Chalcogenide glass, preparation method thereof, optical element and infrared thermal imaging device

Abstract

The invention discloses chalcogenide glass and a preparation method thereof, an optical element and an imaging device. The chalcogenide glass comprises the following constituent elements: germanium (Ge) with the molar percentage of 5 mol% to 15 mol%; arsenic As, the molar percentage of which is 40 mol% to 55 mol%; tellurium (Te), the molar percentage of which is 30 mol% to 50 mol%; and selenium Se, the molar percentage of which is 0.1 mol% to 10 mol%. The refractive index of the chalcogenide glass in the infrared band is larger than 3, and the refractive index is uniform. The refractive index of the chalcogenide glass can be improved, the application scene of the chalcogenide glass is expanded, germanium glass can be replaced by the chalcogenide glass in an infrared optical system using the germanium glass, and therefore the cost of the infrared optical system can be reduced.

Description

Technical Field

[0001] Embodiments of the present application relate to the technical field of optical materials, and in particular, to a chalcogenide glass, a preparation method thereof, an optical element, and an infrared thermal imaging device. Background Art

[0002] In recent years, with the development of infrared optical technology, especially in applications such as vehicle-mounted, security, and smart home, it has great market potential. Chalcogenide glass is a very important infrared optical material, and its excellent properties have been generally recognized. However, the refractive index of chalcogenide glass currently used in infrared optical systems is generally between 2.5 and 2.8, far lower than the refractive index of germanium glass as high as 4.0 for infrared optical materials, which greatly limits the application of chalcogenide glass in infrared optical systems. Summary of the Invention

[0003] The chalcogenide glass, a preparation method thereof, an optical element, and an infrared thermal imaging device provided by the embodiments of the present application can solve or partially solve the above-mentioned deficiencies in the prior art or other deficiencies in the prior art.

[0004] According to a first aspect of the present application, a chalcogenide glass is provided. The constituent elements of the chalcogenide glass include: germanium (Ge) with a molar percentage of 5 mol% to 15 mol%; arsenic (As) with a molar percentage of 40 mol% to 55 mol%; tellurium (Te) with a molar percentage of 30 mol% to 50 mol%; and selenium (Se) with a molar percentage of 0.1 mol% to 9 mol%. The refractive index of the chalcogenide glass in the infrared band is greater than 3 and the refractive index is uniform.

[0005] In an embodiment of the present application, the molar percentage of germanium (Ge) is 7 mol% to 10 mol%; the molar percentage of arsenic (As) is 43 mol% to 50 mol%; the molar percentage of tellurium (Te) is 35 mol% to 45 mol%; and the molar percentage of selenium (Se) is 0.5 mol% to 9 mol%.

[0006] In an embodiment of the present application, the sum of the molar percentages of germanium (Ge) and selenium (Se) is less than or equal to 20 mol%.

[0007] In an embodiment of the present application, the elements further include antimony (Sb), tin (Sn), and gallium (Ga), and the sum of the molar percentages of antimony (Sb), tin (Sn), and gallium (Ga) is 0 to 5 mol%.

[0008] In an embodiment of the present application, the sum of the molar percentages of antimony (Sb), tin (Sn), and gallium (Ga) is 0.1 mol% to 2 mol%.

[0009] In one embodiment of the present application, the oxygen content inside the chalcogenide glass is less than 1 ppm.

[0010] In one embodiment of the present application, there are no streaks with a length of 400 μm or more inside the chalcogenide glass, and the cross-sectional area ratio of the defects inside the chalcogenide glass is less than 0.1%.

[0011] In one embodiment of the present application, the average transmittance of the chalcogenide glass in the 2 μm - 17 μm band is greater than or equal to 50%.

[0012] In one embodiment of the present application, the glass transition temperature of the chalcogenide glass is 160°C - 210°C.

[0013] According to a second aspect of the present application, a chalcogenide glass is provided. The constituent elements of the chalcogenide glass include: germanium Ge, with a molar percentage of 5 mol% - 14 mol%; arsenic As, with a molar percentage of 41 mol% - 55 mol%; tellurium Te, with a molar percentage of 30 mol% - 47 mol%; and selenium Se, with a molar percentage of 0.2 mol% - 9 mol%. The average transmittance of the chalcogenide glass in the 2 μm - 17 μm band is greater than or equal to 50%, and the refractive index is greater than 3 and the refractive index is uniform.

[0014] In one embodiment of the present application, the molar percentage of germanium Ge is 6 mol% - 10 mol%; the molar percentage of arsenic As is 43.5 mol% - 50 mol%; the molar percentage of tellurium Te is 40 mol% - 45 mol%; the molar percentage of selenium Se is 5 mol% - 9 mol%.

[0015] In one embodiment of the present application, the sum of the molar percentages of germanium Ge and selenium Se is less than or equal to 20 mol%.

[0016] In one embodiment of the present application, the elements further include antimony Sb, tin Sn, and gallium Ga, and the sum of the molar percentages of antimony Sb, tin Sn, and gallium Ga is 0 - 4 mol%.

[0017] In one embodiment of the present application, the sum of the molar percentages of antimony Sb, tin Sn, and gallium Ga is 0.2 mol% - 2 mol%.

[0018] In one embodiment of the present application, the oxygen content inside the chalcogenide glass is less than 1 ppm.

[0019] In one embodiment of the present application, there are no streaks with a length of 400 μm or more inside the chalcogenide glass, and the cross-sectional area ratio of the defects inside the chalcogenide glass is less than 0.1%.

[0020] In one embodiment of the present application, the glass transition temperature of the chalcogenide glass is 160°C to 210°C.

[0021] According to a third aspect of the present application, a method for preparing a chalcogenide glass is provided. The preparation method includes: mixing raw materials according to the predetermined molar percentages of the constituent elements in the chalcogenide glass; melting the mixed raw materials in a vacuum-sealed environment; cooling the molten glass obtained; and annealing the cooled glass to obtain the chalcogenide glass. The refractive index of the chalcogenide glass in the infrared band is greater than 3 and the refractive index is uniform. Wherein, the elements include germanium (Ge), arsenic (As), tellurium (Te) and selenium (Se), and are configured according to the following molar percentages: the molar percentage of germanium (Ge) is 5 mol% to 15 mol%; the molar percentage of arsenic (As) is 40 mol% to 55 mol%; the molar percentage of tellurium (Te) is 30 mol% to 50 mol%; the molar percentage of selenium (Se) is 0.1 mol% to 9 mol%.

[0022] In one embodiment of the present application, annealing the cooled glass includes: annealing the cooled glass at an annealing temperature reduction rate of 10°C / hour to 20°C / hour.

[0023] In one embodiment of the present application, melting the mixed raw materials in a vacuum-sealed environment includes: performing the melting treatment on the mixed raw materials in a vacuum-sealed environment for 15 hours to 20 hours.

[0024] In one embodiment of the present application, the molar percentage of germanium (Ge) is 7 mol% to 10 mol%; the molar percentage of arsenic (As) is 43 mol% to 50 mol%; the molar percentage of tellurium (Te) is 35 mol% to 45 mol%; the molar percentage of selenium (Se) is 0.5 mol% to 9 mol%.

[0025] In one embodiment of the present application, the sum of the molar percentages of germanium (Ge) and selenium (Se) is less than or equal to 20 mol%.

[0026] In one embodiment of the present application, the elements further include antimony (Sb), tin (Sn) and gallium (Ga), and the sum of the molar percentages of antimony (Sb), tin (Sn) and gallium (Ga) is 0 to 5 mol%.

[0027] In one embodiment of the present application, the sum of the molar percentages of antimony (Sb), tin (Sn) and gallium (Ga) is 0.1 mol% to 2 mol%.

[0028] According to a fourth aspect of the present application, a method for preparing a chalcogenide glass is provided. The preparation method includes: mixing raw materials according to the predetermined molar percentages of the constituent elements in the chalcogenide glass; melting the mixed raw materials in a vacuum-sealed environment; cooling the molten glass obtained by melting; and annealing the cooled glass to obtain the chalcogenide glass. The chalcogenide glass has an average transmittance greater than or equal to 50% in the wavelength range of 2 μm to 17 μm, a refractive index greater than 3 and the refractive index is uniform. Among them, the elements include germanium (Ge), arsenic (As), tellurium (Te) and selenium (Se), and are configured according to the following molar percentages: germanium (Ge) with a molar percentage of 5 mol% to 14 mol%; arsenic (As) with a molar percentage of 41 mol% to 55 mol%; tellurium (Te) with a molar percentage of 30 mol% to 47 mol%; and selenium (Se) with a molar percentage of 0.2 mol% to 9 mol%.

[0029] In an embodiment of the present application, the annealing of the cooled glass includes: annealing the cooled glass at an annealing cooling rate of 10 °C / hour to 20 °C / hour.

[0030] In an embodiment of the present application, the melting of the mixed raw materials in a vacuum-sealed environment includes: subjecting the mixed raw materials to the melting treatment for 15 hours to 20 hours in a vacuum-sealed environment.

[0031] In an embodiment of the present application, the molar percentage of germanium (Ge) is 6 mol% to 10 mol%; the molar percentage of arsenic (As) is 43.5 mol% to 50 mol%; the molar percentage of tellurium (Te) is 40 mol% to 45 mol%; and the molar percentage of selenium (Se) is 5 mol% to 9 mol%.

[0032] In an embodiment of the present application, the sum of the molar percentages of germanium (Ge) and selenium (Se) is less than or equal to 20 mol%.

[0033] In an embodiment of the present application, the elements further include antimony (Sb), tin (Sn) and gallium (Ga), and the sum of the molar percentages of antimony (Sb), tin (Sn) and gallium (Ga) is 0 to 4 mol%.

[0034] In an embodiment of the present application, the sum of the molar percentages of antimony (Sb), tin (Sn) and gallium (Ga) is 0.2 mol% to 2 mol%.

[0035] According to a fifth aspect of the present application, an optical element is provided. The optical element is made of the chalcogenide glass described in the first aspect.

[0036] According to a sixth aspect of the present application, an infrared thermal imaging device is provided, which includes an optical lens and an infrared detector, and the optical lens includes the optical element described in the fifth aspect.

[0037] The chalcogenide glass, its preparation method, optical element and infrared thermal imaging device provided according to the embodiments of the present application can increase the refractive index of the chalcogenide glass, expand the application scenarios of the chalcogenide glass, and the chalcogenide glass can be used instead of germanium glass in an infrared optical system using germanium glass, thereby reducing the cost of the infrared optical system.

[0038] The content described in this part is not intended to identify the key or important features of the embodiments of the present application, nor is it used to limit the scope of the present application. Other features of the present application will become easily understood through the following description. Description of the Drawings

[0039] By reading the detailed description of the non-limiting embodiments with reference to the following drawings, other features, objectives and advantages of the present application will become more obvious. The drawings are used to better understand the solution and do not constitute a limitation to the present application. Among them:

[0040] Figure 1 is a schematic diagram of the curve of wavelength and transmittance of the exemplary chalcogenide glass of the embodiment of the present application;

[0041] Figure 2 is a schematic diagram of the composition structure of the infrared thermal imaging device of the embodiment of the present application. Detailed Embodiments

[0042] The following describes the exemplary embodiments of the present application in conjunction with the drawings. Various details of the embodiments of the present application are included to assist in understanding, and they should be considered merely exemplary. Therefore, those of ordinary skill in the art should recognize that various changes and modifications can be made to the embodiments described herein without departing from the scope and spirit of the present application. Similarly, for clarity and conciseness, the description of well-known functions and structures is omitted below.

[0043] In the drawings, for ease of illustration, the thickness, dimensions and shapes of the components have been slightly adjusted. The drawings are only examples and are not drawn strictly to scale. As used herein, terms such as "substantially", "about" and similar terms are used as terms indicating approximation, rather than terms indicating degree, and are intended to illustrate the inherent deviations in measured or calculated values that would be recognized by those of ordinary skill in the art.

[0044] It should also be understood that expressions such as "including", "comprising", "having", "containing" and / or "comprising of" are open-ended rather than closed-ended expressions in this specification, which means that the stated features, elements and / or components exist, but do not exclude the existence of one or more other features, elements, components and / or their combinations. In addition, when an expression such as "at least one of..." appears after a list of listed features, it modifies the entire list of features, rather than just an individual element in the list. In addition, when describing the embodiments of the present application, the use of "may" means "one or more embodiments of the present application". And the term "exemplary" is intended to refer to an example or illustration.

[0045] Unless otherwise defined, all terms used herein (including engineering terms and technical terms) have the same meaning as commonly understood by those of ordinary skill in the art to which this application belongs. It should also be understood that unless clearly stated in this application, words defined in a common dictionary should be interpreted as having a meaning consistent with their meaning in the context of the relevant art, and should not be interpreted in an idealized or overly formal sense.

[0046] It should be noted that, without conflict, the embodiments in this application and the features in the embodiments can be combined with each other. In addition, unless clearly defined or in contradiction with the context, the specific steps included in the methods described in this application do not have to be limited to the recited order, but can be executed in any order or executed in parallel.

[0047] In addition, those skilled in the art can understand that the quantities shown in the drawings and the following text of this application, such as the number of optical films, etc., are only shown for convenience of illustration, and without departing from the teachings of the disclosure of this application, the specific quantities can be set according to actual needs.

[0048] As a very important infrared optical material, the excellent properties of chalcogenide glass have been widely recognized. However, the refractive index of chalcogenide glass currently used in infrared optical systems is generally between 2.5 and 2.8, far lower than the refractive index of germanium glass, which is as high as 4.0, as an infrared optical material. Due to the large gap in refractive index between chalcogenide glass and germanium glass, chalcogenide glass cannot replace germanium glass in many application scenarios, which greatly limits the application of chalcogenide glass in infrared optical systems.

[0049] To solve the above problems, an embodiment of the present application provides a chalcogenide glass.

[0050] The constituent elements of the chalcogenide glass according to the embodiments of the present application include: germanium (Ge), arsenic (As), tellurium (Te), and selenium (Se). Among them, the molar percentage of germanium (Ge) is 5 mol% to 15 mol%, the molar percentage of arsenic (As) is 40 mol% to 55 mol%, the molar percentage of tellurium (Te) is 30 mol% to 50 mol%, and the molar percentage of selenium (Se) is 0.1 mol% to 9 mol%. The chalcogenide glass according to the embodiments of the present application has a refractive index greater than 3 and a uniform refractive index in the infrared band.

[0051] Optionally, among the constituent elements of the chalcogenide glass, the molar percentage of germanium (Ge) can be 5 mol% to 14 mol%. Further, the molar percentage of germanium (Ge) can be 7 mol% to 10 mol% or 6 mol% to 10 mol%.

[0052] The germanium (Ge) element is an important component for forming the glass. If the content of the germanium (Ge) element is too small, vitrification transformation is not likely to occur. If the content of the germanium (Ge) element is too large, germanium (Ge)-based crystals are likely to precipitate in the glass, which will cause infrared light to be difficult to transmit and will also increase the raw material cost. By controlling the content of the germanium (Ge) element in the chalcogenide glass to be 5 mol% to 15 mol%, optionally 5 mol% to 14 mol%, preferably 7 mol% to 10 mol% or 6 mol% to 10 mol%, the occurrence of vitrification transformation can be ensured, the transmittance of the glass to infrared light can be effectively improved, and the cost can be reduced.

[0053] Optionally, among the constituent elements of the chalcogenide glass, the molar percentage of tellurium (Te) can be 30 mol% to 47 mol%. Further, the molar percentage of tellurium (Te) can be 35 mol% to 45 mol% or 40 mol% to 45 mol%.

[0054] If the content of the tellurium (Te) element is too small, glass crystallization will become difficult and the transmittance of the glass to infrared light is likely to decrease. If the content of the tellurium (Te) element is too large, the thermal stability of the glass is likely to decrease, and tellurium (Te)-based crystals are likely to precipitate in the glass, which will cause infrared light to be difficult to transmit. And tellurium (Te) has a relatively large atomic radius, and the glass transition temperature Tg will decrease with the increase of the tellurium (Te) content. By controlling the content of the tellurium (Te) element in the chalcogenide glass to be 30 mol% to 50 mol%, optionally 30 mol% to 47 mol%, preferably 35 mol% to 45 mol% or 40 mol% to 45 mol%, the glass transition temperature Tg can be significantly reduced, and the transmittance curve of the glass can be shifted towards the long-wave direction, effectively improving the thermal stability of the glass, ensuring glass crystallization, effectively increasing the refractive index of the glass, and making the refractive index n of the glass at a wavelength of 10 μm reach more than 3.25.

[0055] Optionally, among the constituent elements of the chalcogenide glass, the molar percentage of selenium (Se) can be 0.2 mol% to 9 mol%. Further, the molar percentage of selenium (Se) can be 0.5 mol% to 9 mol% or 5 mol% to 9 mol%.

[0056] As a chalcogen element, selenium (Se) is a component that expands the vitrification range and improves the thermal stability of the glass. Selenium (Se) is a good ligand in the glass and can form strong Ge-Se bonds with germanium (Ge) and strong Te-Se bonds with tellurium (Te). By controlling the content of selenium (Se) in the chalcogenide glass to be 0.1 mol% to 9 mol%, optionally 0.2 mol% to 9 mol%, preferably 0.5 mol% to 9 mol% or 5 mol% to 9 mol%, it is beneficial to increase the glass transition temperature Tg, improve the crystallization performance of the glass. At the same time, the introduction of selenium (Se) can also effectively increase the transmittance of the glass to infrared light.

[0057] Optionally, among the constituent elements of the chalcogenide glass, the molar percentage of arsenic (As) can be 41 mol% to 55 mol%. Further, the molar percentage of arsenic (As) can be 43 mol% to 50 mol% or 43.5 mol% to 50 mol%.

[0058] Adding arsenic (As) element to the chalcogenide glass can expand the formation region range of the chalcogenide glass components. Arsenic (As) can form relatively stable multi-component systems with selenium (Se) and tellurium (Te) elements, which is beneficial to the formation of chalcogenide glass. By controlling the content of arsenic (As) in the chalcogenide glass to be 40 mol% to 55 mol%, optionally 41 mol% to 55 mol%, preferably 43 mol% to 50 mol% or 43.5 mol% to 50 mol%, the stability of the chalcogenide glass can be improved. At the same time, the increase in the content of arsenic (As) can also increase the refractive index of the chalcogenide glass.

[0059] In some alternative embodiments of the present application, the sum of the molar percentages of germanium (Ge) and selenium (Se) in the constituent elements of the chalcogenide glass is preferably controlled below 20 mol%.

[0060] In some alternative embodiments of the present application, the constituent elements of the chalcogenide glass further include antimony (Sb), tin (Sn), and gallium (Ga), and the sum of the molar percentages of Sb, Sn, and Ga is 0 to 5 mol%. Optionally, in the constituent elements of the chalcogenide glass, the sum of the molar percentages of Sb, Sn, and Ga can be 0 to 4 mol%. Further, the sum of the molar percentages of Sb, Sn, and Ga can be 0.1 mol% to 2 mol% or 0.2 mol% to 2 mol%. By adding a small amount of elements such as Sb, Sn, and Ga to the glass, the thermal stability and solubility of the glass can be improved. If the content of the elements Sb, Sn, and Ga is too high, crystallization of the glass will occur, affecting the transmittance of the glass to infrared light and also increasing the raw material cost. By controlling the content of the elements Sb, Sn, and Ga in the chalcogenide glass to 0 to 5 mol%, optionally 0 to 4 mol%, preferably 0.1 mol% to 2 mol% or 0.2 mol% to 2 mol%, it is beneficial to the formation of the glass, can effectively improve the transmittance of the glass to infrared light, reduce the cost, and enable the refractive index n of the glass at a wavelength of 10 μm to reach 3.25 to 3.45.

[0061] In some alternative embodiments of the present application, the oxygen content inside the chalcogenide glass is less than 1 ppm. By controlling the oxygen content inside the chalcogenide glass to less than 1 ppm, the average transmittance of the glass can be effectively improved.

[0062] In some alternative embodiments of the present application, there are no streaks with a length of more than 400 μm inside the chalcogenide glass, and the cross-sectional area ratio of the defects inside the chalcogenide glass is less than 0.1%, which can effectively improve the average transmittance of the glass.

[0063] The chalcogenide glass provided by the embodiments of the present application can have an average transmittance greater than or equal to 50% in the wavelength range of 2 μm to 17 μm, its refractive index n can be greater than 3 and the refractive index is uniform, and the difference in refractive index can be less than 10 -4 , which can increase the refractive index of the chalcogenide glass, expand the application scenarios of the chalcogenide glass, and the chalcogenide glass can be used instead of germanium glass in infrared optical systems using germanium glass, thereby reducing the cost of the infrared optical system, and the cost reduction can reach more than 30%.

[0064] The glass transition temperature Tg of the chalcogenide glass provided by the embodiments of the present application can be 160°C to 210°C. The chalcogenide glass having a glass transition temperature Tg of 160°C to 210°C is beneficial for the glass to adapt to high-temperature scenarios, can make the glass suitable for precision molding, and can also meet the requirements of coating.

[0065] The embodiments of the present application also provide a preparation method of a chalcogenide glass, and the preparation method includes the following steps:

[0066] Step 1, mix the raw materials according to the predetermined molar percentages of the constituent elements in the chalcogenide glass.

[0067] Step 2, melt the mixed raw materials in a vacuum-sealed environment.

[0068] Step 3, cool the glass melt obtained by melting.

[0069] Step 4, anneal the cooled glass to obtain a chalcogenide glass, and the refractive index of the chalcogenide glass in the infrared band is greater than 3 and the refractive index is uniform.

[0070] Among them, the constituent elements of the chalcogenide glass include germanium (Ge), arsenic (As), tellurium (Te) and selenium (Se), and are configured according to the following molar percentages: the molar percentage of germanium (Ge) is 5 mol% to 15 mol%, the molar percentage of arsenic (As) is 40 mol% to 55 mol%, the molar percentage of tellurium (Te) is 30 mol% to 50 mol%, and the molar percentage of selenium (Se) is 0.1 mol% to 9 mol%.

[0071] Optionally, the configuration of the constituent elements of the chalcogenide glass: the molar percentage of germanium (Ge) is 5 mol% to 14 mol%, the molar percentage of arsenic (As) is 41 mol% to 55 mol%, the molar percentage of tellurium (Te) is 30 mol% to 47 mol%, and the molar percentage of selenium (Se) is 0.2 mol% to 9 mol%. The average transmittance of the chalcogenide glass in the 2 μm to 17 μm band is greater than or equal to 50%.

[0072] In some alternative embodiments of the present application, step 4 of annealing the cooled glass may include: annealing the cooled glass at an annealing cooling rate of 10 °C / hour to 20 °C / hour. Annealing and cooling at this speed is beneficial to better eliminate internal stress.

[0073] In some alternative embodiments of the present application, step 2 of melting the mixed raw materials in a vacuum-sealed environment may include: melting the mixed raw materials in a vacuum-sealed environment for 15 hours to 20 hours. By controlling the melting time of the raw materials within 15 hours to 20 hours, the melting time is effectively shortened.

[0074] In some other alternative embodiments of the present application, the sum of the molar percentages of germanium (Ge) and selenium (Se) in the constituent elements of the chalcogenide glass is preferably controlled below 20 mol%.

[0075] In some alternative embodiments of the present application, the configuration of the constituent elements of the chalcogenide glass is as follows: the molar percentage of germanium (Ge) is 7 mol% to 10 mol%, the molar percentage of arsenic (As) is 43 mol% to 50 mol%, the molar percentage of tellurium (Te) is 35 mol% to 45 mol%, and the molar percentage of selenium (Se) is 0.5 mol% to 9 mol%.

[0076] In some other alternative embodiments of the present application, the configuration of the constituent elements of the chalcogenide glass is as follows: the molar percentage of germanium (Ge) is 6 mol% to 10 mol%, the molar percentage of arsenic (As) is 43.5 mol% to 50 mol%, the molar percentage of tellurium (Te) is 40 mol% to 45 mol%, and the molar percentage of selenium (Se) is 5 mol% to 9 mol%.

[0077] In some alternative embodiments of the present application, the constituent elements of the chalcogenide glass may further include antimony (Sb), tin (Sn), and gallium (Ga), and the sum of the molar percentages of antimony (Sb), tin (Sn), and gallium (Ga) may be 0 to 5 mol%. Optionally, the sum of the molar percentages of antimony (Sb), tin (Sn), and gallium (Ga) may be 0 to 4 mol%. Further, the sum of the molar percentages of antimony (Sb), tin (Sn), and gallium (Ga) may be 0.1 mol% to 2 mol% or 0.2 mol% to 2 mol%.

[0078] The preparation method of the chalcogenide glass provided by the embodiments of the present application can obtain a large-diameter glass ingot. For example, the diameter of the glass ingot can be 150 mm and the thickness can be 80 mm; or the diameter of the glass ingot can be 130 mm and the thickness can be 90 mm, etc., and the embodiments of the present application do not limit this.

[0079] It should be understood that the steps shown in the method of the embodiments of the present application are not exclusive, and other steps can also be executed before, after, or between the steps shown in the method.

[0080] Hereinafter, the chalcogenide glass and its preparation method provided by the embodiments of the present application will be described in conjunction with specific examples.

[0081] Example 1

[0082] The molar percentages of the constituent elements of the chalcogenide glass provided in this example are as follows:

[0083] The molar percentage of germanium (Ge) is 7 mol%;

[0084] The molar percentage of arsenic (As) is 43 mol%;

[0085] The molar percentage of tellurium (Te) is 45 mol%;

[0086] The molar percentage of selenium (Se) is 5 mol%.

[0087] The preparation method of chalcogenide glass includes the following steps:

[0088] Step 1: Weigh and mix the raw materials according to the above-mentioned molar percentages of the constituent elements in the chalcogenide glass.

[0089] Step 2: Put the mixed raw materials into a quartz bottle, seal it and evacuate it to obtain a vacuum-sealed environment with a vacuum degree higher than 5×10 -1 Pa.

[0090] Step 3: Melting treatment is carried out on the raw materials in the evacuated and sealed quartz bottle at a temperature of 800°C to 1000°C for 15 hours to 20 hours.

[0091] Step 4: Rapidly cool the molten glass. When rapidly cooling, the temperature of the molten glass is not lower than 400°C, and the temperature of the glass obtained after cooling is not higher than 250°C.

[0092] Step 5: Anneal the glass obtained by rapid cooling at an annealing cooling rate of 10°C / hour to 20°C / hour, and the annealing temperature is 160°C to 210°C.

[0093] Measure the annealed chalcogenide glass, and the refractive index n of the glass at a wavelength of 10μm is 3.45, and the glass transition temperature of the glass is 160°C.

[0094] The diameter of the glass ingot of the annealed chalcogenide glass is 150mm, and the thickness is 80mm. Compared with the same type of glass ingot in the industry, the diameter is increased by 50%, and the volume reaches 3 times that of the same type of glass ingot. It can solve the problem of crystallization during the melting process of large-diameter glass. At the same time, after inspection, there are no stripes with a length of more than 400μm inside the prepared glass, and the cross-sectional area ratio of defects such as internal impurity bubbles in the glass is less than 0.1%.

[0095] By measuring the glass with a thickness of 2mm, the curve of wavelength and transmittance as shown in Figure 1 can be obtained. From the curve in Figure 1 , it can be seen that the average transmittance of the glass in the 2μm to 17μm band is greater than or equal to 50%.

[0096] Example 2

[0097] The molar percentages of the constituent elements of the chalcogenide glass provided in this example are:

[0098] The molar percentage of germanium Ge is 7.5mol%;

[0099] The molar percentage of arsenic As is 44mol%;

[0100] The molar percentage of tellurium Te is 41 mol%;

[0101] The molar percentage of selenium Se is 7 mol%;

[0102] The sum of the molar percentages of antimony Sb, tin Sn, and gallium Ga is 0.5 mol%.

[0103] The preparation method of the chalcogenide glass comprises the following steps:

[0104] Step 1, weighing and mixing the raw materials according to the above-mentioned molar percentages of the constituent elements in the chalcogenide glass.

[0105] Step 2, putting the mixed raw materials into a quartz bottle, sealing it, and evacuating it to obtain a vacuum-sealed environment with a vacuum degree higher than 5×10 -1 Pa.

[0106] Step 3, melting the raw materials in the sealed and evacuated quartz bottle at a temperature of 800 °C to 1000 °C for 15 hours to 20 hours.

[0107] Step 4, rapidly cooling the molten glass. When rapidly cooling, the temperature of the molten glass is not lower than 400 °C, and the temperature of the glass obtained after cooling is not higher than 250 °C.

[0108] Step 5, annealing the glass obtained by rapid cooling at an annealing temperature reduction rate of 10 °C / hour to 20 °C / hour, and the annealing temperature is 160 °C to 210 °C.

[0109] Measuring the annealed chalcogenide glass, the refractive index n of the glass at a wavelength of 10 μm is 3.4, and the glass transition temperature of the glass is 170 °C.

[0110] The diameter of the glass ingot of the annealed chalcogenide glass is 150 mm, and the thickness is 80 mm. Compared with the caliber of the same type of glass ingot in the industry, it has increased by 50%, and the volume has reached 3 times that of the same type of glass ingot. It can solve the problem of crystallization during the melting of large-caliber glass. At the same time, it is inspected that there are no stripes with a length of more than 400 μm inside the prepared glass, and the cross-sectional area ratio of defects such as internal impurities and air bubbles in the glass is less than 0.1%.

[0111] By measuring the glass with a thickness of 2 mm, the average transmittance of the glass in the 2 μm to 17 μm band can be obtained to be greater than or equal to 50%.

[0112] Example 3

[0113] The molar percentages of the constituent elements of the chalcogenide glass provided in this example:

[0114] The molar percentage of germanium Ge is 8 mol%;

[0115] The molar percentage of arsenic As is 45 mol%;

[0116] The molar percentage of tellurium Te is 41 mol%;

[0117] The molar percentage of selenium Se is 5 mol%;

[0118] The sum of the molar percentages of antimony Sb, tin Sn, and gallium Ga is 1 mol%.

[0119] The preparation method of the chalcogenide glass includes the following steps:

[0120] Step 1, weigh and mix the raw materials according to the above molar percentages of the constituent elements in the chalcogenide glass.

[0121] Step 2, put the mixed raw materials into a quartz bottle, seal it, and evacuate it to obtain a vacuum-sealed environment with a vacuum degree higher than 5*10 -1 pa.

[0122] Step 3, melt the raw materials in the sealed and evacuated quartz bottle at a temperature of 800 °C to 1000 °C for 15 hours to 20 hours.

[0123] Step 4, rapidly cool the molten glass. When rapidly cooling, the temperature of the molten glass is not lower than 400 °C, and the temperature of the glass obtained after cooling is not higher than 250 °C.

[0124] Step 5, anneal the glass obtained by rapid cooling at an annealing cooling rate of 10 °C / hour to 20 °C / hour, and the annealing temperature is 160 °C to 210 °C.

[0125] Measure the annealed chalcogenide glass, and obtain that the refractive index n of the glass at a wavelength of 10 μm is 3.43, and the glass transition temperature of the glass is 175 °C.

[0126] The diameter of the glass ingot of the annealed chalcogenide glass is 130 mm, and the thickness is 90 mm. Compared with the caliber of the same type of glass ingot in the industry, it has increased by 50%, and the volume has reached 3 times that of the same type of glass ingot. It can solve the problem of crystallization during the melting of large-caliber glass. At the same time, it is inspected that there are no stripes with a length of more than 400 μm inside the prepared glass, and the cross-sectional area ratio of defects such as internal impurities and air bubbles in the glass is less than 0.1%.

[0127] By measuring the glass with a thickness of 2 mm, it can be obtained that the average transmittance of the glass in the 2 μm to 17 μm band is greater than or equal to 50%.

[0128] Example 4

[0129] The molar percentages of the constituent elements of the chalcogenide glass provided in this example:

[0130] The molar percentage of germanium Ge is 8.5 mol%;

[0131] The molar percentage of arsenic As is 46 mol%;

[0132] The molar percentage of tellurium Te is 39 mol%;

[0133] The molar percentage of selenium Se is 5 mol%;

[0134] The sum of the molar percentages of antimony Sb, tin Sn, and gallium Ga is 1.5 mol%.

[0135] The preparation method of the chalcogenide glass comprises the following steps:

[0136] Step 1, weighing and mixing the raw materials according to the above-mentioned molar percentages of the constituent elements in the chalcogenide glass.

[0137] Step 2, putting the mixed raw materials into a quartz bottle, sealing it, and evacuating it to obtain a vacuum-sealed environment with a vacuum degree higher than 5*10 -1 Pa.

[0138] Step 3, melting the raw materials in the sealed and evacuated quartz bottle at a temperature of 800 °C to 1000 °C for 15 hours to 20 hours.

[0139] Step 4, rapidly cooling the molten glass. When rapidly cooling, the temperature of the molten glass is not lower than 400 °C, and the temperature of the obtained glass after cooling is not higher than 250 °C.

[0140] Step 5, annealing the glass obtained by rapid cooling at an annealing temperature reduction rate of 10 °C / hour to 20 °C / hour, and the annealing temperature is 160 °C to 210 °C.

[0141] Measuring the refractive index of the annealed chalcogenide glass, and obtaining that the refractive index n of the glass at a wavelength of 10 μm is 3.37.

[0142] Measuring the annealed chalcogenide glass, obtaining that the refractive index n of the glass at a wavelength of 10 μm is 3.37, and the glass transition temperature of the glass is 172 °C.

[0143] The diameter of the glass ingot of the annealed chalcogenide glass is 140 mm, and the thickness is 85 mm. Compared with the caliber of the same type of glass ingot in the industry, it has increased by 50%, and the volume has reached 3 times that of the same type of glass ingot. It can solve the problem of crystallization during the melting of large-caliber glass. At the same time, it is inspected that there are no stripes with a length of more than 400 μm inside the obtained glass, and the cross-sectional area ratio of defects such as internal impurities and air bubbles in the glass is less than 0.1%.

[0144] By measuring the glass with a thickness of 2 mm, the average transmittance of the glass in the wavelength range of 2 μm to 17 μm is greater than or equal to 50%.

[0145] Example 5

[0146] The molar percentages of the constituent elements of the chalcogenide glass provided in this example are as follows:

[0147] The molar percentage of germanium (Ge) is 9 mol%;

[0148] The molar percentage of arsenic (As) is 47 mol%;

[0149] The molar percentage of tellurium (Te) is 39 mol%;

[0150] The molar percentage of selenium (Se) is 3 mol%;

[0151] The sum of the molar percentages of antimony (Sb), tin (Sn), and gallium (Ga) is 2 mol%.

[0152] The preparation method of the chalcogenide glass includes the following steps:

[0153] Step 1: Weigh and mix the raw materials according to the above molar percentages of the constituent elements in the chalcogenide glass.

[0154] Step 2: Put the mixed raw materials into a quartz bottle, seal it, and evacuate it to obtain a vacuum-sealed environment with a vacuum degree higher than 5×10 -1 Pa.

[0155] Step 3: Melt the raw materials in the sealed and evacuated quartz bottle at a temperature of 800°C to 1000°C for 15 hours to 20 hours.

[0156] Step 4: Rapidly cool the molten glass. When rapidly cooling, the temperature of the molten glass is not lower than 400°C, and the temperature of the glass obtained after cooling is not higher than 250°C.

[0157] Step 5: Anneal the glass obtained by rapid cooling at an annealing temperature reduction rate of 10°C / h to 20°C / h, and the annealing temperature is 160°C to 210°C.

[0158] Measure the annealed chalcogenide glass, and the refractive index n of the glass at a wavelength of 10 μm is 3.38, and the glass transition temperature of the glass is 185°C.

[0159] The diameter of the glass ingot of the chalcogenide glass obtained by annealing is 150 mm, and the thickness is 80 mm. Compared with the same type of glass ingots in the industry, the caliber has increased by 50%, and the volume has reached 3 times that of the same type of glass ingots. It can solve the problem of crystallization during the melting of large-caliber glass. At the same time, after inspection, there are no streaks longer than 400 μm inside the prepared glass, and the cross-sectional area ratio of defects such as impurity bubbles inside the glass is less than 0.1%.

[0160] By measuring the glass with a thickness of 2 mm, it can be obtained that the average transmittance of the glass in the wavelength range of 2 μm to 17 μm is greater than or equal to 50%.

[0161] Example 6

[0162] The molar percentages of the constituent elements of the chalcogenide glass provided in this example are as follows:

[0163] The molar percentage of germanium (Ge) is 9.5 mol%;

[0164] The molar percentage of arsenic (As) is 48 mol%;

[0165] The molar percentage of tellurium (Te) is 36.5 mol%;

[0166] The molar percentage of selenium (Se) is 5 mol%;

[0167] The sum of the molar percentages of antimony (Sb), tin (Sn), and gallium (Ga) is 1 mol%.

[0168] The preparation method of the chalcogenide glass includes the following steps:

[0169] Step 1: Weigh and mix the raw materials according to the above molar percentages of the constituent elements in the chalcogenide glass.

[0170] Step 2: Put the mixed raw materials into a quartz bottle, seal it, and evacuate to obtain a vacuum-sealed environment with a vacuum degree higher than 5×10 -1 Pa.

[0171] Step 3: Melt the raw materials in the quartz bottle after sealing and evacuating at a temperature of 800 °C to 1000 °C for 15 hours to 20 hours.

[0172] Step 4: Rapidly cool the molten glass. When rapidly cooling, the temperature of the molten glass is not lower than 400 °C, and the temperature of the glass obtained after cooling is not higher than 250 °C.

[0173] Step 5: Anneal the glass obtained by rapid cooling at an annealing cooling rate of 10 °C / h to 20 °C / h, and the annealing temperature is 160 °C to 210 °C.

[0174] The obtained chalcogenide glass after annealing was measured, and the refractive index n of the glass at a wavelength of 10 μm was 3.25, and the glass transition temperature of the glass was 210 °C.

[0175] The diameter of the glass ingot of the chalcogenide glass obtained by annealing was 130 mm, and the thickness was 90 mm. Compared with the same type of glass ingots in the industry, the caliber increased by 50%, and the volume reached 3 times that of the same type of glass ingots. It can solve the problem of crystallization during the melting of large-caliber glass. At the same time, it was inspected that there were no stripes longer than 400 μm inside the obtained glass, and the cross-sectional area ratio of defects such as impurity bubbles inside the glass was less than 0.1%.

[0176] By measuring the glass with a thickness of 2 mm, it can be obtained that the average transmittance of the glass in the 2 μm - 17 μm band is greater than or equal to 50%.

[0177] Example 7

[0178] The molar percentages of the constituent elements of the chalcogenide glass provided in this example are as follows:

[0179] The molar percentage of germanium Ge is 10 mol%;

[0180] The molar percentage of arsenic As is 43 mol%;

[0181] The molar percentage of tellurium Te is 38 mol%;

[0182] The molar percentage of selenium Se is 9 mol%.

[0183] The preparation method of the chalcogenide glass includes the following steps:

[0184] Step 1, weigh and mix the raw materials according to the above molar percentages of the constituent elements in the chalcogenide glass.

[0185] Step 2, put the mixed raw materials into a quartz bottle, seal it and evacuate it to obtain a vacuum-sealed environment with a vacuum degree higher than 5×10 -1 Pa.

[0186] Step 3, melt the raw materials in the sealed and evacuated quartz bottle at a temperature of 800 °C - 1000 °C for 15 hours - 20 hours.

[0187] Step 4, rapidly cool the molten glass. When rapidly cooling, the temperature of the molten glass is not lower than 400 °C, and the temperature of the obtained glass after cooling is not higher than 250 °C.

[0188] Step 5, anneal the glass obtained by rapid cooling at an annealing cooling rate of 10 °C / hour - 20 °C / hour, and the annealing temperature is 160 °C - 210 °C.

[0189] The obtained chalcogenide glass after annealing was measured, and the refractive index n of the glass at a wavelength of 10 μm was 3.26, and the glass transition temperature of the glass was 185 °C.

[0190] The diameter of the glass ingot of the annealed chalcogenide glass was 150 mm and the thickness was 80 mm. Compared with the same type of glass ingots in the industry, the caliber increased by 50%, and the volume reached 3 times that of the same type of glass ingots. It can solve the problem of crystallization during the melting of large-caliber glass. At the same time, after inspection, there are no stripes longer than 400 μm inside the obtained glass, and the cross-sectional area ratio of defects such as internal impurity bubbles in the glass is less than 0.1%.

[0191] By measuring the glass with a thickness of 2 mm, it can be obtained that the average transmittance of the glass in the 2 μm - 17 μm band is greater than or equal to 50%.

[0192] The embodiments of the present application also provide an optical element, and this optical element can be made of the chalcogenide glass provided by the above embodiments.

[0193] Optionally, the optical element made of the chalcogenide glass provided by the above embodiments can be a lens. For example, a convex lens or a concave lens, etc. The embodiments of the present application do not limit the type of the lens.

[0194] The embodiments of the present application also provide an infrared thermal imaging device, as Figure 2 shown, this infrared thermal imaging device may include an optical lens 100 and an infrared detector 200, wherein the optical lens 100 may include the optical element provided by the above embodiments.

[0195] In some optional embodiments of the present application, infrared light can be focused on the infrared detector 200 through the lens made of the chalcogenide glass provided by the above embodiments in the optical lens 100 to form an infrared image.

[0196] It should be noted that the imaging device of the embodiments of the present application can be an independent imaging device or an imaging module integrated on a mobile electronic device such as a mobile phone. The embodiments of the present application do not limit this.

[0197] The above specific embodiments do not constitute a limitation to the protection scope of the present application. Those skilled in the art should understand that various modifications, combinations, sub-combinations and substitutions can be made according to design requirements and other factors. Any modifications, equivalent substitutions and improvements made within the spirit and principle of the present application shall be included within the protection scope of the present application.

Claims

1. A chalcogenide glass, characterized in that, The constituent elements of the chalcogenide glass include: Germanium (Ge) with a molar percentage of 5 mol% to 15 mol%; Arsenic (As) with a molar percentage of 40 mol% to 55 mol%; Tellurium (Te) with a molar percentage of 30 mol% to 50 mol%; and Selenium (Se) with a molar percentage of 0.1 mol% to 9 mol%; The chalcogenide glass has a refractive index greater than 3 in the infrared band and the refractive index is uniform.

2. The chalcogenide glass according to claim 1, wherein The molar percentage of the germanium (Ge) is 7 mol% to 10 mol%; the molar percentage of the arsenic (As) is 43 mol% to 50 mol%; the molar percentage of the tellurium (Te) is 35 mol% to 45 mol%; the molar percentage of the selenium (Se) is 0.5 mol% to 9 mol%.

3. The chalcogenide glass according to claim 1, characterized in that, The sum of the molar percentages of the germanium (Ge) and selenium (Se) is less than or equal to 20 mol%.

4. The chalcogenide glass according to any one of claims 1 to 3, characterized in that The elements also include antimony (Sb), tin (Sn), and gallium (Ga), and the sum of the molar percentages of the antimony (Sb), tin (Sn), and gallium (Ga) is 0 to 5 mol%.

5. The chalcogenide glass according to claim 4, wherein, The sum of the molar percentages of the antimony (Sb), tin (Sn), and gallium (Ga) is 0.1 mol% to 2 mol%.

6. A chalcogenide glass, characterized in that, The constituent elements of the chalcogenide glass include: Germanium (Ge) with a molar percentage of 5 mol% to 14 mol%; Arsenic (As) with a molar percentage of 41 mol% to 55 mol%; Tellurium (Te) with a molar percentage of 30 mol% to 47 mol%; and Selenium (Se) with a molar percentage of 0.2 mol% to 9 mol%; The chalcogenide glass has an average transmittance greater than or equal to 50% in the 2 μm to 17 μm band, a refractive index greater than 3 and the refractive index is uniform.

7. A method for preparing a chalcogenide glass, characterized in that, The preparation method includes: Mixing raw materials according to the predetermined molar percentages of the constituent elements in the chalcogenide glass; Melting the mixed raw materials in a vacuum-sealed environment; Cooling the molten glass obtained; and Annealing the cooled glass to obtain the chalcogenide glass, the chalcogenide glass has a refractive index greater than 3 in the infrared band and the refractive index is uniform, wherein the elements include germanium (Ge), arsenic (As), tellurium (Te), and selenium (Se), and are configured according to the following molar percentages: Germanium (Ge) has a molar percentage of 5 mol% to 15 mol%; Arsenic (As) has a molar percentage of 40 mol% to 55 mol%; Tellurium (Te) has a molar percentage of 30 mol% to 50 mol%; Selenium (Se) has a molar percentage of 0.1 mol% to 9 mol%.

8. A method for preparing a chalcogenide glass, characterized in that, The preparation method includes: Mixing raw materials according to the predetermined molar percentages of the constituent elements in the chalcogenide glass; Melting the mixed raw materials in a vacuum-sealed environment; Cooling the molten glass obtained; and Annealing the cooled glass to obtain the chalcogenide glass, the chalcogenide glass has an average transmittance greater than or equal to 50% in the 2 μm to 17 μm band, a refractive index greater than 3 and the refractive index is uniform, wherein the elements include germanium (Ge), arsenic (As), tellurium (Te), and selenium (Se), and are configured according to the following molar percentages: Germanium (Ge), with a molar percentage of 5 mol% to 14 mol%; Arsenic As, with a molar percentage of 41 mol% to 55 mol%; Tellurium Te, with a molar percentage of 30 mol% to 47 mol%; and Selenium Se, with a molar percentage of 0.2 mol% to 9 mol%.

9. An optical element, characterized in that, The optical element is made of the chalcogenide glass according to any one of claims 1 to 7.

10. An infrared thermal imaging device, characterized in that, It includes an optical lens and an infrared detector, and the optical lens includes the optical element according to claim 9.

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