Si-containing chalcogenide glass with optimized absorption peak as well as preparation method and application of Si-containing chalcogenide glass

Abstract

The invention provides Si-containing chalcogenide glass with an optimized absorption peak as well as a preparation method and application of the Si-containing chalcogenide glass, and belongs to the technical field of special glass. Compared with common commercial chalcogenide glass As2Se3, the Si-containing chalcogenide glass provided by the invention is doped with a high-coordination Si element, the hardness is higher than that of common commercial chalcogenide glass As2Se3, meanwhile, a Sn-O bond is introduced by adopting a mode of doping Sn element, the Sn-O bond is stronger than a Si-O bond, and the absorption peak position of the Sn-O bond is mainly in a 20-30mu m wave band and does not influence an infrared window, so that the absorption peak of the Si-containing chalcogenide glass can be effectively optimized, and the absorption performance of the Si-containing chalcogenide glass is improved. Therefore, the high-hardness chalcogenide glass which can be applied to infrared windows is obtained. The result of the embodiment shows that the absorption peak of the Si-containing chalcogenide glass provided by the invention at an infrared window of 8-12 microns is obviously reduced, the hardness can reach 221.9 kg mm <-2 > at most, and the infrared window transmittance reaches 60%.

Description

Technical Field

[0001] The present invention relates to the technical field of special glass, and particularly relates to a Si-containing chalcogenide glass with optimized absorption peak, a preparation method thereof, and an application thereof. Background Art

[0002] Chalcogenide glasses have a wide range of applications in fields such as people's livelihood and military, and play an important role in optical materials. The material properties can be adjusted according to requirements and are suitable for various optical lens designs. However, the surface hardness of chalcogenide glasses is relatively low, and commonly used Ge single crystals are used as the outermost lens design of optical lenses, which greatly increases the cost of the lenses. By doping low-cost Si elements in chalcogenide glasses, the hardness can be effectively improved. However, due to the large bond strengths of Si-O and Si-H, the absorption peak of Si-containing chalcogenide glasses in the infrared window is very strong. Therefore, how to optimize the absorption peak of Si-containing chalcogenide glasses and make them have high hardness at the same time has become a technical problem to be solved urgently in this field. Summary of the Invention

[0003] The purpose of the present invention is to provide a Si-containing chalcogenide glass with optimized absorption peak, a preparation method thereof, and an application thereof. The Si-containing chalcogenide glass provided by the present invention has a significantly reduced absorption peak at the 8-12 μm infrared window and has high hardness at the same time.

[0004] In order to achieve the above-mentioned invention purpose, the present invention provides the following technical solutions:

[0005] The present invention provides a Si-containing chalcogenide glass with optimized absorption peak, including the following components: Cu: 2.5-12 at%; Si: 1.5-8 at%; As: 25-40 at%; Se: 40-55 at%; and Sn: 3-10 at%.

[0006] The present invention provides a preparation method of the Si-containing chalcogenide glass with optimized absorption peak according to the above technical solution, including the following steps:

[0007] (1) Mix Cu6Si4 alloy powder, As element, Se element, Sn element and a deoxidizer to obtain a mixture to be purified, and then purify the mixture to be purified to obtain a purified mixture;

[0008] (2) Melt, quench and anneal the purified mixture obtained in step (1) in sequence to obtain a Si-containing chalcogenide glass with optimized absorption peak.

[0009] Preferably, in step (1), the deoxidizer is Mg element or Al element, and the mass of the deoxidizer is 0.03-0.1% of the total mass of As element, Se element and Sn element.

[0010] Preferably, in step (1), the purification method is vacuum distillation combined with the deoxidizer method.

[0011] Preferably, in the step (1), the mixture to be purified is first placed in a quartz reactor, and then the quartz reactor is placed in a two-temperature-zone distillation furnace for purification.

[0012] Preferably, the vacuum degree for purification in the step (1) is ≥5×10 -5 Pa; during purification, the cold-end temperature of the two-temperature-zone distillation furnace is 300-500 °C, the hot-end temperature of the two-temperature-zone distillation furnace is 950-1000 °C; the purification time is 10-30 h.

[0013] Preferably, in the step (2), the melting temperature is 950-1000 °C, and the melting time is 30-35 h.

[0014] Preferably, in the step (2), the quenching temperature is 400-450 °C, and the quenching method is water-cooled quenching.

[0015] Preferably, in the step (2), the annealing temperature is 200-250 °C, the annealing time is 6-12 h, and the annealing cooling rate is 2-10 °C / h.

[0016] The present invention provides the application of the Si-containing chalcogenide glass with optimized absorption peak described in the above technical solution or the Si-containing chalcogenide glass with optimized absorption peak prepared by the preparation method described in the above technical solution in infrared optics.

[0017] The present invention provides a Si-containing chalcogenide glass with optimized absorption peak, comprising the following components: Cu: 2.5-12 at%; Si: 1.5-8 at%; As: 25-40 at%; Se: 40-55 at% and Sn: 3-10 at%. The Si-containing chalcogenide glass provided by the present invention has a higher hardness than the common commercial chalcogenide glass As2Se3 due to the doping of the high-coordination Si element. At the same time, the Sn-O bond is introduced by doping the Sn element. Since the Sn-O bond is stronger than the Si-O bond, and the absorption peak position of the Sn-O bond is mainly in the 20-30 μm band and does not affect the infrared window, the absorption peak of the Si-containing chalcogenide glass can be effectively optimized, so as to obtain a high-hardness chalcogenide glass applicable to the infrared window. The results of the examples show that the absorption peak of the Si-containing chalcogenide glass provided by the present invention is significantly reduced at the 8-12 μm infrared window, and the highest hardness can reach 221.9 kgmm -2 , and the infrared window transmittance reaches 60%. Description of the Drawings

[0018] Figure 1 It is a graph of the infrared window transmittance of the Si-containing chalcogenide glass prepared in Example 1 and Comparative Example 1. Detailed Embodiments

[0019] The present invention provides a Si-containing chalcogenide glass with optimized absorption peak, which comprises the following components: Cu: 2.5-12 at%; Si: 1.5-8 at%; As: 25-40 at%; Se: 40-55 at% and Sn: 3-10 at%.

[0020] The Si-containing chalcogenide glass with optimized absorption peak provided by the present invention comprises Cu: 2.5-12 at%. As an embodiment of the present invention, the content of Cu can be 2.5 at%, 3 at%, 3.5 at%, 4 at%, 4.5 at%, 5 at%, 5.5 at%, 6 at%, 6.5 at%, 7 at%, 7.5 at%, 8 at%, 8.5 at%, 9 at%, 9.5 at%, 10 at%, 10.5 at%, 11 at%, 11.5 at% or 12 at%. In the present invention, the Cu element is a basic element of the chalcogenide glass.

[0021] The Si-containing chalcogenide glass with optimized absorption peak provided by the present invention further comprises Si: 1.5-8 at%. As an embodiment of the present invention, the content of Si can be 1.5 at%, 2 at%, 2.5 at%, 3 at%, 3.5 at%, 4 at%, 4.5 at%, 5 at%, 5.5 at%, 6 at%, 6.5 at%, 7 at%, 7.5 at% or 8 at%. The chalcogenide glass provided by the present invention is doped with a high-coordination Si element, which can significantly improve the hardness of the chalcogenide glass.

[0022] The Si-containing chalcogenide glass with optimized absorption peak provided by the present invention further comprises As: 25-40 at%. As an embodiment of the present invention, the content of As can be 25 at%, 28 at%, 30 at%, 32 at%, 35 at%, 38 at% or 40 at%. In the present invention, the As element is a basic element of the chalcogenide glass.

[0023] The Si-containing chalcogenide glass with optimized absorption peak provided by the present invention further comprises Se: 40-55 at%. As an embodiment of the present invention, the content of Se can be 40 at%, 42 t%, 45 t%, 48 t%, 50 t%, 52 t% or 55 t%. In the present invention, the Se element is a basic element of the chalcogenide glass.

[0024] The Si-containing chalcogenide glass with optimized absorption peak provided by the present invention further includes Sn: 3-10 at%. As an implementation manner of the present invention, the content of Sn can be 3 at%, 3.5 at%, 4 at%, 4.5 at%, 5 at%, 5.5 at%, 6 at%, 6.5 at%, 7 at%, 7.5 at%, 8 at%, 8.5 at%, 9 at%, 9.5 at% or 10 at%. By doping Sn element into the Si-containing chalcogenide glass, since the Sn-O bond is stronger than the Si-O bond, and the absorption peak position of the Sn-O bond is mainly in the 20-30 μm band without affecting the infrared window, the absorption peak of the Si-containing chalcogenide glass can be effectively optimized, so as to obtain a high-hardness chalcogenide glass applicable to the infrared window.

[0025] The Si-containing chalcogenide glass provided by the present invention has a higher hardness than the common commercial chalcogenide glass As2Se3 due to the doping of high-coordination Si element. However, due to the absorption peaks of Si-O bond and Si-H bond, the application of this material at the infrared window is limited. Therefore, the Sn-O bond is introduced by doping Sn element. Since the Sn-O bond is stronger than the Si-O bond, and the absorption peak position of the Sn-O bond is mainly in the 20-30 μm band without affecting the infrared window, the absorption peak of the Si-containing chalcogenide glass can be effectively optimized, so as to obtain a high-hardness chalcogenide glass applicable to the infrared window.

[0026] The absorption peak of the Si-containing chalcogenide glass provided by the present invention is significantly reduced at the 8-12 μm infrared window, and the Si-containing chalcogenide glass has a higher hardness than the commercially available As2Se3 infrared chalcogenide glass material in the market.

[0027] The present invention provides a preparation method of the Si-containing chalcogenide glass with optimized absorption peak described in the above technical solution, including the following steps:

[0028] (1) Mix Cu6Si4 alloy powder, As element, Se element, Sn element and deoxidizer to obtain a mixture to be purified, and then purify the mixture to be purified to obtain a purified mixture;

[0029] (2) Melt, quench and anneal the purified mixture obtained in step (1) in sequence to obtain the Si-containing chalcogenide glass with optimized absorption peak.

[0030] The present invention mixes Cu6Si4 alloy powder, As element, Se element, Sn element and deoxidizer to obtain a mixture to be purified, and then purifies the mixture to be purified to obtain a purified mixture.

[0031] In the present invention, the Cu6Si4 alloy powder is preferably a high-purity Cu6Si4 alloy powder; the As element is preferably a high-purity As element; the Se element is preferably a high-purity Se element; the Sn element is preferably a high-purity Sn element; the purities of the Cu6Si4 alloy powder, As element, Se element, and Sn element are independently preferably ≥5N. The present invention has no special limitation on the specific sources of the Cu6Si4 alloy powder, As element, Se element, and Sn element, and raw materials commercially available to those skilled in the art or prepared by methods well-known to those skilled in the art can be used. The present invention has no special limitation on the particle sizes of the Cu6Si4 alloy powder, As element, Se element, and Sn element, which can be determined according to the common general knowledge of those skilled in the art. By using high-purity materials as raw materials, the present invention can reduce the contents of impurities and oxides in the raw materials, thereby further improving the purity of the glass.

[0032] In the present invention, the deoxidizer is preferably an Mg element or an Al element; the mass of the deoxidizer is preferably 0.03-0.1% of the total mass of the As element, Se element, and Sn element. As an embodiment of the present invention, the mass of the deoxidizer can be 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, or 0.1% of the total mass of the As element, Se element, and Sn element. By using an Mg element or an Al element as the deoxidizer in the present invention, both the Mg element and the Al element are active elements and have the ability to preferentially combine with oxygen to form bonds during the purification process, so that the X-O bonds existing in the chalcogenide glass and causing a series of harmful absorptions in the near, middle, and far infrared regions can be eliminated. Moreover, the oxides generated by the deoxidizer have a low vapor pressure and can volatilize without remaining in the chalcogenide glass, and will not affect the composition of the chalcogenide glass. By controlling the dosage of the deoxidizer, it is possible to avoid the problem that the oxygen impurities in the chalcogenide glass cannot be fully removed due to too little dosage of the deoxidizer, and to avoid the problem that the glass crystallizes due to too much dosage of the deoxidizer, resulting in devitrification during glass drawing.

[0033] In the present invention, the operation of mixing the Cu6Si4 alloy powder, As element, Se element, Sn element, and deoxidizer preferably includes: first mixing the As element, Se element, and Sn element, then adding the deoxidizer and mixing, and finally adding the Cu6Si4 alloy powder to obtain the material to be purified. By mixing in the above manner, the present invention can ensure that the raw materials are mixed evenly, so as to facilitate the full elimination of X-O bonds by the deoxidizer during the subsequent purification process.

[0034] In the present invention, the purification method is preferably vacuum distillation combined with an oxygen scavenger method. By purifying the raw materials, the present invention can eliminate [-OH] and [H-O-H] impurities in the chalcogenide glass, and reduce the influence of non-intrinsic absorption loss in the chalcogenide glass on its infrared characteristics.

[0035] In the present invention, the mixture to be purified is preferably first placed in a quartz reactor, and then the quartz reactor is placed in a two-temperature-zone distillation furnace for purification.

[0036] In the present invention, the quartz reactor is preferably an H-type double-tube quartz ampoule. In the present invention, the H-type double-tube quartz ampoule preferably includes a raw material tube, a purification tube, and a connecting tube; the connecting tube preferably connects the raw material tube and the purification tube; one end of the raw material tube is preferably provided with an opening, or one end of the raw material tube and one end of the purification tube are preferably both provided with openings. By using the quartz reactor with the above structure for purification in the present invention, it is convenient to seal the opening of the raw material tube during purification, thereby providing a vacuum environment for the mixture and the oxygen scavenger placed in the H-type double-tube quartz ampoule, avoiding the introduction of impurities due to oxidation of the raw materials, and thus reducing the non-intrinsic absorption of the chalcogenide glass in the infrared region.

[0037] In the present invention, the quartz reactor is preferably pretreated by dehydroxylation. In the present invention, the method of dehydroxylation pretreatment preferably includes: sequentially cleaning the quartz reactor with hydrofluoric acid, deionized water, and absolute ethanol, and finally drying it. The present invention has no special limitation on the number and time of the cleaning, which is determined according to the common technical knowledge of those skilled in the art and can remove the impurity oxygen. In the present invention, the drying is preferably carried out in an oven. The present invention has no special limitation on the temperature and time of the drying, which is determined according to the common technical knowledge of those skilled in the art and only needs to be dried to a constant weight. By pretreating the quartz reactor by dehydroxylation in the present invention, it is possible to avoid the introduction of impurity oxygen into the reaction by the quartz reactor.

[0038] In the present invention, after the mixture to be purified is placed in the quartz reactor, it is preferably first evacuated and preheated, and then the opening on the raw material tube in the quartz reactor is sealed.

[0039] In the present invention, the degree of vacuum for evacuation is preferably ≥5×10 -5 Pa, more preferably 5×10 -5 ~1×10 - 3 Pa; the time for evacuation is preferably ≥3 h; the preheating temperature is preferably 50 - 100 °C; the evacuation and preheating are preferably carried out simultaneously. As an embodiment of the present invention, the degree of vacuum for evacuation can be 5×10 -5 Pa, 1×10 - 4 Pa, 5×10 -4Pa or 1×10 -3 Pa; the evacuation time can be 3 h, 4 h or 5 h; the preheating temperature can be 50 °C, 60 °C, 70 °C, 80 °C, 90 °C or 100 °C. By evacuating the air, a vacuum environment can be provided for subsequent purification in the present invention. By controlling the degree of vacuum and time during evacuation, the degree of vacuum during purification can meet the requirements; by performing purification in a vacuum atmosphere, the influence brought by oxygen in the air can be avoided.

[0040] There are no special limitations on the specific model and source of the dual-temperature zone distillation furnace in the present invention, and a commercially available dual-temperature zone distillation furnace well-known to those skilled in the art can be used.

[0041] In the present invention, the degree of vacuum for purification is preferably ≥5×10 -5 Pa, more preferably 5×10 -5 ~1×10 -3 Pa; the cold-end temperature of the dual-temperature zone distillation furnace during purification is preferably 300 - 500 °C, more preferably 350 - 450 °C, and further preferably 420 °C; the hot-end temperature of the dual-temperature zone distillation furnace is preferably 950 - 1000 °C, more preferably 960 - 990 °C, and further preferably 980 °C; the purification time is preferably 10 - 30 h, more preferably 18 - 28 h, and further preferably 22 - 24 h. As an implementation mode of the present invention, the degree of vacuum for purification can be 5×10 -5 Pa, 1×10 -4 Pa, 5×10 - 4 Pa or 1×10 -3 Pa. By performing purification in a dual-temperature zone distillation furnace in the present invention, taking advantage of the large difference in vapor pressure between the element and its oxide in the raw material at a certain temperature, distillation treatment is carried out to remove oxygen and other non-volatile impurities, thereby achieving the effect of deoxidation; by controlling the purification parameters, impurities can be further removed.

[0042] After obtaining the purified mixture, the present invention melts, quenches and anneals the purified mixture in sequence to obtain a Si-containing chalcogenide glass with optimized absorption peaks.

[0043] In the present invention, the melting temperature is preferably 950 - 1000 °C; the melting time is preferably 30 - 35 h. As an implementation mode of the present invention, the melting temperature can be 950 °C, 960 °C, 970 °C, 980 °C, 990 °C or 1000 °C; the melting time can be 30 h, 31 h, 32 h, 33 h, 34 h or 35 h. By controlling the melting parameters in the present invention, the raw materials can be completely melted and mixed together to form a glassy state, and then a chalcogenide glass with short-range order and long-range disorder can be formed.

[0044] After the melting is completed, the present invention preferably cools the melted product to the quenching temperature for quenching. The present invention has no special limitation on the cooling method, which is determined according to the common technical knowledge of those skilled in the art, as long as the end temperature of the cooling can be the quenching temperature. As an embodiment of the present invention, the cooling method can be natural cooling.

[0045] In the present invention, the quenching temperature is preferably 400-450 °C; the quenching method is preferably water-cooling quenching. The present invention has no special limitation on the quenching time, and it can be quenched to room temperature. As an embodiment of the present invention, the quenching temperature can be 400 °C, 410 °C, 420 °C, 430 °C, 440 °C or 450 °C. Through the quenching treatment, the present invention can make the structure of the glass short-range ordered and long-range disordered, so that it has excellent mechanical properties.

[0046] In the present invention, the annealing temperature is preferably 200-250 °C; the annealing time is preferably 6-12 h; the annealing cooling rate is preferably 2-10 °C / h. As an embodiment of the present invention, the annealing temperature can be 200 °C, 210 °C, 220 °C, 230 °C, 240 °C or 250 °C; the annealing holding time can be 6 h, 7 h, 8 h, 9 h, 10 h, 11 h or 12 h; the annealing cooling rate can be 2 °C / h, 3 °C / h, 4 °C / h, 5 °C / h, 6 °C / h, 7 °C / h, 8 °C / h, 9 °C / h or 10 °C / h. In the present invention, the annealing is preferably carried out in an annealing furnace. The present invention has no special limitation on the specific model and source of the annealing furnace, and a commercially available annealing furnace well-known to those skilled in the art can be used. By annealing the chalcogenide glass, the present invention can reduce or eliminate the non-uniform permanent thermal stress formed during the quenching process of the chalcogenide glass, thereby improving the mechanical strength and thermal stability of the chalcogenide glass.

[0047] The preparation method provided by the present invention first purifies the raw materials to remove the excess impurities in the raw materials, so that the X-O bonds that exist in the chalcogenide glass and cause a series of harmful absorptions in the near, middle and far infrared regions are eliminated, and then melting, quenching and annealing are carried out in sequence. Through melting, the components are mixed evenly, through quenching treatment, a glass with short-range order and long-range disorder is formed, and through annealing treatment, the mechanical properties and physical properties of the glass are further improved, and then a high-hardness chalcogenide glass is obtained; the preparation method provided by the present invention is simple, and the equipment used is common equipment, without the need to introduce large and expensive equipment, which is convenient for large-scale industrial production.

[0048] The present invention also provides an application of the Si-containing chalcogenide glass with optimized absorption peak described in the above technical solution or the Si-containing chalcogenide glass with optimized absorption peak prepared by the preparation method described in the above technical solution in infrared optics.

[0049] The present invention has no special limitation on the specific manner of the application, and the application can be carried out in a manner well-known to those skilled in the art.

[0050] Next, the technical solutions in the present invention will be clearly and completely described in conjunction with the embodiments in the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the protection scope of the present invention.

[0051] Example 1

[0052] A Si-containing chalcogenide glass with optimized absorption peak is composed of the following components: Cu: 5.82 at%; Si: 3.88 at%; As: 32.98 at%; Se: 49.47 at%; Sn: 7.85 at%.

[0053] The preparation method of the Si-containing chalcogenide glass with optimized absorption peak is the following steps:

[0054] (1) First, mix As elemental substance, Se elemental substance and Sn elemental substance, then add a deoxidizer and mix, and finally add Cu6Si4 alloy powder to obtain a substance to be purified; the purities of the Cu6Si4 alloy powder, As elemental substance, Se elemental substance and Sn elemental substance are all ≥ 5N; the deoxidizer is Mg elemental substance, and the mass of the deoxidizer is 0.1% of the total mass of As elemental substance, Se elemental substance and Sn elemental substance; the purification method is vacuum distillation combined with the deoxidizer method;

[0055] Put the above-mentioned substance to be purified into a quartz reactor through the opening on the raw material tube of the quartz reactor. Then, evacuate and preheat the quartz reactor. Evacuation and preheating are carried out simultaneously. Then, seal the opening on the raw material tube of the quartz reactor. Finally, put the quartz reactor into a two-temperature zone distillation furnace for purification to obtain a purified mixture; the quartz reactor is an H-type double-tube quartz ampoule; the H-type double-tube quartz ampoule is composed of a raw material tube, a purification tube and a connecting tube. The connecting tube connects the raw material tube and the purification tube, and one end of the raw material tube is provided with an opening; the quartz reactor is subjected to a dehydroxylation pretreatment before purification. The method of dehydroxylation pretreatment is: clean the quartz reactor successively with hydrofluoric acid, deionized water and absolute ethanol, and finally dry it in an oven; the vacuum degree of evacuation is 1×10 -3Pa, the vacuum pumping time is 3 h, and the preheating temperature is 90 °C; the cold end temperature of the double-temperature zone distillation furnace is 400 °C, the hot end temperature of the double-temperature zone distillation furnace is 950 °C, and the purification time in the double-temperature zone distillation furnace is 24 h;

[0056] (2) Melt the purified mixture obtained in the step (1) at a melting temperature of 980 °C for 35 h, then naturally cool it to 420 °C and then water quench it to room temperature, and then anneal it in an annealing furnace at 220 °C for 6 h, and finally cool it to room temperature at a cooling rate of 10 °C / h to obtain a Si-containing chalcogenide glass with optimized absorption peaks.

[0057] Example 2

[0058] A Si-containing chalcogenide glass with optimized absorption peaks consists of the following components: Cu: 2.91 at%; Si: 1.94 at%; As: 35.696 at%; Se: 53.544 at%; Sn: 5.91 at%;

[0059] The preparation method of the Si-containing chalcogenide glass with optimized absorption peaks is the following steps:

[0060] (1) First, mix As elemental substance, Se elemental substance and Sn elemental substance, then add a deoxidizer and mix, and finally add Cu6Si4 alloy powder to obtain a substance to be purified; the purities of the Cu6Si4 alloy powder, As elemental substance, Se elemental substance and Sn elemental substance are all ≥ 5N; the deoxidizer is Mg elemental substance, and the mass of the deoxidizer is 0.1% of the total mass of the As elemental substance, Se elemental substance and Sn elemental substance; the purification method is vacuum distillation combined with the deoxidizer method;

[0061] Put the above-mentioned substance to be purified into the quartz reactor through the opening on the raw material tube of the quartz reactor, then evacuate and preheat the quartz reactor simultaneously, then seal the opening on the raw material tube of the quartz reactor, and finally put the quartz reactor into a double-temperature zone distillation furnace for purification to obtain a purified mixture; the quartz reactor is an H-type double-tube quartz ampoule; the H-type double-tube quartz ampoule consists of a raw material tube, a purification tube and a connecting tube, the connecting tube connects the raw material tube and the purification tube, and one end of the raw material tube is provided with an opening; the quartz reactor is subjected to a dehydroxylation pretreatment before purification, and the dehydroxylation pretreatment method is: clean the quartz reactor successively with hydrofluoric acid, deionized water and absolute ethanol, and finally dry it in an oven; the vacuum degree of the vacuum pumping is 1×10 -3 Pa, the vacuum pumping time is 3 h, and the preheating temperature is 90 °C; the cold end temperature of the double-temperature zone distillation furnace is 400 °C, the hot end temperature of the double-temperature zone distillation furnace is 950 °C, and the purification time in the double-temperature zone distillation furnace is 24 h;

[0062] (2)Melt the purified mixture obtained in step (1) at a melting temperature of 950 °C for 35 h, then naturally cool it to 420 °C and water quench it to room temperature, then anneal it in an annealing furnace at 220 °C for 6 h, and finally cool it to room temperature at a cooling rate of 10 °C / h to obtain a Si-containing chalcogenide glass with optimized absorption peaks.

[0063] Example 3

[0064] A Si-containing chalcogenide glass with optimized absorption peaks is composed of the following components: Cu: 2.85 at%; Si: 1.9 at%; As: 34.96 at%; Se: 52.44 at%; Sn: 7.85 at%.

[0065] The preparation method of the Si-containing chalcogenide glass with optimized absorption peaks is the following steps:

[0066] (1) First, mix elemental As, elemental Se and elemental Sn, then add a deoxidizer and mix, and finally add Cu6Si4 alloy powder to obtain a material to be purified; the purities of the Cu6Si4 alloy powder, elemental As, elemental Se and elemental Sn are all ≥ 5N; the deoxidizer is elemental Mg, and the mass of the deoxidizer is 0.1% of the total mass of elemental As, elemental Se and elemental Sn; the purification method is vacuum distillation combined with the deoxidizer method;

[0067] Put the above material to be purified into a quartz reactor through the opening on the raw material tube of the quartz reactor, then evacuate and preheat the quartz reactor, evacuating and preheating are carried out simultaneously, then seal the opening on the raw material tube of the quartz reactor, and finally put the quartz reactor into a two-temperature zone distillation furnace for purification to obtain a purified mixture; the quartz reactor is an H-type double-tube quartz ampoule; the H-type double-tube quartz ampoule consists of a raw material tube, a purification tube and a connecting tube, the connecting tube connects the raw material tube and the purification tube, and one end of the raw material tube is provided with an opening; the quartz reactor is subjected to a dehydroxylation pretreatment before purification, and the method of dehydroxylation pretreatment is: wash the quartz reactor successively with hydrofluoric acid, deionized water and absolute ethanol, and finally dry it in an oven; the vacuum degree of evacuation is 1×10 -3 Pa, the evacuation time is 3 h, the preheating temperature is 90 °C; the cold-end temperature of the two-temperature zone distillation furnace is 400 °C, the hot-end temperature of the two-temperature zone distillation furnace is 950 °C, and the purification time in the two-temperature zone distillation furnace is 24 h;

[0068] (2) Melt the purified mixture obtained in step (1) at a melting temperature of 950 °C for 35 h, then naturally cool it to 420 °C and then perform water quenching to room temperature, and then anneal it in an annealing furnace at 220 °C for 6 h. Finally, cool it to room temperature at a cooling rate of 10 °C / h to obtain a Si-containing chalcogenide glass with optimized absorption peaks.

[0069] Use an indentation hardness tester to test the hardness of the Si-containing chalcogenide glass with optimized absorption peaks prepared in Examples 1 to 3 by the indentation method. The results are shown in Table 1:

[0070] Table 1 Hardness of the Si-containing chalcogenide glass with optimized absorption peaks prepared in Examples 1 to 3

[0071] Example <![CDATA[Hardness / kgmm -2 > Example 1 221.9 Example 2 206.8 Example 3 212.5

[0072] Comparative Example 1

[0073] A Si-containing chalcogenide glass is composed of the following components: Cu: 6 at%; Si: 4 at%; As: 36 at%; Se: 54 at%;

[0074] The preparation method of the Si-containing chalcogenide glass is the following steps:

[0075] (1) First, mix As elemental substance and Se elemental substance, then add a deoxidizer and mix, and finally add Cu6Si4 alloy powder to obtain a substance to be purified; the purities of the Cu6Si4 alloy powder, As elemental substance and Se elemental substance are all ≥5N; the deoxidizer is Mg elemental substance, and the mass of the deoxidizer is 0.1% of the total mass of As elemental substance and Se elemental substance; the purification method is vacuum distillation combined with the deoxidizer method;

[0076] Put the above-mentioned substance to be purified into a quartz reactor through the opening on the raw material tube of the quartz reactor. Then, evacuate and preheat the quartz reactor simultaneously. Then, seal the opening on the raw material tube of the quartz reactor. Finally, put the quartz reactor into a two-temperature zone distillation furnace for purification to obtain a purified mixture; the quartz reactor is an H-type double-tube quartz ampoule; the H-type double-tube quartz ampoule is composed of a raw material tube, a purification tube and a connecting tube. The connecting tube connects the raw material tube and the purification tube, and one end of the raw material tube is provided with an opening; the quartz reactor is subjected to a dehydroxylation pretreatment before purification. The method of the dehydroxylation pretreatment is: wash the quartz reactor successively with hydrofluoric acid, deionized water and absolute ethanol, and finally dry it in an oven; the vacuum degree of the evacuation is 1×10 -3 Pa, the evacuation time is 3 h, and the preheating temperature is 90 °C; the cold end temperature of the two-temperature zone distillation furnace is 400 °C, the hot end temperature of the two-temperature zone distillation furnace is 950 °C, and the purification time in the two-temperature zone distillation furnace is 24 h;

[0077] (2) Melt the purified mixture obtained in step (1) at a melting temperature of 950 °C for 35 h, then naturally cool it to 420 °C and then water quench it to room temperature, and then anneal it in an annealing furnace at 190 °C for 6 h, and finally cool it to room temperature at a cooling rate of 10 °C / h to obtain Si-containing chalcogenide glass.

[0078] Use a Fourier transform infrared spectrometer to test the properties of the Si-containing chalcogenide glass prepared in Example 1 and Comparative Example 1 by the Fourier transform method, and the obtained infrared window transmittance curve diagram is as Figure 1 shown. Figure 1 In the figure, curve 1 is the infrared window transmittance curve diagram of the Si-containing chalcogenide glass prepared in Example 1, and curve 2 is the infrared window transmittance curve diagram of the Si-containing chalcogenide glass prepared in Comparative Example 1. It can be Figure 1 seen that the Si-containing chalcogenide glass prepared in Example 1 of the present invention has an infrared window transmittance of 60%, and the absorption peak in the 8-12 μm infrared window is significantly reduced; the Si-containing chalcogenide glass prepared in Comparative Example 1 has an excessive absorption peak in the 8-12 μm infrared window.

[0079] Comparative Example 2

[0080] A Si-containing chalcogenide glass is composed of the following components: Cu: 6 at%; Si: 4 at%; As: 28 at%; Se: 42 at%; Sn: 20 at%;

[0081] The preparation method of the Si-containing chalcogenide glass is the following steps:

[0082] (1) First, mix As elemental, Se elemental and Sn elemental, then add a deoxidizer and mix, and finally add Cu6Si4 alloy powder to obtain a material to be purified; the purities of the Cu6Si4 alloy powder, As elemental, Se elemental and Sn elemental are all ≥ 5N; the deoxidizer is Mg elemental, and the mass of the deoxidizer is 0.1% of the total mass of As elemental, Se elemental and Sn elemental; the purification method is vacuum distillation combined with the deoxidizer method;

[0083] Put the above-mentioned substance to be purified into a quartz reactor through the opening on the raw material tube in the quartz reactor. Then, evacuate and preheat the quartz reactor. The evacuation and preheating are carried out simultaneously. Then, seal the opening on the raw material tube in the quartz reactor. Finally, put the quartz reactor into a two-temperature-zone distillation furnace for purification to obtain a purified mixture; the quartz reactor is an H-type double-tube quartz ampoule; the H-type double-tube quartz ampoule consists of a raw material tube, a purification tube, and a connecting tube. The connecting tube connects the raw material tube and the purification tube, and one end of the raw material tube is provided with an opening; the quartz reactor is subjected to a dehydroxylation pretreatment before purification. The method of the dehydroxylation pretreatment is: clean the quartz reactor successively with hydrofluoric acid, deionized water, and absolute ethanol, and finally dry it in an oven; the degree of vacuum for evacuation is 1×10 -3 Pa, the evacuation time is 3 h, and the preheating temperature is 90 °C; the cold-end temperature of the two-temperature-zone distillation furnace is 400 °C, the hot-end temperature of the two-temperature-zone distillation furnace is 950 °C, and the purification time in the two-temperature-zone distillation furnace is 24 h;

[0084] (2) Melt the purified mixture obtained in step (1). The melting temperature is 950 °C, and the melting time is 35 h. Then, naturally cool it to 420 °C and then perform water quenching to room temperature. Then, anneal it in an annealing furnace at 230 °C for 6 h. Finally, cool it to room temperature at a cooling rate of 10 °C / h to obtain a Si-containing chalcogenide glass.

[0085] The Si-containing chalcogenide glass prepared in Comparative Example 2 crystallizes and cannot form a glass, indicating that when the doping amount of Sn element is too high, the stability of the glass will become poor.

[0086] It can be seen from the comparison of Examples 1 to 3 and Comparative Examples 1 to 2 that when an appropriate amount of Sn element is used for doping, the absorption peak of the Si-containing chalcogenide glass in the 8-12 μm infrared window can be effectively reduced, and the hardness of the Si-containing chalcogenide glass is improved; while excessive Sn doping may lead to too many internal co-polar bonds in the Si-containing chalcogenide glass, making the stability of the Si-containing chalcogenide glass poor and not easy to form a glass.

[0087] The above is only the preferred embodiment of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A Si-containing chalcogenide glass with optimized absorption peak, comprising the following components: Cu: 2.5 - 12 at%; Si: 1.5 - 8 at%; As: 25 - 40 at%; Se: 40 - 55 at%; and Sn: 3 - 10 at%.

2. A method for preparing the Si-containing chalcogenide glass with optimized absorption peak according to claim 1, comprising the following steps: (1) Mix Cu6Si4 alloy powder, As elemental, Se elemental, Sn elemental and a deoxidizer to obtain a mixture to be purified, and then purify the mixture to be purified to obtain a purified mixture; (2) Melt, quench and anneal the purified mixture obtained in step (1) in sequence to obtain a Si-containing chalcogenide glass with optimized absorption peak.

3. The preparation method according to claim 2, wherein In step (1), the deoxidizer is Mg elemental or Al elemental, and the mass of the deoxidizer is 0.03 - 0.1% of the total mass of As elemental, Se elemental and Sn elemental.

4. The preparation method according to claim 2, characterized in that, In step (1), the purification method is vacuum distillation combined with the deoxidizer method.

5. The preparation method according to claim 2, wherein, In step (1), the mixture to be purified is first placed in a quartz reactor, and then the quartz reactor is placed in a two-temperature-zone distillation furnace for purification.

6. The preparation method according to claim 5, characterized in that, The vacuum degree for purification in the step (1) is ≥5×10 -5 Pa; during purification, the cold-end temperature of the double-temperature-zone distillation furnace is 300 to 500 °C, and the hot-end temperature of the double-temperature-zone distillation furnace is 950 to 1000 °C; the purification time is 10 to 30 h.

7. The preparation method according to claim 2, characterized in that, In step (2), the melting temperature is 950 - 1000 °C, and the melting time is 30 - 35 h.

8. The preparation method according to claim 2, wherein In step (2), the quenching temperature is 400 - 450 °C, and the quenching method is water-cooled quenching.

9. The preparation method according to claim 2, characterized in that, In step (2), the annealing temperature is 200 - 250 °C, the annealing time is 6 - 12 h, and the annealing cooling rate is 2 - 10 °C / h.

10. Application of the Si-containing chalcogenide glass with optimized absorption peak according to claim 1 or the Si-containing chalcogenide glass with optimized absorption peak prepared by the preparation method according to any one of claims 2 - 9 in infrared optics.

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