CN114671609A - Cu-containing high-refractive-index chalcogenide glass and preparation method thereof - Google Patents

Cu-containing high-refractive-index chalcogenide glass and preparation method thereof Download PDF

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CN114671609A
CN114671609A CN202210175158.7A CN202210175158A CN114671609A CN 114671609 A CN114671609 A CN 114671609A CN 202210175158 A CN202210175158 A CN 202210175158A CN 114671609 A CN114671609 A CN 114671609A
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tube
chalcogenide glass
refractive index
containing high
raw materials
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顾杰荣
沈祥
贾光
仵苗苗
夏克伦
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Ningbo Institute Of Oceanography
Ningbo University
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Ningbo Institute Of Oceanography
Ningbo University
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
    • C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/02—Pretreated ingredients
    • C03C1/022—Purification of silica sand or other minerals

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Abstract

The invention discloses Cu-containing high-refractive-index chalcogenide glass which comprises the following components in parts by weight: cu: 1 At% -15 At%; as: 30 At% -40 At%; se: 30 At% -40 At%; te: 15 At% -25 At%; the invention also discloses a preparation method of the Cu-containing high-refractive-index chalcogenide glass, which comprises the following steps of: s1, weighing the raw materials, putting the raw materials into a quartz reactor, and removing impurities from the raw materials to obtain a purified product; s2, high-temperature melting and quenching; and S3, annealing the quenched quartz reactor to obtain the Cu-containing high-refractive-index chalcogenide glass. The invention aims to provide chalcogenide glass containing Cu and high in refractive index, which is prepared by replacing Ge with Cu and doping element Te with high polarizability on the basis of the existing Ge-Sb-Se chalcogenide glass, so that the problems of low refractive index, high glass preparation cost and the like of chalcogenide glass in the current market are solved, and the application economic benefit of the chalcogenide glass is improved.

Description

Cu-containing high-refractive-index chalcogenide glass and preparation method thereof
Technical Field
The invention relates to the technical field of special chalcogenide glass, in particular to Cu-containing high-refractive-index chalcogenide glass and a preparation method thereof, and belongs to the field of infrared optical materials.
Background
Chalcogenide glass is used as an infrared optical material with excellent performance. The material has the advantages of good infrared transmission performance, adjustable components, stable thermochemistry and the like, and has wide application prospect in the field of infrared optics. The refractive index is one of the most basic optical material performance parameters and one of the important optical design parameters, has very important significance for simplifying an optical system and improving the imaging quality, and has profound significance for further miniaturization of mobile phones and digital cameras and improvement of optical communication.
The common chalcogenide glass on the market generally has low refractive index, for example, As-Se, Ge-Sb-Se, Ge-As-Se and other glasses have good middle and far infrared transmission capability and near infrared transmission characteristics, and are examined and accepted by the market. However, the refractive index of the glass at 10um is not more than 2.8, the lens thickness obtained by preparation does not meet the requirement of current times for simplification of the lens, and the high-price Ge simple substance is doped, so that the production cost is high. With the increase of market demand, development of chalcogenide glass with lower cost and higher refractive index is imperative.
Disclosure of Invention
In view of the defects in the prior art, one of the objectives of the present invention is to provide a chalcogenide glass with high refractive index containing Cu, which is based on the existing Ge-Sb-Se chalcogenide glass, and the Cu is used to replace Ge and is doped with element Te with high polarizability, so as to alleviate the technical problem of low linear refractive index of the Ge-Sb-Se chalcogenide glass in the prior art.
The technical scheme adopted by the embodiment of the invention is as follows: the Cu-containing high-refractive-index chalcogenide glass comprises the following components in parts by weight:
Cu：1At％～15At％；
As：30At％～40At％；
Se：30At％～40At％；
Te：15At％～25At％；
wherein the Cu-containing high refractive index chalcogenide glass has a refractive index of > 3at a wavelength of 10 [ mu ] m.
Optionally, the transition temperature of the Cu-containing high-refractive-index chalcogenide glass is 150-175 ℃; the Cu-containing high-refractive-index chalcogenide glass in the temperature range is suitable for die stamping.
Alternatively, Cu: 10 At%; as: 36 At%; se: 31.5 At%; te: 22.5 At%; or
Cu: 7.5 At%; as: 37 At%; se: 32.5 At%; te: 23 At%; or
Cu: 12.5 At%; as: 35 At%; se: 30.5 At%; te: 22 At%; or
Cu：10At％；As：36At％；Se：31.5At％；Te：22.5At％。
Optionally, the density of the Cu-containing high-refractive-index chalcogenide glass is 4.99g/cm3～5.35g/cm3The refractive index of the film is 3.16 to 3.29 at a wavelength of 10 μm.
By adopting the scheme, the element Te is introduced into the Cu-containing high-refractive-index chalcogenide glass, the element Te is taken as the element with the largest relative atomic mass in chalcogen elements (oxygen element and polonium element), the infrared cut-off wavelength of the Te-based chalcogenide glass can reach about 25 micrometers, the cut-off edge of an optical fiber is about 23 micrometers, but the glass transition temperature is relatively low, the heat stability and the mechanical strength are poor, and the glass can not be formed independently, so the glass modifier is often used as a glass modifier to be introduced into other glass components, so as to obtain the glass meeting the corresponding requirements, has very high atomic weight and polarizability, can effectively improve the linear refractive index of the glass, in the scheme, Cu is adopted to replace Ge element, the cost of the Cu simple substance is far lower than that of Ge, the proposal greatly reduces the economic cost of glass preparation, and the prepared glass has refractive index far higher than that of As which is most widely applied in the market. 2Se3Glass, can further reduce the thickness of the lens, simplify the optical system and improve the yieldThe image quality has very important significance.
The second purpose of the present invention is to provide a method for producing a chalcogenide glass having a high refractive index and containing Cu.
The technical scheme adopted by the embodiment of the invention is as follows: the preparation method of the chalcogenide glass containing Cu and high refractive index comprises the following steps:
s1, weighing raw materials, wherein the raw materials comprise simple substances of Cu, As, Se and Te, putting the raw materials into a quartz reactor, vacuumizing, sealing the quartz reactor by melting, and removing impurities and purifying the raw materials to obtain a purified product;
s2, high-temperature melting and quenching, namely putting the quartz tube packaged with the purified raw materials into a heating furnace for high-temperature melting at 850-950 ℃ for 30-35 h, obtaining a melt in the quartz tube after heating, cooling the packaged melt to 400-450 ℃, and then quenching, curing and molding;
and S3, annealing the quenched quartz reactor to obtain the Cu-containing high-refractive-index chalcogenide glass.
Optionally, the step S1 includes the following steps:
s11, uniformly mixing the weighed Cu, As, Se and Te simple substances to obtain a mixture, and weighing a deoxidant, wherein the weighing amount of the deoxidant is 0.03-0.1 wt% of the total amount of the mixture; the dosage of the oxygen scavenger is less than 0.03 wt%, oxygen impurities in the chalcogenide glass cannot be sufficiently removed, and if the dosage of the oxygen scavenger is more than 0.1 wt%, the glass is crystallized due to excessive mixing of the oxygen scavenger, so that the glass is devitrified during drawing;
S12, the quartz reactor is an H-shaped double-tube quartz ampoule which comprises a raw material tube, a purifying tube and a connecting tube for connecting the raw material tube and the purifying tube, one end of the raw material tube is provided with an opening, the mixture and the deoxidant are uniformly mixed and placed in the raw material tube, and the opening of the raw material tube is sealed by fusion after the H-shaped double-tube quartz ampoule is vacuumized; the operation of the step is to provide a vacuum environment for the raw materials placed in the H-shaped double-tube quartz ampoule, avoid the raw materials from being oxidized and introducing impurities into the materials, thereby reducing the extrinsic absorption of chalcogenide glass in an infrared region;
s13, placing the H-shaped double-tube quartz ampoule into a double-temperature-zone distillation furnace, performing distillation purification, obtaining purified substances of Cu, As, Se and Te in the purification tube, and then sealing the connection tube by flame; the raw materials are purified by adopting the raw material distillation mode, so that the extrinsic loss of the chalcogenide glass finished product is reduced.
Optionally, the purities of the simple substances Cu, As, Se, and Te in step S11 are not lower than 5N; the higher the purity of the feedstock, the less the impurity oxygen content from the feedstock.
Optionally, in step S11, the oxygen scavenger is Mg or Al; the deoxidant is magnesium element simple substance or aluminum element simple substance, the two elements are active elements, the two elements have the capability of combining with oxygen preferentially to form bonds, a series of harmful absorbed X-O bonds existing in chalcogenide glass and caused in near, middle and far infrared regions are eliminated, and the generated oxide has lower vapor pressure, so that trace deoxidant can remove oxide impurities in chalcogenide glass.
Optionally, in step S12, preheating is performed during the process of evacuating the H-shaped double-tube quartz ampoule, and the degree of vacuum of evacuation is not higher than 5 × 10-5mbar, for not less than 3 hours.
Optionally, the preheating temperature in the process of vacuumizing the H-shaped double-tube quartz ampoule is 90 ℃.
Optionally, the quenching in step S2 is air cooling quenching.
Drawings
FIG. 1 is a graph showing the refractive index profile of a Cu-containing high-refractive-index chalcogenide glass in example 1 of the present invention;
FIG. 2 is a transmission curve of a Cu-containing high-refractive-index chalcogenide glass in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The application aims to provide the chalcogenide glass containing Cu and having the high refractive index, and the Cu-As-Se-Te chalcogenide glass with the high refractive index is prepared by utilizing the element Te with the high polarizability and the Cu with the low cost, so that the problems of low refractive index, high glass preparation cost and the like of the chalcogenide glass in the current market are solved, and the application economic benefit of the chalcogenide glass is improved.
The application also aims to provide a preparation method of the Cu-containing high-refractive-index chalcogenide glass, which comprises the following steps:
s1, weighing raw materials, wherein the raw materials comprise simple substances of Cu, As, Se and Te, putting the raw materials into a quartz reactor, vacuumizing, sealing the quartz reactor by melting, and removing impurities and purifying the raw materials to obtain a purified product;
s2, high-temperature melting and quenching, namely putting the quartz tube packaged with the purified raw materials into a heating furnace for high-temperature melting at 850-950 ℃ for 30-35 h, obtaining a melt in the quartz tube after heating, cooling the packaged melt to 400-450 ℃, and then quenching, curing and molding;
and S3, annealing the quenched quartz reactor to obtain the Cu-containing high-refractive-index chalcogenide glass.
Further, annealing the quenched quartz reactor, in fact, the refined product is annealed under vacuum conditions in order to form chalcogenide glass.
Further, step S1 is to obtain a purified raw material, and is to remove oxygen impurities from the raw material and reduce the influence of extrinsic absorption loss in chalcogenide glass on its infrared characteristics. In the field of chalcogenide glass preparation, three purification methods, namely a vacuum distillation method, an oxygen scavenger method and a vacuum distillation combined oxygen scavenger method, mainly exist, and the method for removing impurities and purifying raw materials to obtain purified products belongs to the protection range of the application.
Furthermore, the chalcogenide glass is purified by a vacuum distillation method, namely the chalcogenide glass is distilled by utilizing the characteristic that the vapor pressure of a simple substance in the raw materials is greatly different from that of an oxide of the simple substance at a certain temperature, so that oxygen and other non-volatile impurities are removed, and the effect of removing oxygen is achieved.
Furthermore, the oxygen scavenger method is to add oxygen scavenger, such as at least one element simple substance raw material of aluminum, magnesium and the like, into the quartz reactor under the vacuum condition or under the protection of inert gas, wherein the elements are all active elements, the ability of preferentially combining with oxygen is that X-O bonds existing in chalcogenide glass and causing a series of harmful absorption in near, middle and far infrared regions are eliminated, and the generated oxide has lower vapor pressure. Therefore, trace elemental substances of magnesium, aluminum and the like are added into the chalcogenide glass to remove oxide impurities in the chalcogenide glass.
Specifically, in the scheme of the present invention, a purification method combining vacuum distillation with an oxygen scavenger is adopted, that is, the step S1 includes the following steps:
s11, uniformly mixing the weighed Cu, As, Se and Te simple substances to obtain a mixture, and weighing a deoxidant, wherein the weighing amount of the deoxidant is 0.03-0.1 wt% of the total amount of the mixture;
S12, enabling the quartz reactor to be an H-shaped double-tube quartz ampoule, wherein the H-shaped double-tube quartz ampoule comprises a raw material tube, a purification tube and a connecting tube for connecting the raw material tube and the purification tube, one end of the raw material tube is provided with an opening, the mixture and the deoxidant are uniformly mixed and placed in the raw material tube, and after the H-shaped double-tube quartz ampoule is vacuumized, the opening of the raw material tube is sealed by fusing;
s13, placing the H-shaped double-tube quartz ampoule into a double-temperature-zone distillation furnace, distilling and purifying to obtain purified Cu, As, Se and Te in the purification tube, and then sealing the connecting tube with flame.
Specifically, step S12 may be replaced by the following: the quartz reactor is the double-barrelled quartz ampoule of H type, and this double-barrelled quartz ampoule of H type includes raw material tube, purification pipe and the connecting pipe of switch-on raw material tube and purification pipe, and the one end of raw material tube and the one end of purification pipe all are equipped with the opening, and in placing mixture and deoxidant misce bene into the raw material tube, melt the opening on the raw material tube, behind the double-barrelled quartz ampoule of evacuation H type, melt the opening on the purification pipe.
Specifically, the purities of the simple substances Cu, As, Se and Te are not less than 5N; namely, the high-refractivity glass raw materials adopt high-purity copper, high-purity arsenic, high-purity selenium and high-purity tellurium.
Specifically, in step S11, the oxygen scavenger is Mg or Al; .
Specifically, in step S12, preheating is performed during the process of vacuumizing the H-shaped double-tube quartz ampoule, and the degree of vacuum of the vacuumizing is not higher than 5 × 10-5mbar, in not less than 3 hours.
Specifically, the preheating temperature in the process of vacuumizing the H-shaped double-tube quartz ampoule is 90 ℃.
Specifically, the quenching in step S2 is air-cooled quenching.
Specifically, the steps S11-S13 are to remove impurities and purify the raw materials, and eliminate the [ -OH ] and [ H-O-H ] impurities in the chalcogenide glass. The above steps omit some routine experimental operations during the experiment, such as dehydroxylation pretreatment of the H-type double-tube quartz ampoule before step S1.
Further, the dehydroxylation pretreatment is specifically that the H-shaped double-tube quartz ampoule is sequentially cleaned by hydrofluoric acid, deionized water and absolute ethyl alcohol, and finally the H-shaped double-tube quartz ampoule is placed into a dry oven to be completely dried, so that the H-shaped double-tube quartz ampoule is prevented from bringing impurity oxygen to the reaction.
Furthermore, oxyhydrogen flame or oxyacetylene flame is adopted when the quartz material is fused and sealed and broken in the whole process, so that the impurity oxygen brought to the reaction in the sealing process is reduced.
For better technical solutions, the technical solutions will be described in detail below with reference to the drawings and specific embodiments of the specification.
Example 1
The embodiment provides a preparation method of Cu-containing chalcogenide glass with high refractive index, which comprises the following steps: the method is characterized in that a Cu, As, Se and Te simple substance with 5N purity is used As a raw material, and the raw material is prepared according to the following atomic percentage:
Cu：10At％；
As：36At％；
Se：31.5At％；
Te：22.5At％；
weighing 100g of raw materials in a glove box filled with inert gas and uniformly mixing; then the uniformly mixed raw materials are put into a glass raw material tube of an H-shaped double-tube quartz ampoule, the quartz ampoule is dried in advance and is pre-filled with 0.03-0.1 wt% of magnesium strips, in the embodiment, 0.1 wt% of magnesium strips are specifically adopted, the 0.1 wt% of magnesium strips is the weight percentage concentration of the magnesium strips in the glass mixture, the magnesium strips can react with oxides in the raw materials to remove oxygen impurities in the raw materials, the purpose of purifying the raw materials is achieved, and meanwhile, magnesium does not participate in the melting of glass. The quartz ampoule was evacuated to 1.0 x 10-3Pa, then sealing the quartz ampoule by oxyhydrogen flame; and (3) putting the sealed quartz ampoule into a double-temperature-zone distillation furnace, setting the temperature of the cold end to be 400 ℃ and the temperature of the hot end to be 950 ℃, and performing distillation and purification. Obtaining purified substances of Cu, As, Se and Te in a purified glass tube of a quartz ampoule, and then sealing off a double tube by oxyhydrogen flame; and (3) putting the quartz tube packaged with the purified raw materials into a heating furnace for high-temperature melting, wherein the heating temperature is 950 ℃, the heating time is 30 hours, obtaining a melt in the quartz tube after the heating is finished, cooling the packaged melt to 400 ℃, taking out the quartz tube, and carrying out air cooling solidification and molding to obtain a glass semi-finished product. And then placing the semi-finished glass product in an annealing furnace for annealing at the annealing temperature of 160 ℃ at the annealing speed of-5 ℃/h to obtain the Cu-containing high-refractive-index chalcogenide glass.
And (3) test results:
as shown in the combined FIG. 1 and FIG. 2, the Cu-containing chalcogenide glass with high refractive index obtained in the example has a transmittance of 58% in an infrared window, and has a density of 5.30g/cm at 25 DEG C3The refractive index of the glass at the wavelength of 10 mu m is 3.2641, which is far higher than that of the common chalcogenide glass in the market, and the transition temperature of the glass is 162 ℃, so that the glass is suitable for die stamping.
Example 2
The embodiment provides a preparation method of Cu-containing high-refractive-index chalcogenide glass, which comprises the following steps: taking 5N-purity Cu, As, Se and Te simple substances As raw materials, and proportioning according to the following atomic percentage:
Cu：7.5At％；
As：37At％；
Se：32.5At％；
Te：23At％；
weighing 100g of raw materials in a glove box filled with inert gas and uniformly mixing; then the uniformly mixed raw materials are put into a glass raw material tube of an H-shaped double-tube quartz ampoule, the quartz ampoule is dried in advance and is pre-filled with 0.03-0.1 wt% of magnesium strips, in the embodiment, 0.1 wt% of magnesium strips are specifically adopted, the 0.1 wt% of magnesium strips is the weight percentage concentration of the magnesium strips in the glass mixture, the magnesium strips can react with oxides in the raw materials to remove oxygen impurities in the raw materials, the purpose of purifying the raw materials is achieved, and meanwhile, magnesium does not participate in the melting of glass. The quartz ampoule was evacuated to 1.0 x 10 -3Pa, then sealing the quartz ampoule by oxyhydrogen flame; and (3) putting the sealed quartz ampoule into a double-temperature-zone distillation furnace, setting the temperature of the cold end to be 400 ℃ and the temperature of the hot end to be 950 ℃, and performing distillation purification. Purified substances of Cu, As, Se and Te are obtained in a purified glass tube of a quartz ampoule, and then a double tube is sealed off by oxyhydrogen flame; and (3) putting the quartz tube packaged with the purified raw materials into a heating furnace for high-temperature melting, wherein the heating temperature is 950 ℃, the heating time is 30 hours, obtaining a melt in the quartz tube after the heating is finished, cooling the packaged melt to 400 ℃, taking out the quartz tube, and carrying out air cooling solidification and molding to obtain a glass semi-finished product. And then placing the semi-finished glass product in an annealing furnace for annealing at the annealing temperature of 155 ℃ at the annealing speed of-5 ℃/h to obtain the Cu-containing chalcogenide glass with high refractive index.
The refractive index of the Cu-containing high-refractive-index chalcogenide glass with the wavelength of 10 mu m is 3.2204, which is far higher than that of the common chalcogenide glass on the market, the transition temperature of the glass is 157 ℃, and the density of the glass is 5.25g/cm3。
Example 3
The embodiment provides a preparation method of Cu-containing high-refractive-index chalcogenide glass, which comprises the following steps: taking 5N-purity Cu, As, Se and Te simple substances As raw materials, and proportioning according to the following atomic percentage:
Cu：12.5At％；
As：35At％；
Se：30.5At％；
Te：22At％；
Weighing 100g of raw materials in a glove box filled with inert gas and uniformly mixing; then the uniformly mixed raw materials are put into a glass raw material tube of an H-shaped double-tube quartz ampoule, the quartz ampoule is dried in advance and is pre-filled with 0.03-0.1 wt% of magnesium strips, in the embodiment, 0.1 wt% of magnesium strips are specifically adopted, the weight percentage concentration of the magnesium strips in the glass mixture is 0.1 wt%, the magnesium strips can react with oxides in the raw materials, oxygen impurities in the raw materials are removed, the purpose of purifying the raw materials is achieved, and meanwhile, magnesium does not participate in melting of glass. The quartz ampoule was evacuated to 1.0 x 10-3Pa, then sealing the quartz ampoule by oxyhydrogen flame; and (3) putting the sealed quartz ampoule into a double-temperature-zone distillation furnace, setting the temperature of the cold end to be 400 ℃ and the temperature of the hot end to be 950 ℃, and performing distillation purification. Purified substances of Cu, As, Se and Te are obtained in a purified glass tube of a quartz ampoule, and then a double tube is sealed off by oxyhydrogen flame; and (3) putting the quartz tube packaged with the purified raw materials into a heating furnace for high-temperature melting, wherein the heating temperature is 950 ℃, the heating time is 30 hours, obtaining a melt in the quartz tube after the heating is finished, cooling the packaged melt to 400 ℃, taking out the quartz tube, and carrying out air cooling solidification and molding to obtain a glass semi-finished product. And then placing the semi-finished glass product in an annealing furnace for annealing at the annealing temperature of 160 ℃ at the annealing speed of-5 ℃/h to obtain the Cu-containing high-refractive-index chalcogenide glass.
The refractive index of the Cu-containing high-refractive-index chalcogenide glass with the wavelength of 10 mu m is 3.2866, while the refractive index of As2Se3 glass which is most widely applied in the market at the wavelength of 10 mu m is only 2.7795, the transition temperature of the multi-element glass is 168 ℃, and the density of the multi-element glass is 5.40g/cm3。
Example 4
The embodiment provides a preparation method of Cu-containing high-refractive-index chalcogenide glass, which comprises the following steps: taking 5N-purity Cu, As, Se and Te simple substances As raw materials, and proportioning according to the following atomic percentage:
Cu：10At％；
As：36At％；
Se：31.5At％；
Te：22.5At％；
100g of the raw materials were weighed in a glove box filled with inert gas andmixing uniformly; then the uniformly mixed raw materials are put into a glass raw material tube of an H-shaped double-tube quartz ampoule, the quartz ampoule is dried in advance and is pre-filled with 0.03-0.1 wt% of magnesium strips, in the embodiment, 0.1 wt% of magnesium strips are specifically adopted, the 0.1 wt% of magnesium strips is the weight percentage concentration of the magnesium strips in the glass mixture, the magnesium strips can react with oxides in the raw materials to remove oxygen impurities in the raw materials, the purpose of purifying the raw materials is achieved, and meanwhile, magnesium does not participate in the melting of glass. The quartz ampoule was evacuated to 1.0 x 10-3Pa, then sealing the quartz ampoule by oxyhydrogen flame; and (3) putting the sealed quartz ampoule into a double-temperature-zone distillation furnace, setting the temperature of the cold end to be 400 ℃ and the temperature of the hot end to be 950 ℃, and performing distillation and purification. Obtaining purified substances of Cu, As, Se and Te in a purified glass tube of a quartz ampoule, and then sealing off a double tube by oxyhydrogen flame; and (3) putting the quartz tube packaged with the purified raw materials into a heating furnace for high-temperature melting, wherein the heating temperature is 950 ℃, the heating time is 30 hours, obtaining a melt in the quartz tube after the heating is finished, cooling the packaged melt to 400 ℃, taking out the quartz tube, and carrying out air cooling solidification and molding to obtain a glass semi-finished product. And then placing the semi-finished glass product in an annealing furnace for annealing at the annealing temperature of 160 ℃ at the annealing speed of-5 ℃/h to obtain the Cu-containing high-refractive-index chalcogenide glass.
The Cu-containing high-refractive-index chalcogenide glass has a refractive index of 3.2714 at a wavelength of 10 μm, a transition temperature of 174 ℃, and a density of 5.35g/cm3。
Comparative example 1
The comparative example provides a preparation method of Ge-doped chalcogenide glass, which comprises the following steps: the preparation method comprises the following steps of taking Ge, As and Se simple substances with 5N purity As raw materials, and proportioning according to the following atomic percentage:
Ge：10At％；
As：40At％；
Se：50At％；
weighing 100g of raw materials in a glove box filled with inert gas; then, the uniformly mixed raw materials were charged into two glass raw material tubes of an H-type double-tube quartz ampoule, which was previously dried and previously charged with 0.03 to 0.1 wt% of magnesium rod, specifically 0.1 wt% of magnesium rod in this comparative example, 0.1 wt% beingThe magnesium rods are in weight percentage concentration in the glass mixture and can react with oxides in the raw materials to remove oxygen impurities in the raw materials. The quartz ampoule was evacuated to 1.0 x 10- 3Pa, sealing the quartz ampoule by oxyhydrogen flame; and (3) putting the sealed quartz ampoule into a double-temperature-zone distillation furnace, setting the temperature of the cold end to be 400 ℃ and the temperature of the hot end to be 900 ℃, and performing distillation purification. Obtaining purified substances of Ge, As and Se in a purified glass tube of a quartz ampoule, and sealing off a double tube by oxyhydrogen flame; and (3) putting the quartz tube packaged with the purified raw materials into a heating furnace for high-temperature melting, wherein the heating temperature is 950 ℃, the heating time is 24 hours, obtaining a melt in the quartz tube after the heating is finished, cooling the packaged melt to 450 ℃, taking out the quartz tube, and carrying out air cooling solidification and molding to obtain a glass semi-finished product. And then placing the semi-finished glass product in an annealing furnace for annealing at the annealing temperature of 220 ℃ at the annealing speed of-5 ℃/h to obtain the chalcogenide glass.
And (3) test results:
the Ge-doped chalcogenide glass obtained by the comparative example has the transmittance reaching 60 percent in an infrared window, the refractive index of 10um wavelength of the Ge-doped chalcogenide glass is 2.6089, and the refractive index is lower.
Comparative example 2
The comparative example provides a method for preparing Ge-doped chalcogenide glass, comprising the following steps: taking 5N-purity Ge, As, Se and Te simple substances As raw materials, and proportioning according to the following atomic percentage:
Ge：10At％；
As：20At％；
Se：15At％；
Te：55At％；
weighing 100g of raw materials in a glove box filled with inert gas; then the evenly mixed raw materials are respectively filled into two glass raw material tubes of an H-shaped double-tube quartz ampoule, the quartz ampoule is dried in advance and is filled with 0.03-0.1 wt% magnesium strips in advance, 0.1 wt% magnesium strips are specifically adopted in the comparative example, the weight percentage concentration of the magnesium strips in the glass mixture is 0.1 wt%, and the magnesium strips can react with oxides in the raw materials to remove oxygen impurities in the raw materials. The quartz ampoule was evacuated to 1.0 x 10- 3Pa, flame-melting with hydrogen and oxygenSealing the quartz ampoule; and (3) putting the sealed quartz ampoule into a double-temperature-zone distillation furnace, setting the temperature of the cold end to be 400 ℃ and the temperature of the hot end to be 850 ℃, and performing distillation purification. Purified materials of Ge, As, Se and Te are obtained in a purified glass tube of a quartz ampoule, and a double tube is sealed off by oxyhydrogen flame; and (3) putting the quartz tube packaged with the purified raw materials into a heating furnace for high-temperature melting, wherein the heating temperature is 950 ℃, the heating time is 24 hours, obtaining a melt in the quartz tube after the heating is finished, cooling the packaged melt to 400 ℃, taking out the quartz tube, and carrying out air cooling solidification and molding to obtain a glass semi-finished product. And then placing the semi-finished glass product in an annealing furnace for annealing at the annealing temperature of 150 ℃ at the annealing speed of-5 ℃/h to obtain the Cu-containing high-refractive-index chalcogenide glass.
And (3) test results:
the Ge-doped chalcogenide glass obtained in this comparative example has a transmittance of only 50% in the infrared window and a refractive index of 3.2264 at a wavelength of 10um, and although the refractive index is increased by doping Te element, the transmittance is significantly decreased.
The foregoing has described preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary, and various changes made within the scope of the independent claims of the present invention are within the scope of the present invention.

Claims (10)

1. A Cu-containing chalcogenide glass with high refractive index is characterized in that: comprises the following components and proportions:
Cu：1At％～15At％；
As：30At％～40At％；
Se：30At％～40At％；
Te：15At％～25At％；
wherein the Cu-containing high refractive index chalcogenide glass has a refractive index of > 3at a wavelength of 10 [ mu ] m.
2. The Cu-containing high refractive index chalcogenide glass according to claim 1, characterized in that: the transition temperature of the Cu-containing high-refractive-index chalcogenide glass is 150-175 ℃.
3. The Cu-containing high refractive index chalcogenide glass according to claim 2, characterized in that: comprises the following components and proportions:
cu: 10 At%; as: 36 At%; se: 31.5 At%; te: 22.5 At%; or
Cu: 7.5 At%; as: 37 At%; se: 32.5 At%; te: 23 At%; or
Cu: 12.5 At%; as: 35 At%; se: 30.5 At%; te: 22 At%; or
Cu：10At％；As：36At％；Se：31.5At％；Te：22.5At％。
4. A method for producing a Cu-containing high refractive index chalcogenide glass according to any of claims 1 to 3, comprising the steps of:
s1, weighing raw materials, wherein the raw materials comprise simple substances of Cu, As, Se and Te, putting the raw materials into a quartz reactor, vacuumizing, sealing the quartz reactor by melting, and removing impurities and purifying the raw materials to obtain a purified product;
s2, high-temperature melting and quenching, namely putting the quartz tube packaged with the purified raw materials into a heating furnace for high-temperature melting at 850-950 ℃ for 30-35 h, obtaining a melt in the quartz tube after heating, cooling the packaged melt to 400-450 ℃, and then quenching, curing and molding;
and S3, annealing the quenched quartz reactor to obtain the Cu-containing high-refractive-index chalcogenide glass.
5. The method for producing a Cu-containing high refractive index chalcogenide glass according to claim 4, wherein the step S1 comprises the steps of:
s11, uniformly mixing the weighed Cu, As, Se and Te simple substances to obtain a mixture, and weighing a deoxidant, wherein the weighing amount of the deoxidant is 0.05-0.1 wt% of the total amount of the mixture;
S12, the quartz reactor is an H-shaped double-tube quartz ampoule which comprises a raw material tube, a purifying tube and a connecting tube for connecting the raw material tube and the purifying tube, one end of the raw material tube is provided with an opening, the mixture and the deoxidant are uniformly mixed and placed in the raw material tube, and the opening of the raw material tube is sealed by fusion after the H-shaped double-tube quartz ampoule is vacuumized;
s13, placing the H-shaped double-tube quartz ampoule into a double-temperature-zone distillation furnace, distilling and purifying to obtain purified substances of the simple substances Cu, As, Se and Te in the purification tube, and then sealing off the connecting tube by flame.
6. The method for producing a Cu-containing high refractive index chalcogenide glass according to claim 5, characterized in that: the purities of the elementary substances Cu, As, Se and Te in the step S11 are not lower than 5N.
7. The method for producing a Cu-containing high refractive index chalcogenide glass according to claim 5, characterized in that: in step S11, the oxygen scavenger is Mg or Al.
8. The method for producing a Cu-containing high refractive index chalcogenide glass according to claim 5, characterized in that: preheating is carried out in the process of vacuumizing the H-shaped double-tube quartz ampoule in the step S12, and the vacuum degree of vacuumizing is not higher than 5 x 10-5mbar, for not less than 3 hours.
9. The method for producing a Cu-containing high refractive index chalcogenide glass according to claim 8, characterized in that: the preheating temperature of the H-shaped double-tube quartz ampoule in the vacuumizing process is 90 ℃.
10. The method for producing a Cu-containing high refractive index chalcogenide glass according to claim 4, characterized in that: the quenching in step S2 is air-cooled quenching.
CN202210175158.7A 2022-02-25 2022-02-25 Cu-containing high-refractive-index chalcogenide glass and preparation method thereof Pending CN114671609A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6208792B1 (en) * 1999-09-20 2001-03-27 Lucent Technologies Inc. Article comprising a planar optical waveguide with optically non-linear core

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6208792B1 (en) * 1999-09-20 2001-03-27 Lucent Technologies Inc. Article comprising a planar optical waveguide with optically non-linear core

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JUEJUN HU, ETAL.: "Studies on structural, electrical, and optical properties of Cu doped As–Se–Te chalcogenide glasses", JOURNAL OF APPLIED PHYSICS, vol. 101, no. 6, pages 063520 - 1 *
孙敏 等: "《智能材料技术》", vol. 1, 国防工业出版社, pages: 315 - 317 *

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