization furnace, and performing a two-stage crystallization heat treatment on the base glass. The first stage of the crystallization heat treatment temperature is 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 quickly lowered to 240°C for crystallization heat treatment 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 is different from that in Embodiment 8 only in that the second stage of crystallization heat treatment in step 2 is performed for 80 hours, and the rest is the same as in Embodiment 8 and will not be described again.

[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 basic glass: Weigh Ge, As, Se and CsCl as raw materials respectively, and the ratio is in accordance with 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, and evacuate the quartz ampoule to a vacuum degree of less than 10 -3 Pa, and then seal the quartz ampoule with acetylene-oxygen flame; put the quartz ampoule into a swing heating furnace for glass melting treatment, heat it to the glass melting temperature of 900°C at a heating rate of 100°C / h, and keep it at the glass melting temperature for 15 hours, then take out the quartz ampoule and put it into ice water for quenching or quench it with compressed air for 5 seconds, and then quickly put it in an annealing furnace at 200°C for 3 hours, cool it to below 50°C with the furnace and take it out of the furnace, that is, the basic glass is obtained in the quartz ampoule;

[0064] Step 2, preparation of Ge-As-Se-CsCl glass-ceramics: placing a quartz ampoule in a crystallization furnace. As a comparative example, Example 10 performs a one-step crystallization heat treatment on the base glass. The crystallization heat treatment temperature is 300°C. The crystallization heat treatment is performed at this temperature 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] Embodiment 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 glass ceramics in this embodiment includes the following two steps:

[0068] Step 1: Preparation of basic glass: Weigh Ge, As, Se and CsCl as raw materials respectively, 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, and evacuate the quartz ampoule to a vacuum degree of less than 10 -3Pa, and then seal the quartz ampoule with acetylene-oxygen flame; put the quartz ampoule into a swing heating furnace for glass melting treatment, heat it to the glass melting temperature of 900°C at a heating rate of 100°C / h, and keep it at the glass melting temperature for 15 hours, then take out the quartz ampoule and put it into ice water for quenching or quench it with compressed air for 5 seconds, and then quickly put it in an annealing furnace at 200°C for 3 hours, cool it to below 50°C with the furnace and take it out of the furnace, that is, the basic glass is obtained in the quartz ampoule;

[0069] Step 2, preparation of Ge-As-Se-CsCl glass-ceramics: placing a quartz ampoule in a crystallization furnace, performing a two-stage crystallization heat treatment on the base glass, wherein the first stage crystallization heat treatment temperature is 350°C, and the crystallization heat treatment is performed at this temperature for 10 minutes, and CsCl nanocrystals are precipitated inside the base glass, and then the second stage crystallization temperature is rapidly reduced to 240°C, and the crystallization heat treatment is performed at this temperature for 50 hours, and finally the glass is cooled to below 50°C and taken out of the furnace, and the quartz ampoule is removed to obtain a Ge-As-Se-CsCl nanocrystalline composite chalcogenide glass-ceramic material.

[0070] Example 12

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

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

[0073] Step 1: Preparation of basic glass: Weigh Ge, As, Se and CsCl as raw materials respectively, according to the chemical formula 0.9Ge 0.2 As 0.2 Se 0.6 -0.1CsCl; mix the weighed raw materials evenly and place them in a quartz ampoule, and evacuate the quartz ampoule to a vacuum degree of less than 10 -3 Pa, and then seal the quartz ampoule with acetylene-oxygen flame; put the quartz ampoule into a swing heating furnace for glass melting treatment, heat it to the glass melting temperature of 900°C at a heating rate of 100°C / h, and keep it at the glass melting temperature for 15 hours, then take out the quartz ampoule and put it into ice water for quenching or quench it with compressed air for 5 seconds, and then quickly put it in an annealing furnace at 200°C for 3 hours, cool it to below 50°C with the furnace and take it out of the furnace, that is, the basic glass is obtained in the quartz ampoule;

[0074] Step 2, preparation of Ge-As-Se-CsCl glass-ceramics: placing a quartz ampoule in a crystallization furnace, performing a two-stage crystallization heat treatment on the base glass, wherein the first stage crystallization heat treatment temperature is 350°C, and the crystallization heat treatment is performed at this temperature for 10 minutes, and CsCl nanocrystals are precipitated inside the base glass, and then the second stage crystallization temperature is rapidly reduced to 240°C, and the crystallization heat treatment is performed at this temperature for 50 hours, and finally the glass is cooled to below 50°C and taken out of the furnace, and 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] It can be seen from the above results that 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, and the grain size of the precipitated CsCl crystals is controlled within the range of 5-30nm and is uniformly 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 has both good infrared transmittance and high hardness.

[0080] Although the disclosure is disclosed as above, the protection scope of the 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 disclosure, and these changes and modifications will fall within the protection scope of the present invention.

Claims

1. A Ge-As-Se-CsCl glass ceramic, characterized in that: 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, and 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 0.1-0.7 and y ranges from 0.05-0.

2.

2. The Ge-As-Se-CsCl glass ceramic according to claim 1, characterized in that: The grain size of the CsCl crystal is 5-30 nm.

3. A method for preparing the Ge-As-Se-CsCl glass ceramic according to claim 1 or 2, 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, weigh Ge, As, Se and CsCl as raw materials respectively, mix the weighed raw materials evenly and put them in a quartz ampoule, evacuate the quartz ampoule to a vacuum degree of less than 10 -3 Pa, and then seal the quartz ampoule with 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 basic glass in the quartz ampoule; S3, placing the quartz ampoule of step S2 in a crystallization furnace, performing a two-stage crystallization heat treatment on the base glass, and then cooling it to below 50° C. and taking it out of the furnace, removing the quartz ampoule, and obtaining Ge-As-Se-CsCl glass ceramics.

4. The method for preparing Ge-As-Se-CsCl glass ceramics according to claim 3, characterized in that: In step S2, the specific steps of glass melting treatment are as follows: heating to the glass melting temperature of 830-950°C at a heating rate of 80-100°C / h, and keeping the temperature at the glass melting temperature for 8-18 hours.

5. The method for preparing Ge-As-Se-CsCl glass ceramics according to claim 3, characterized in that: 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.

6. The method for preparing Ge-As-Se-CsCl glass ceramics according to claim 3, characterized in that: In step S2, the specific steps of annealing treatment are: placing in an annealing furnace at 180-205° C. for 2-5 hours.

7. The method for preparing Ge-As-Se-CsCl glass ceramics according to claim 3, characterized in that: 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 rapidly lowering the temperature to the second stage crystallization heat treatment temperature for crystallization heat treatment for 10-100 hours.

8. The method for preparing Ge-As-Se-CsCl glass ceramics according to claim 7, characterized in that: The first stage crystallization heat treatment temperature is 80-100° C. higher than the glass transition temperature of the base glass, and the second stage crystallization heat treatment temperature is 10-20° C. higher than the glass transition temperature of the base glass.

9. The method for preparing Ge-As-Se-CsCl glass ceramics according to claim 7, characterized in that: 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.

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