KR20230061825A - Infrared Transmitting Chalcogenide Glass Composition Containing Zn and Glass Manufacturing Method Using the Same - Google Patents

Abstract

Disclosed are a Zn-containing composition for infrared-transmitting chalcogenide glass and a method for manufacturing optical glass using the same.
According to one embodiment of the present invention, in the composition for infrared-transmitting chalcogenide glass that transmits light in an infrared wavelength band above a predetermined reference value, it is characterized in that it is composed of Ge, Zn, In, and Se in a predetermined ratio A composition for glass is provided.

Description

Infrared Transmitting Chalcogenide Glass Composition Containing Zn and Glass Manufacturing Method Using the Same}

The present invention relates to a composition for chalcogenide glass containing Zn and transmitting light in an infrared wavelength band and a method for manufacturing optical glass using the composition.

The contents described in this part merely provide background information on the present embodiment and do not constitute prior art.

Infrared transmission lenses have been mainly used in the military field for the purpose of image processing for missile tracking. Since the infrared transmission lens used in the military field must maintain excellent performance even in a high-temperature environment, it is manufactured by processing crystals such as germanium one by one into the shape of a lens. Accordingly, the material is expensive and the productivity is low, so it is difficult to use such a military infrared transmission lens in the civilian field.

On the other hand, even in the private sector, demand for infrared lenses that can be used by being mounted on small terminals such as cameras or smart phones is increasing in order to measure far-infrared light emitted by humans or animals.

However, as conventional infrared lenses contain heavy metals such as antimony (Sb) or arsenic (As) or components harmful to the human body as raw materials, they may be harmful to the human body during the manufacturing process, during use after manufacturing, or during the disposal of the lens. . Due to these problems, there is a demand for an eco-friendly infrared lens that does not contain heavy metal components.

Infrared lenses can be manufactured by molding 1 to as many as 20 lenses using separate upper and lower molds through a glass molding machine, and most of the lenses have a diameter of 20 mm or more. On the other hand, in order to become an infrared lens suitable for civilian devices such as smart devices, it is advantageous if the infrared lens can be miniaturized and mass-produced.

For this purpose, an infrared lens manufacturing method is a wafer lens manufacturing method, and it is possible to manufacture about 100 infrared lenses each having a diameter of about 5 mm using wide wafer-shaped upper and lower molds. Infrared-transmitting chalcogenide glass suitable for the wafer lens forming method is advantageous for the process when the glass transition temperature is low.

An object of the present invention is to provide a composition for eco-friendly infrared-transmitting chalcogenide glass capable of securing an excellent glass transition temperature while containing Zn, and a method for manufacturing an optical glass using the same.

According to one aspect of the present invention, in a composition for infrared-transmitting chalcogenide glass that transmits light in an infrared wavelength band above a predetermined reference value, the glass is characterized in that it is composed of Ge, Zn, In, and Se in a predetermined ratio. A composition for

According to one aspect of the present invention, the preset ratio is when the contents of Ge, Zn, In, and Se are set to x (at%), y (at%), z (at%), and w (at%), respectively , characterized in that it satisfies 1≤x≤40 (at%), 1≤y+z≤15 (at%) and 50≤w≤85 (at%), respectively.

According to one aspect of the present invention, the predetermined ratio is 10at%: xat%: 5at%: (85-x)at% in the order of Ge, Zn, In and Se, and x is 2.5, 5 or 7.5. to be

According to one aspect of the present invention, in the method for manufacturing an infrared-transmitting chalcogenide glass that transmits light in an infrared wavelength band above a predetermined reference value, a predetermined ratio of Ge, Zn, In, and Se as raw materials is charged into a container. A sealing process of sealing by sealing, a melting process of melting raw materials in a container that has undergone the sealing process in a first preset environment, a quenching process of rapidly cooling raw materials melted in the melting process in a second preset environment, and a quenching process. It provides a method for manufacturing infrared-transmitting chalcogenide glass, characterized in that it comprises a slow cooling process of slowly cooling the raw materials in a third preset environment.

According to one aspect of the present invention, the first preset environment is characterized in that it has a temperature within a preset range based on 850 ℃.

According to one aspect of the present invention, the first preset environment is characterized in that it is formed by increasing several degrees Celsius per minute.

According to one aspect of the present invention, the melting process is characterized in that the container that has undergone the sealing process is mounted on a rocking device, and the raw materials in the container are mixed and melted in a first preset environment.

According to one aspect of the present invention, the melting process is characterized in that the raw materials in the container are mixed and melted for 12 hours in a first preset environment by the rocking device.

According to one aspect of the present invention, in the method for manufacturing a chalcogenide glass ingot in a wafer form, the chalcogenide glass ingot produced by the above method is prepared in a wafer form by sawing and polishing A characterized wafer manufacturing method is provided.

According to one aspect of the present invention, in the method of manufacturing a chalcogenide wafer as an infrared transmission wafer lens, the chalcogenide wafer is seated in a lower mold and the temperature after the seating process is set to the chalcogenide The raising process of raising the glass softening temperature of the wafer, the pressing process of compressing the chalcogenide wafers seated in the upper mold and the lower mold, the lowering process of lowering the temperature raised to the glass softening temperature again, and the manufactured infrared-transmitting wafer lens It provides an infrared transmission wafer lens manufacturing method comprising a separation process of separating from the upper mold and the lower mold.

According to one aspect of the present invention, the upper mold and the lower mold are characterized in that they include a coating film on the surface so that the manufactured infrared transmission wafer lens can be easily separated.

According to one aspect of the present invention, the coating film is characterized in that it has heat resistance up to at least the glass softening temperature of the chalcogenide wafer.

As described above, according to one aspect of the present invention, by containing Zn, there is an advantage in that the infrared-transmitting chalcogenide glass to be produced can secure an excellent glass transition temperature.

According to one aspect of the present invention, if the glass transition temperature of the chalcogenide glass to be molded is high, the material of the molding mold should be an expensive tungsten carbide material, but the infrared-transmitting chalcogenide glass containing Zn has a low glass transition temperature There is an advantage in that the manufacturing cost of lens molding can be lowered because a relatively inexpensive mold made of bronze, stainless, or aluminum can be used.

1 is a flowchart illustrating a method of manufacturing an infrared ray transmitting chalcogenide glass according to an embodiment of the present invention.
2 is a diagram showing the contents of components constituting the composition for infrared transmitting chalcogenide glass according to the first embodiment of the present invention.
FIG. 3 is a graph showing the glass transition temperatures of the infrared-transmitting chalcogenide glass according to the first embodiment of the present invention and the conventional infrared-transmitting glass.
4 is a diagram illustrating a process of manufacturing a chalcogenide glass ingot into a wafer for manufacturing an infrared transmission wafer lens according to an embodiment of the present invention.
5 is a diagram illustrating a process of manufacturing a wafer lens using a chalcogenide wafer according to an embodiment of the present invention.

Since the present invention can make various changes and have various embodiments, specific embodiments will be illustrated in the drawings and described in detail. However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all modifications, equivalents, or substitutes included in the spirit and technical scope of the present invention. Like reference numerals have been used for like elements throughout the description of each figure.

Terms such as first, second, A, and B may be used to describe various components, but the components should not be limited by the terms. These terms are only used for the purpose of distinguishing one component from another. For example, a first element may be termed a second element, and similarly, a second element may be termed a first element, without departing from the scope of the present invention. The terms and/or include any combination of a plurality of related recited items or any of a plurality of related recited items.

It is understood that when an element is referred to as being "connected" or "connected" to another element, it may be directly connected or connected to the other element, but other elements may exist in the middle. It should be. On the other hand, when an element is referred to as “directly connected” or “directly connected” to another element, it should be understood that no intervening element exists.

Terms used in this application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. It should be understood that terms such as "include" or "having" in this application do not exclude in advance the possibility of existence or addition of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification. .

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs.

Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, they should not be interpreted in an ideal or excessively formal meaning. don't

In addition, each configuration, process, process or method included in each embodiment of the present invention may be shared within a range that does not contradict each other technically.

1 is a flowchart illustrating a method of manufacturing an infrared ray transmitting chalcogenide glass according to an embodiment of the present invention.

The composition for glass is made of infrared-transmitting chalcogenide glass through a manufacturing process to be described later. The infrared-transmitting chalcogenide glass has, in particular, a transmittance equal to or higher than a preset reference value for light in an infrared wavelength band among incident lights. Infrared-transmitting chalcogenide glass can be adopted and used in various forms not only in the military field but also in the civilian field, such as being embedded in an infrared camera, smart device, or home appliance. In this case, the infrared transmitting chalcogenide glass may be used as a glass itself in order to be used in each field, but more often it is used after being molded into an optical component such as a lens from glass. Accordingly, raw materials forming the composition for infrared transmitting chalcogenide glass according to an embodiment of the present invention are mixed in a predetermined ratio and subjected to a manufacturing process to be described later, thereby forming As (arsenic), Sb (antimony), and Pb (lead) , Br (bromine) or La (lanthanum), etc., can be made of infrared-transmitting chalcogenide glass that secures excellent optical and physical properties without containing heavy metals or harmful elements.

Pre-set raw materials are charged into a container by a pre-set amount and sealed (S110).

The composition for infrared-transmitting chalcogenide glass is composed of predetermined raw materials. Pre-set raw materials include Ge, Zn, In and Se. It does not contain heavy metal components or components harmful to the human body as raw materials, and is processed into a composition containing only the above-mentioned components.

Each component is included in a predetermined amount. Here, when the contents of Ge, Zn, In, and Se are set as x (at%), y (at%), z (at%), and w (at%), respectively, 1≤x≤40 (at%) , 1≤y+z≤15 (at%) and 50≤w≤85 (at%). By including the raw material in the above-mentioned content, it is possible to secure a glass forming region. In addition, as Zn is included within the above-described content range, it is possible to secure a significantly lower glass transition temperature (Tg) than the prior art, as will be described later.

Each raw material is loaded into a container by a predetermined amount. Here, the container may be a quartz tube of a size that can sufficiently contain all the raw materials. When all the raw materials are loaded into the quartz tube, the quartz tube is sealed in a vacuum state to prevent a separate (gas) component from flowing into the quartz tube.

The raw material in the container is melted in a first preset environment (S120).

After the raw material is loaded into the container and sealed, the raw material is melted in a first preset environment. The first preset environment may have a temperature of around 850°C. At this time, when a temperature of around 850 ° C is formed in the first preset environment, the temperature is not raised at one time, but by several ° C per minute (eg, 4 ° C per minute) to form the corresponding temperature. can The raw material is melted in a first predetermined environment (in the vessel).

Raw materials in the container may be melted in a first preset environment by a rocking electric furnace. A container is installed in the rocking electric furnace, and each raw material in the container is mixed. The raw materials are mixed by a rocking electric furnace, exposed to a temperature of around 850°C for around 12 hours and melted.

The molten raw material is rapidly cooled in a second preset environment (S130).

The container installed in the locking electric furnace is separated from the locking electric furnace and rapidly cooled in a second preset environment. The second preset environment may be an environment in which the container is exposed to air or water, and may have a temperature of around 600°C. The container is exposed to air or water at a high temperature of 850 ° C in a locking electric furnace and begins to rapidly cool. Rapid cooling is performed until the temperature of the container is around 600°C.

The quenched raw material is slowly cooled in a third preset environment (S140).

The rapidly cooled vessel is slowly cooled in a third preset environment. The third preset environment may have a time of about 3 hours at about 200 ° C. The rapidly cooled container is slowly cooled in a slow cooling furnace preheated to around 200°C for around 3 hours.

Through the above process, the raw material is prepared as a composition for infrared transmitting chalcogenide glass.

2 is a diagram showing the contents of components constituting the composition for infrared transmitting chalcogenide glass according to the first embodiment of the present invention.

2 illustrates an example in which the composition for infrared transmitting chalcogenide glass (hereinafter, abbreviated as 'composition for glass') according to an embodiment of the present invention includes only Ge, Zn, In, and Se. If the composition for glass is implemented as Ge _x Zn _y In _z Se _w , as described above, the content of each component is implemented as 1≤x≤40, 1≤y+z≤15, and 50≤w≤85 (at%) . Each composition may be included as shown in FIG. 2 (below) as an example.

1) Ge: 10at%, Zn: 2.5at%, In: 5at%, Se: 82.5at% (Ge ₁₀ Zn _2.5 In ₅ Se _82.5 )

2) Ge: 10at%, Zn: 5at%, In: 5at%, Se: 80at% (Ge ₁₀ Zn ₅ In ₅ Se ₈₀ )

3) Ge: 10at%, Zn: 7.5at%, In: 5at%, Se: 77.5at% (Ge ₁₀ Zn _7.5 In ₅ Se _77.5 )

In preparing each composition for glass, the Ge content was included by 10 at%, the Zn content by xat%, the In content by 5 at%, and the Se content by (85-x)at%, respectively. According to the change in the content of Se, the content of Se was also varied.

3 shows the glass transition temperatures of infrared-transmitting chalcogenide glass and conventional infrared-transmitting glass prepared from glass compositions containing the above-mentioned amounts of each raw material.

FIG. 3 is a graph showing the glass transition temperatures of the infrared-transmitting chalcogenide glass according to the first embodiment of the present invention and the conventional infrared-transmitting glass.

The lower the glass transition temperature, the more advantageous the glass composition can be molded at a relatively low temperature.

Referring to FIG. 3 , the compositions for glass (Ge ₁₀ Zn _2.5 In ₅ Se _82.5 , Ge ₁₀ Zn ₅ In ₅ Se ₈₀ , Ge ₁₀ Zn _7.5 In ₅ Se _77.5 ) according to an embodiment of the present invention are prepared at 110° C. to 110° C. It was confirmed to have a glass transition temperature (Tg) of 120 °C. Relatively, as the content of Zn increased, the glass transition temperature tended to increase.

On the other hand, it can be seen that the conventional compositions (Ge ₃₃ As ₁₂ Se ₅₅ , Ge ₁₀ As ₄₀ Se ₅₀ , Ge ₂₈ Sb ₁₂ Se ₆₀ , As ₄₀ Se ₆₀ ) secure a glass transition temperature of 185°C to 368°C, respectively. there was. It was confirmed that the composition implemented with As and Se had a glass transition temperature of 185 ° C despite containing As components, and when As or Sb was included together with Ge and Se, all of them had a high glass transition temperature of 220 ° C. It was confirmed that the .

4 is a diagram illustrating a process of manufacturing a chalcogenide glass ingot into a wafer for manufacturing an infrared transmission wafer lens according to an embodiment of the present invention.

Referring to FIG. 4 , the following processes are performed to manufacture a chalcogenide glass ingot into an infrared transmission wafer lens.

As shown in FIGS. 4(a) to (c), the chalcogenide glass ingot goes through a sawing process and a polishing process, and a large area chalcogenide wafer as shown in FIG. 4(d) are manufactured

The chalcogenide wafer manufactured in this way goes through the process of FIG. 5 and is manufactured as a wafer lens.

5 is a diagram illustrating a method of manufacturing a wafer lens using a chalcogenide wafer according to an embodiment of the present invention.

The chalcogenide wafer 530 manufactured through the process of FIG. 4 is placed on the lower mold 520 . At this time, surfaces of the upper mold 510 and the lower mold 520 facing each other each have a shape complementary to that of the wafer lens. Accordingly, when the wafer 530 seated on the lower mold 520 is compressed by both molds 510 and 520, it may be manufactured in the form of a wafer lens.

When the chalcogenide wafer 530 is seated on the lower mold 520, the temperature rises to near the glass softening temperature of the chalcogenide glass composition, and then the upper mold 510 and the lower mold 520 are compressed and The cogenide wafer 530 is molded into a wafer lens. After the temperature is lowered again, the molds 510 and 520 and the wafer lens are separated, so that the chalcogenide wafer 530 is manufactured as a wafer lens.

At this time, as described above, since the chalcogenide wafer 530 according to an embodiment of the present invention has a significantly lower glass transition temperature than the prior art, the wafer lens can be manufactured at a relatively low temperature. This has the following advantages.

Not only the surrounding environment, but also the molds 510 and 520 directly in contact with the chalcogenide wafer 530 must be heated to a temperature close to the glass softening temperature, which is about 30% higher than the glass transition temperature, so that molding can proceed. As shown in FIG. 3 , when the infrared transmitting chalcogenide glass according to an embodiment of the present invention has a glass transition temperature of 110° C., the glass softening temperature is approximately 150° C. At this time, the higher the glass softening temperature, the more difficult it is for each mold to have a uniform temperature (glass softening temperature). Alternatively, a fairly long time elapses until the temperature of each mold becomes uniform to the corresponding temperature. On the other hand, since the chalcogenide wafer 530 according to an embodiment of the present invention has a significantly low glass softening temperature, it has the advantage of being relatively easy to heat each mold to around the glass softening temperature, and is relatively easy to manufacture. can be completed in time.

If the glass transition temperature of the chalcogenide glass to be molded is high, the material of the molding mold must be made of expensive tungsten carbide. However, since the composition for chalcogenide glass according to an embodiment of the present invention contains Zn and has a relatively remarkably low glass transition temperature, the mold may be made of relatively inexpensive bronze, stainless, or aluminum. Accordingly, according to an embodiment of the present invention, there is an advantage of lowering the manufacturing cost of lens molding.

In addition, a coating film is coated on the surface of each mold so that the manufactured wafer lens can be easily separated. Due to the coating film, the manufactured wafer lens can be completely separated from the mold without sticking to the surface of the mold. These coating films also have a certain heat resistance, and can withstand up to a certain temperature without changing their components or state, but at a temperature higher than that, a change in their components or state occurs. Since the chalcogenide wafer 530 according to an embodiment of the present invention has a significantly low glass transition temperature, manufacturing of a wafer lens can be performed at a significantly low temperature. Accordingly, the deformation problem of the coating film does not occur, and the lifespan of each mold or the coating films coated thereon can be improved.

Although the composition for glass according to an embodiment of the present invention does not contain heavy metals, it contains Ge, Zn, In, and Se in predetermined amounts, and thus has a significantly lower glass transition temperature than conventional compositions for glass containing heavy metals. It was confirmed that the . Accordingly, the composition for glass according to an embodiment of the present invention can be molded even at a low temperature, and can be molded in the form of a wide-area wafer.

Although each process is described as sequentially executed in FIG. 1 , this is merely an example of the technical idea of one embodiment of the present invention. In other words, those skilled in the art to which an embodiment of the present invention pertains may change and execute the order described in each drawing or perform one or more processes of each process without departing from the essential characteristics of an embodiment of the present invention. Since it will be possible to apply various modifications and variations by executing in parallel, FIG. 1 is not limited to a time-series sequence.

Meanwhile, the processes shown in FIG. 1 can be implemented as computer readable codes on a computer readable recording medium. A computer-readable recording medium includes all types of recording devices in which data that can be read by a computer system is stored. That is, computer-readable recording media include storage media such as magnetic storage media (eg, ROM, floppy disk, hard disk, etc.) and optical reading media (eg, CD-ROM, DVD, etc.). In addition, the computer-readable recording medium may be distributed to computer systems connected through a network to store and execute computer-readable codes in a distributed manner.

The above description is merely an example of the technical idea of the present embodiment, and various modifications and variations can be made to those skilled in the art without departing from the essential characteristics of the present embodiment. Therefore, the present embodiments are not intended to limit the technical idea of the present embodiment, but to explain, and the scope of the technical idea of the present embodiment is not limited by these embodiments. The scope of protection of this embodiment should be construed according to the claims below, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of rights of this embodiment.

510: upper mold
520: lower mold
530: chalcogenide wafer

Claims (12)

In the composition for infrared-transmitting chalcogenide glass that transmits light in the infrared wavelength band above a predetermined reference value,
A composition for glass characterized in that it is composed of Ge, Zn, In and Se in a predetermined ratio. According to claim 1,
The preset ratio is,
If the contents of Ge, Zn, In and Se are set as x(at%), y(at%), z(at%) and w(at%), respectively, 1≤x≤40(at%), 1 A composition for glass characterized in that it satisfies ≤y+z≤15 (at%) and 50≤w≤85 (at%). According to claim 2,
The preset ratio is,
10at% : xat% : 5at% : (85-x)at% in the order of Ge, Zn, In and Se,
A composition for glass, characterized in that x is 2.5, 5 or 7.5. In the method for producing an infrared ray-transmitting chalcogenide glass that transmits light in an infrared wavelength band above a predetermined reference value,
A sealing process of charging Ge, Zn, In, and Se at a predetermined ratio as raw materials into a container and sealing it;
a melting process of melting the raw materials in the container that have undergone the sealing process in a first preset environment;
a quenching process of rapidly cooling the raw materials melted in the melting process in a second preset environment; and
Slow cooling process of slowly cooling the raw materials that have undergone the rapid cooling process in a third preset environment
Infrared transmission chalcogenide glass manufacturing method comprising a. According to claim 4,
The first preset environment,
Infrared transmission chalcogenide glass manufacturing method characterized by having a temperature within a predetermined range based on 850 ℃. According to claim 5,
The first preset environment,
Infrared transmission chalcogenide glass manufacturing method, characterized in that formed by increasing several ℃ per minute (min). According to claim 4,
The melting process is
Infrared transmission chalcogenide glass manufacturing method, characterized in that the container that has undergone the sealing process is mounted on a rocking device, and the raw materials in the container are mixed and melted in a first preset environment. According to claim 7,
The melting process is
Infrared transmission chalcogenide glass manufacturing method, characterized in that the raw materials in the container are mixed and melted for 12 hours in a first preset environment by the rocking device. In the method for producing a chalcogenide glass ingot in a wafer form,
A wafer manufacturing method characterized in that the chalcogenide glass ingot manufactured by the method of any one of claims 4 to 8 is manufactured in a wafer form by sawing and polishing. In the method for manufacturing a chalcogenide wafer into an infrared transmission wafer lens,
A seating process of seating the chalcogenide wafer on a lower mold;
a step of raising the temperature to a glass softening temperature of the chalcogenide wafer after the settling step;
a compression process of compressing the chalcogenide wafers seated in the upper mold and the lower mold;
A lowering process of lowering the temperature raised to the glass softening temperature again; and
Separation process of separating the manufactured infrared transmission wafer lens from the upper mold and the lower mold
Infrared transmission wafer lens manufacturing method comprising a. According to claim 10,
The upper mold and the lower mold,
An infrared transmission wafer lens manufacturing method comprising a coating film on a surface so that the manufactured infrared transmission wafer lens can be easily separated. According to claim 11,
The coating film,
An infrared transmission wafer lens manufacturing method, characterized in that it has heat resistance at least up to the glass softening temperature of the chalcogenide wafer.

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