CHALCOGENIDE GLASS COMPOSITION INCLUDING SILICON, GALLIUM AND TELLURIUM, AND INFRARED TRANSMITTING LENS INCLUDING THE SAME
20240059603 ยท 2024-02-22
Inventors
Cpc classification
C03C3/323
CHEMISTRY; METALLURGY
International classification
Abstract
The present disclosure relates to a chalcogenide glass composition and a lens including a molded article of the same, which are capable of guaranteeing excellent refractive index, Vickers hardness, and price competitiveness without including an element such as arsenic harmful to the human body.
Claims
1. A chalcogenide glass composition comprising: silicon (Si), gallium (Ga), and tellurium (Te), wherein with respect to the total elements, the content of the tellurium element ranges from 65.0 at % to 85.0 at %.
2. The chalcogenide glass composition of claim 1, wherein, with respect to the total elements, the content of the gallium element is greater than 2.5 at % and less than 20.0 at %.
3. The chalcogenide glass composition of claim 1, wherein, with respect to the total elements, the content of the silicon element is greater than 2.5 at % and less than 17.5 at %.
4. The chalcogenide glass composition of claim 1, further comprising one or more elements selected from the group consisting of germanium (Ge), selenium (Se), bismuth (Bi), indium (In), tin (Sn), antimony (Sb), aluminum (Al), and iodine (I).
5. The chalcogenide glass composition of claim 1 having a Vickers hardness ranging from 1.00 GPa to 1.35 GPa.
6. The chalcogenide glass composition of claim 1 having a refractive index of 3.0 or more at 10 m in wavelength.
7. A lens made of a chalcogenide glass with compositions according to claim 1.
8. The lens of claim 7 that is formed via a direct machining process, a molding process, a wafer-level molding process, or an imprinting process.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0015]
[0016]
[0017]
[0018]
MODE FOR DISCLOSURE
[0019] Throughout the specification of the present application, when a part includes or comprises a component, it means not that the part excludes other component, but instead that the part may further include other component unless expressly stated to the contrary.
[0020] Hereinafter, the present invention will be described in more detail.
[0021] An embodiment of the present disclosure provides a chalcogenide glass composition including silicon (Si), gallium (Ga), and tellurium (Te).
[0022] According to an embodiment of the present disclosure, the content of the tellurium element may be 65.0 at % or more and less than 85.0 at %, 65.0 at % or more and 82.5 at % or less, 70.0 at % or more and less than 85.0 at %, 70.0 at % or more and 82.5 at % or less, 72.5 at % or more and less than 85.0 at %, 72.5 at % or more and 82.5 at % or less, 75.0 at % or more and less than 85.0 at %, or 75.0 at % or more and 82.5 at % or less with respect to the total elements.
[0023] According to an embodiment of the present disclosure, the content of the gallium element may be greater than 2.5 at % and less than 20.0 at %, or greater than 2.5 at % and less than or equal to 17.5 at %, preferably 5.0 at % or more and 17.5 at % or less, with respect to the total elements.
[0024] According to an embodiment of the present disclosure, the content of the silicon element may be greater than 2.5 at % and less than 17.5 at %, or 5.0 at % or more and less than 17.5 at %, preferably 5.0 at % or more and 15.0 at % or less, with respect to the total elements.
[0025] When the contents of tellurium, gallium, and silicon included in the chalcogenide glass composition are within the above-mentioned ranges, respectively, the chalcogenide glass composition can form stable bulk glass with excellent hardness, refractive index at a wavelength of 10 m, and price competitiveness.
[0026] Specifically, since the chalcogenide glass composition of the present disclosure is devoid of germanium, it may have excellent price competitiveness compared to conventional commercially available compositions including germanium. Further, even though it is devoid of germanium, it can exhibit excellent hardness compared to commercially available compositions including germanium.
[0027] According to an embodiment of the present disclosure, the chalcogenide glass composition may further include one or more elements selected from the group consisting of germanium (Ge), selenium (Se), bismuth (Bi), indium (In), tin (Sn), antimony (Sb), aluminum (Al), and iodine (I).
[0028] According to an embodiment of the present disclosure, the content of the germanium element may be greater than 0 at % and less than 10.0 at %, or 0.5 at % or more and 8.0 at % or less, preferably 1.0 at % or more and 7.0 at % or less, with respect to the total elements.
[0029] According to an embodiment of the present disclosure, the content of the selenium element may be greater than 0 at % and less than 7.0 at %, or 0.5 at % or more and 6.0 at % or less, preferably 1.0 at % or more and 5.0 at % or less, with respect to the total elements. In this case, the content of silicon may be 12.0 at % or more and 15.0 at % or less.
[0030] According to an embodiment of the present disclosure, the content of the bismuth element may be greater than 0 at % and less than 3.0 at %, or 0.1 at % or more and 2.0 at % or less, preferably 0.5 at % or more and 1.5 at % or less, with respect to the total elements.
[0031] According to an embodiment of the present disclosure, the content of the indium element may be greater than 0 at % and less than 10.0 at %, or 0.5 at % or more and 8.0 at % or less, preferably 1.0 at % or more and 7.0 at % or less, or 1.0 at % or more and 5.0 at % or less, with respect to the total elements.
[0032] According to an embodiment of the present disclosure, the content of the tin element may be greater than 0 at % and less than 10.0 at %, or 0.5 at % or more and 8.0 at % or less, preferably 1.0 at % or more and 7.0 at % or less, or 1.0 at % or more and 3.0 at % or less, with respect to the total elements.
[0033] According to an embodiment of the present disclosure, the content of the antimony element may be greater than 0 at % and less than 9.0 at %, or 0.5 at % or more and 8.0 at % or less, preferably 1.0 at % or more and 7.0 at % or less, or 1.0 at % or more and 5.0 at % or less, with respect to the total elements. In this case, the content of silicon may be 8.0 at % or more and 14.0 at % or less.
[0034] According to an embodiment of the present disclosure, the content of the aluminum element may be greater than 0 at % and less than 10.0 at %, 1.0 at % or more and 9.0 at % or less, 2.0 at % or more and 8.0 at % or less, or 2.5 at % or more and 7.0 at % or less, preferably 3.0 at % or more and 6.0 at % or less, with respect to the total elements.
[0035] According to an embodiment of the present disclosure, the content of the iodine element may be greater than 0 at % and less than or equal to 15.0 at %, 0.1 at % or more and 13.0 at % or less, 0.5 at % or more and 11.0 at % or less, preferably, 1.0 at % or more and 10.0 at % or less, 7.5 at % or more and 12.5 at % or less, or 9.0 at % or more and 11.0 at % or less, with respect to the total elements.
[0036] When the contents of germanium, selenium, bismuth, indium, tin or antimony included in the chalcogenide glass composition are within the above-mentioned ranges, respectively, the chalcogenide glass composition can form stable bulk glass with excellent hardness, refractive index at a wavelength of 10 m, and price competitiveness.
[0037] According to an embodiment of the present disclosure, the chalcogenide glass composition may have a glass transition temperature of 130 C. to 190 C. The chalcogenide glass composition having a glass transition temperature within the above-mentioned range can make the molding process easy and reduce the molding process cost. In the molding process, the glass transition temperature of the glass material can be assumed to be a very important factor when considering the mold material. That is, as the glass transition temperature becomes higher, the mold material should be selected from materials, such as tungsten carbide, silicon carbide, or others, which can maintain high mechanical strength at high temperatures, and however it is difficult to perform direct machining on these materials, which are expensive. On the other hand, as the glass transition temperature becomes lower, a stainless steel material or even a cheap polymer material such as PDMS can be used as a mold material, through which the process costs can be significantly reduced. Thus, the glass transition temperature range of the chalcogenide glass can advantageously lead to an increase in the freedom of selection of the mold material and a reduction in the thermal energy inputted to the molding process.
[0038] According to an embodiment of the present disclosure, the chalcogenide glass composition may have a thermal stability of 40 C. to 150 C., 45 C. to 150 C., or 50 C. to 150 C. The thermal stability may satisfy Equation 1 below.
Thermal Stability (T)=Onset Temperature of Crystallization (T.sub.x)Glass Transition Temperature (T.sub.g)[Equation 1]
[0039] When the chalcogenide glass composition has the thermal stability of the above-mentioned range, it may be suitable for a molding process. In general, the molding process is performed between the glass transition temperature and the onset temperature of crystallization. Here, as the difference between the onset temperature of crystallization and the glass transition temperature increases, the possibility that crystallization of the glass does not occur during the molding process increases.
[0040] According to an embodiment of the present disclosure, the chalcogenide glass composition may have a Vickers hardness ranging from 1.00 GPa to 1.35 GPa. The average coordination number for each composition was calculated under the assumption that the coordination numbers of the silicon atom and the gallium atom are commonly 4 and the coordination number of the tellurium atom is maintained at 2, and it can be seen that as the mean coordination number increases, the hardness tends to increase generally. Further, in contrast to the existing commercially available chalcogenide glasses mainly containing either toxic element like As or expensive element like Ge, this composition is devoid of those elements and, in addition, it was confirmed that it maintained the hardness at a level higher than or similar to that of the commercially available composition, and that it obtained a similar level of hardness compared to the GeGaTe ternary chalcogenide glass composition.
[0041] According to an embodiment of the present disclosure, the chalcogenide glass composition may have a refractive index of 3.25 or more, 3.15 or more, preferably 3.0 or more at a wavelength of 10 m. It can be seen that the chalcogenide glass composition according to the present disclosure has excellent optical properties compared to the chalcogenide glass compositions with the existing commercially available composition having a refractive index of 2.4 to 2.8 at a wavelength of 10 m.
[0042] The refractive index may be a measured refractive index or a calculated refractive index, wherein the calculated refractive index of the chalcogenide glass composition can be calculated by quantifying the atomic polarizability of the glass constituents and measuring the apparent density thereof, which will be described in detail later.
[0043] An embodiment of the present disclosure provides a lens including a molded article of the chalcogenide glass composition.
[0044] The lens may be a refractive lens or a diffractive lens.
[0045] Details mentioned in the chalcogenide glass composition and lens of the present disclosure are equally applied to each other unless it causes the contradiction.
[0046] According to an embodiment of the present disclosure, the lens including a molded article of the chalcogenide glass composition may be a lens for use in a LWIR camera. As described above, the chalcogenide glass composition can have excellent hardness, refractive index at a wavelength of 10 m, and price competitiveness. Additionally, the chalcogenide glass composition has physical properties suitable for a wafer-level molding process or a imprinting process, so that a lens for use in a LWIR camera can be easily manufactured using the chalcogenide glass composition. Thus, the lens can be used for a thermal imaging camera utilizing infrared wavelengths.
[0047] According to an embodiment of the present disclosure, the molded article may be formed by performing a direct machining process, a molding process, a dry/wet etching process, a wafer-level molding process, or a imprinting process on the chalcogenide glass composition. That is, the lens may be manufactured by molding the chalcogenide glass composition through the direct machining process, the molding process, the dry/wet etching process, the wafer-level molding process, or the imprinting process. Specifically, the lens may be manufactured by molding the chalcogenide glass composition through the wafer-level molding process or the imprinting process.
[0048] Silicon, gallium, and tellurium used in the method for manufacturing a chalcogenide glass composition according to an embodiment of the present disclosure are as described in the chalcogenide glass composition.
[0049] When the process temperature is adjusted in the method for manufacturing a chalcogenide glass composition according to an embodiment of the present disclosure, impurity absorption (SiO impurity vibration absorption) that may occur in the 11 m can be effectively reduced.
[0050] Hereinafter, the present disclosure will be described specifically with reference to examples. However, it should be noted that the examples according to the present disclosure may be modified into various other forms, and the scope of the present disclosure is not construed as being limited to the examples to be described below. The examples of the present specification are provided to more completely explain the present disclosure to those of ordinary skill in the art.
Manufacturing of Example 1-1
[0051] Manufacturing of Glass Specimens
[0052] All specimens of the present disclosure were manufactured by a typical melt-quenching method applied to the synthesis of chalcogenide glass. The glass specimen of each composition is a circular rod, commonly 10 mm in diameter, and 6 cm or more in length.
[0053] After washing with acetone as a pretreatment process to remove possible contaminants present in the silica ampoule, heat treatment was performed at 600 C. for 3 hours or more. In a glove box filled with argon gas, starting materials were weighed in a composition of 5 at % silicon, 15 at % gallium, and 80 at % tellurium, and then charged into a silica ampoule, which was melted and sealed while maintaining its inside in a vacuum state. After that, the sealed silica ampoule was heated to 1000 C. at a rate of 100 C./hr through a locking electric furnace and its temperature was maintained for 12 hours or more, and was lowered to 600 C. and maintained for 2 hours, then it was quenched in the air for 1 hour or more. Afterwards, an annealing process was performed to minimize thermal stress inside the specimen and improve homogeneity, wherein the annealing temperature was maintained at a temperature generally 20 C. lower than the glass transition temperature for 3 hours, and then was furnace cooled.
Experimental Example 1. Bulk Glass Formation Evaluation
[0054] With respect to the manufactured glass specimen, an XRD pattern was analyzed and long-wavelength infrared range transmission spectrum was measured using FT-IR equipment to determine whether or not bulk glass was formed in the glass specimen. Specifically, first, by using XRD equipment (Ultima IV, Rigaku Co.), the XRD pattern of the glass specimen was analyzed to check whether a crystallization peak was generated. After that, by using FT-IR equipment (Spectrum 100, PerkinElmer Co.), the long-wavelength infrared range transmission spectrum of the glass specimen was measured, and when the transmittance was less than 10%, it was evaluated that bulk glass was not formed, and the results are shown in Table 1 below (Good: bulk glass was formed, Moderate: bulk glass was formed but low transmittance was obtained, Bad: bulk glass was not formed).
Manufacturing of Examples 1-2 to 1-11
[0055] Examples 1-2 to 1-11 were manufactured in the same manner as the glass specimen manufacturing method of Example 1-1 above, with the exception that the starting materials were adjusted to the composition of silicon, gallium and tellurium shown in Table 1 below. Additionally, bulk glass formation evaluation was performed in the same manner as in Experimental Example 1 above, and the results are shown in Table 1 below.
TABLE-US-00001 TABLE 1 Si Ga Te Quality of glass (at %) (at %) (at % ) formation EXAMPLE 1-1 5 15 80 Good EXAMPLE 1-2 7.5 12.5 80 Good EXAMPLE 1-3 10 10 80 Good EXAMPLE 1-4 12.5 7.5 80 Good EXAMPLE 1-5 15 5 80 Good EXAMPLE 1-6 7.5 17.5 75 Moderate EXAMPLE 1-7 10 15 75 Good EXAMPLE 1-8 12.5 12.5 75 Good EXAMPLE 1-9 15 10 75 Good EXAMPLE 1-10 7.5 10 82.5 Good EXAMPLE 1-11 10 7.5 82.5 Good
Manufacturing of Comparative Example 1-1
[0056] Comparative Example 1-1 was manufactured in the same manner as the glass specimen manufacturing method of Example 1-1 above, with the exception that the starting materials were adjusted to the composition of silicon, gallium and tellurium shown in Table 2 below. Additionally, bulk glass formation evaluation was performed in the same manner as in Experimental Example 1 above, and the results are shown in Table 2 below.
TABLE-US-00002 TABLE 2 Si Ga Te Quality of glass (at %) (at %) (at %) formation Comparative 20 5 75 Bad Example 1-1
[0057] Referring to Comparative Example 1-1 in Table 2, it can be seen that bulk glass is not formed when the composition of the present disclosure is not satisfied even though all of silicon, gallium and tellurium of the present disclosure are included.
Experimental Example 2. Thermal Stability Evaluation
[0058] In order to evaluate the thermal stability (T) of the manufactured glass specimen, the glass transition temperature (T.sub.g) and the onset temperature of crystallization (T.sub.x) of the specimen were measured.
[0059] Specifically, DSC thermal analysis was performed using a DSC thermal analysis device (Exstar 6000, Seiko Co.). At this time, the temperature increase rate at the time of measurement was set to 10 C./min. The thermal stability (T) was calculated through Equation 1 below by using the measured glass transition temperature and the onset temperature of crystallization, and the results are shown in Table 3 below.
Thermal Stability (T)=Onset Temperature of Crystallization (T.sub.x)Glass Transition Temperature (T.sub.g)[Equation 1]
Experimental Example 3. Refractive Index Evaluation
[0060] The refractive index of the manufactured glass specimen was measured in the wavelength range of 2 m to 15 m using Ellipsometer equipment (IR-VASE Mark II, J. A. Woollam Co.), or the refractive index of the glass specimen was calculated by a method described below.
[0061] Specifically, the refractive index is affected by the atomic polarizability of the glass constituents and atomic packing ratio per unit volume of the glass, and was calculated through Equation 2 (a semi-experimental equation) based on the Clausius-Mossotti model, and the results are shown in Table 3 below.
[0062] In Equation 2, n denotes the refractive index, R.sub.m denotes the molar refractivity, M denotes the molar mass, and denotes the density.
Experimental Example 4. Vickers Hardness Measurement
[0063] With respect to the manufactured glass specimens, Vickers hardness was measured using a Vickers hardness tester, and the results are shown in Table 3 below.
TABLE-US-00003 TABLE 3 Calculated refractive Glass Onset temperature index at 10 transition of Thermal Vickers Density m temperature crystallization stability hardness (g/cm.sup.3) n.sub.10(cal) ( C.) ( C.) T ( C.) (GPa) EXAMPLE 5.4602 3.39 139.6 194.5 54.9 1.19 1-1 EXAMPLE 5.4490 3.45 142.7 204.9 62.2 1.22 1-2 EXAMPLE 5.3759 3.42 144.0 205.5 61.5 1.13 1-3 EXAMPLE 5.2994 3.39 147.3 220.7 73.4 1.15 1-4 EXAMPLE 5.2309 3.37 151.3 228.4 77.1 1.05 1-5 EXAMPLE 5.6008 3.65 181.5 252.7 71.2 1.07 1-6 EXAMPLE 5.2987 3.31 181. 2 259.8 78.6 1.22 1-7 EXAMPLE 5.2346 3.30 186.0 331.3 145.3 1.28 1-8 EXAMPLE 5.1485 3.26 189.4 331 141.6 1.28 1-9 EXAMPLE 5.3827 3.37 131.2 190.4 59.2 1.18 1-10 EXAMPLE 5.3201 3.35 133.5 197.4 63.9 1.09 1-11
Manufacturing of Comparative Examples 2-1 to 2-10
[0064] Comparative Examples 2-1 to 2-5 and Comparative Examples 2-7 to 2-10 were manufactured in the same manner as the glass specimen manufacturing method of Example 1-1 above, with the exception that the starting materials were adjusted to the composition of germanium (Ge), gallium (Ga), and tellurium (Te) shown in Table 4 below. Additionally, bulk glass formation evaluation, thermal stability evaluation, refractive index calculation, and Vickers hardness measurement were performed in the same manner as in Experimental Examples 1 to 4 above, and the results are shown in Table 4 below. Comparative Example 2-6 referred to S. Danto, et al., Adv. Funct. Mater. 19 (2006) 1847.
TABLE-US-00004 TABLE 4 Refractive index Glass transition Thermal measured at Ge Ga Te temperature stability Vickers hardness 10 m (at %) (at %) (at %) ( C.) T ( C.) (GPa) n.sub.10(cal) Comparative 17.5 2.5 80 139.6 54.9 1.14 3.46 Example 2-1 Comparative 17.5 5 77.5 142.7 62.2 1.20 3.44 Example 2-2 Comparative 17.5 7.5 75 144.0 61.5 1.27 3.41 Example 2-3 Comparative 15 5 80 147.3 73.4 1.17 3.47 Example 2-4 Comparative 15 7.5 77.5 151.3 77.1 1.27 3.44 Example 2-5 Comparative 15 10 75 181.5 71.2 1.33 Example 2-6 Comparative 15 12.5 72.5 181. 2 78.6 1.41 3.40 Example 2-7 Comparative 12.5 7.5 80 186.0 145.3 1.23 3.49 Example 2-8 Comparative 12.5 10 77.5 189.4 141.6 1.36 3.45 Example 2-9 Comparative 12.5 12.5 75 131. 2 59.2 1.45 3.39 Example 2-10
[0065] Referring to Table 3 and Table 4, it is confirmed that the chalcogenide glass composition including silicon, gallium and tellurium of the present disclosure has a similar level of hardness compared to the GeGaTe ternary chalcogenide glass composition.
Comparative Examples 3-1 to 3-11
[0066] The composition, refractive index and Vickers hardness of currently commercially available chalcogenide glass are shown in Table 5 below.
TABLE-US-00005 TABLE 5 Refractive index Vickers Commercially Chalcogenide measured at 10 m hardness available name composition n.sub.10 (mea) (GPa) Comparative AMTIR-4 As.sub.28Se.sub.72 2.6460 0.72 Example 3-1 Comparative AMTIR-5 As.sub.34S.sub.66 2.7423 0.75 Example 3-2 Comparative AMTIR-7 AsSe* 2.6893 0.74 Example 3-3 Comparative IRG22 Ge.sub.33As.sub.12Se.sub.55 2.4968 1.31 Example 3-4 Comparative IRG24 Ge.sub.10As.sub.40Se.sub.50 2.6090 1.02 Example 3-5 Comparative IRG25 Ge.sub.28Sb.sub.12Se.sub.60 2.6030 1.03 Example 3-6 Comparative IRG26 As.sub.40Se.sub.60 2.7781 0.94 Example 3-7 Comparative IRG27 As.sub.33S.sub.67 2.3842 1.01 Example 3-8 Comparative IRG203 Ge.sub.20Sb.sub.15Se.sub.65 2.5837 (10.6 m) 1.24 Example 3-9 Comparative IRG204 Sb.sub.4As.sub.30Sn.sub.3Se.sub.63 2.7659 (10.6 m) 1.03 Example 3-10 Comparative IG-3 Ge.sub.30Sb.sub.13Se.sub.32Te.sub.25 2.7870 1.26 Example 3-11 *Specific composition unknown
[0067] Referring to Tables 3 and 5, the chalcogenide glass composition including silicon, gallium, and tellurium of the present disclosure has a hardness higher than or similar to that of the chalcogenide glass compositions with the existing commercially available composition. Additionally, it can be seen that the chalcogenide glass composition of the present disclosure has an excellent refractive index of 3.0 or more at a wavelength of 10 m, compared to the chalcogenide glass compositions with the existing commercially available composition having a refractive index of 2.4 to 2.8 at a wavelength of 10 m.
Experimental Example 5. Transmission Spectrum Measurement
[0068] The glass specimens manufactured in Examples 1-1 to 1-4, Examples 1-7, Examples 1-9, Examples 5-3 and 5-4, Examples 8-1 to 8-3, Example 9-1, and Examples 10-5 to 10-7 were polished to a thickness of 2 mm, and transmission spectra thereof were measured in a wavelength range of 3 m to 12 m using FT-IR (Spectrum 100, PerkinElmer) equipment, and the results are shown in
[0069] Referring to
[0070] Referring to
Manufacturing of Examples 4-1 and 4-2
[0071] As shown in Table 6 below, Examples 4-1 and 4-2 were manufactured in the same manner as the glass specimen manufacturing method of Example 1-5 above, with the exception that the process temperature was adjusted to 600 C. or 800 C.
TABLE-US-00006 TABLE 6 Si Ga Te Process (at %) (at %) (at %) temperature ( C.) EXAMPLE 1-5 15 5 80 1000 EXAMPLE 4-1 15 5 80 600 EXAMPLE 4-2 15 5 80 800
Experimental Example 6. Measurement of Transmission Spectrum Change According to Process Temperature
[0072] As in the transmission spectrum measurement method of Experimental Example 5, the transmission spectrum was measured by adjusting the thickness of the glass specimens of Example 1-5, and Examples 4-1 and 4-2 having the above-described composition to 2 mm.
[0073] It can be seen that the size of the SiO impurity absorption peak occurring in the 11 m band decreases as the process temperature decreases. In particular, when the process is performed at 600 C., the absorption peak at 11 m is removed, which can be confirmed by the fact that as the process temperature is lowered, the inflow of impurities from the ampoule is reduced and the reduction of SiO absorption is induced, and it can be utilized to reduce impurity absorption when a silica ampoule is adopted and a highly reactive element are included in the glass batch.
Manufacturing of Examples 5-1 to 5-4 and Comparative Example 5-1
[0074] A glass specimen further including germanium (Ge) in addition to silicon (Si), gallium (Ga), and tellurium (Te) was manufactured. Specifically, Examples 5-1 to 5-4 and Comparative Example 5-1 were manufactured in the same manner as the glass specimen manufacturing method of Example 1-1 above, with the exception that the starting materials were adjusted to the composition of silicon (Si), gallium (Ga), tellurium (Te), and germanium (Ge) shown in Table 7 below. Additionally, bulk glass formation evaluation, thermal stability evaluation, refractive index calculation, and Vickers hardness measurement were performed in the same manner as in Experimental Examples 1 to 4 above, and the results are shown in Table 7 below.
TABLE-US-00007 TABLE 7 Glass Thermal Calculated refractive Quality of transition stability Vickers index at Si Ga Te Ge glass temperature T hardness 10 m (at %) (at %) (at %) (at %) formation ( C.) ( C.) (GPa) n.sub.10(cal) EXAMPLE 14 10 75 1 Good 177.9 144.4 1.10 3.36 5-1 EXAMPLE 12 10 75 3 Good 172. 2 79.8 1.13 3.40 5-2 EXAMPLE 10 10 75 5 Good 180.8 131.3 1.16 3.32 5-3 EXAMPLE 8 10 75 7 Good 179.1 119.6 1.18 3.33 5-4 Comparative 25 25 27.5 22.5 Bad Example 5-1
[0075] Referring to Table 7, it can be seen that when the content of the germanium element is 1.0 at % or more and 7.0 at % or less with respect to the total elements, the chalcogenide glass composition further including germanium of the present disclosure can form a stable bulk glass with excellent thermal stability, hardness and refractive index at a wavelength of 10 m.
Manufacturing of Examples 6-1 to 6-5 and Comparative Examples 6-1 to 6-3
[0076] A glass specimen further including selenium (Se) in addition to silicon (Si), gallium (Ga), and tellurium (Te) was manufactured. Specifically, Examples 6-1 to 6-5 and Comparative Examples 6-1 to 6-3 were manufactured in the same manner as the glass specimen manufacturing method of Example 1-1 above, with the exception that the starting materials were adjusted to the composition of silicon (Si), gallium (Ga), tellurium (Te), and selenium (Se) shown in Table 8 below. Additionally, bulk glass formation evaluation, thermal stability evaluation, refractive index calculation, and Vickers hardness measurement were performed in the same manner as in Experimental Examples 1 to 4 above, and the results are shown in Table 8 below.
TABLE-US-00008 TABLE 8 Calculated Glass Thermal refractive Quality transition stability Vickers index at Si Ga Te Se of glass temperature T hardness 10 m (at %) (at %) (at %) (at %) formation ( C.) ( C.) (GPa) n.sub.10(cal) EXAMPLE 14 10 75 1 Good 185.3 150.5 1.08 3.20 6-1 EXAMPLE 12 10 75 3 Good 188.5 22.2 1.06 3.17 6-2 EXAMPLE 15 10 74 1 Good 179.7 63.9 1.25 3.29 6-3 EXAMPLE 15 10 72 3 Good 160.9 73.4 1.19 3.32 6-4 EXAMPLE 15 10 70 5 Good 141.7 65.7 1.13 3.34 6-5 Comparative 10 10 75 5 Bad Example 6-1 Comparative 8 10 75 7 Bad Example 6-2 Comparative 15 10 68 7 Bad Example 6-3
[0077] Referring to Table 8, it can be seen that when the content of the selenium element is 1.0 at % or more and 5.0 at % or less and the silicon content is 12.0 at % or more and 15.0 at % or less, with respect to the total element, the chalcogenide glass composition further including selenium of the present disclosure can form a stable bulk glass with excellent thermal stability, hardness and refractive index at a wavelength of 10 m.
Manufacturing of Example 7-1 and Comparative Examples 7-1 to 7-3
[0078] A glass specimen further including bismuth (Bi) in addition to silicon (Si), gallium (Ga), and tellurium (Te) was manufactured. Specifically, Examples 7-1 and Comparative Examples 7-1 to 7-3 were manufactured in the same manner as the glass specimen manufacturing method of Example 1-1 above, with the exception that the starting materials were adjusted to the composition of silicon (Si), gallium (Ga), tellurium (Te), and bismuth (Bi) shown in Table 9 below. Additionally, bulk glass formation evaluation, thermal stability evaluation, refractive index calculation, and Vickers hardness measurement were performed in the same manner as in Experimental Examples 1 to 4 above, and the results are shown in Table 9 below.
TABLE-US-00009 TABLE 9 Calculated Glass Thermal refractive Quality transition stability Vickers index at 10 Si Ga Te Bi of glass temperature T hardness m (at %) (at %) (at %) (at %) formation ( C.) ( C.) (GPa) n.sub.10(cal) EXAMPLE 14 10 75 1 Good 180.7 117.6 1.22 3.34 7-1 Comparative 12 10 75 3 Bad Example 7-1 Comparative 10 10 75 5 Bad Example 7-2 Comparative 8 10 75 7 Bad Example 7-3
[0079] Referring to Table 9, it can be seen that when the content of the bismuth element is 0.5 at % or more and 1.5 at % or less with respect to the total elements, the chalcogenide glass composition further including bismuth of the present disclosure can form a stable bulk glass with excellent thermal stability, hardness and refractive index at a wavelength of 10 m.
Manufacturing of Examples 8-1 to 8-4
[0080] A glass specimen further including indium (In) in addition to silicon (Si), gallium (Ga), and tellurium (Te) was manufactured. Specifically, Examples 8-1 to 8-4 were manufactured in the same manner as the glass specimen manufacturing method of Example 1-1 above, with the exception that the starting materials were adjusted to the composition of silicon (Si), gallium (Ga), tellurium (Te), and indium (In) shown in Table 10 below. Additionally, bulk glass formation evaluation, thermal stability evaluation, refractive index calculation, and Vickers hardness measurement were performed in the same manner as in Experimental Examples 1 to 4 above, and the results are shown in Table 10 below.
TABLE-US-00010 TABLE 10 Glass Thermal Quality of transition stability Vickers Si Ga Te In glass temperature T hardness Density (at %) (at %) (at %) (at %) formation ( C.) ( C.) (GPa) (g/cm.sup.3) EXAMPLE 14 10 75 1 Good 185.5 157.9 1.30 5.2076 8-1 EXAMPLE 12 10 75 3 Good 181.5 147.4 1.36 5.2655 8-2 EXAMPLE 10 10 75 5 Good 175.9 129.7 1.31 5.3707 8-3 EXAMPLE 8 10 75 7 Moderate 169.3 66.7 1.18 5.4863 8-4
[0081] Referring to Table 10, it can be seen that when the content of the indium element is 1.0 at % or more and 7.0 at % or less with respect to the total elements, the chalcogenide glass composition further including indium of the present disclosure can form a stable bulk glass with excellent thermal stability, hardness and refractive index at a wavelength of 10 m.
Manufacturing of Examples 9-1 to 9-4
[0082] A glass specimen further including tin (Sn) in addition to silicon (Si), gallium (Ga), and tellurium (Te) was manufactured. Specifically, Examples 9-1 to 9-4 were manufactured in the same manner as the glass specimen manufacturing method of Example 1-1 above, with the exception that the starting materials were adjusted to the composition of silicon (Si), gallium (Ga), tellurium (Te), and tin (Sn) shown in Table 11 below. Additionally, bulk glass formation evaluation, thermal stability evaluation, refractive index calculation, and Vickers hardness measurement were performed in the same manner as in Experimental Examples 1 to 4 above, and the results are shown in Table 11 below.
TABLE-US-00011 TABLE 11 Calculated Thermal refractive Quality of Glass stability Vickers index at 10 Si Ga Te Sn glass transition T hardness m (at %) (at %) (at %) (at %) formation temperature ( C.) (GPa) n.sub.10(cal) EXAMPLE 14 10 75 1 Good 187.7 40.2 1.25 3.31 9-1 EXAMPLE 12 10 75 3 Good 177.4 71.7 1.25 3.37 9-2 EXAMPLE 10 10 75 5 Moderate 163.7 59.7 1.23 3.41 9-3 EXAMPLE 8 10 75 7 Moderate 152.4 50.5 1.17 3.48 9-4
[0083] Referring to Table 11, it can be seen that when the content of the tin element is 1.0 at % or more and 7.0 at % or less with respect to the total elements, the chalcogenide glass composition further including tin of the present disclosure can form a stable bulk glass with excellent thermal stability, hardness and refractive index at a wavelength of 10 m.
Manufacturing of Examples 10-1 to 10-8 and Comparative Examples 10-1 to 10-8
[0084] A glass specimen further including antimony (Sb) in addition to silicon (Si), gallium (Ga), and tellurium (Te) was manufactured. Specifically, Examples 10-1 to 10-8 and Comparative Examples 10-1 to 10-8 were manufactured in the same manner as the glass specimen manufacturing method of Example 1-1 above, with the exception that the starting materials were adjusted to the composition of silicon (Si), gallium (Ga), tellurium (Te), and antimony (Sb) shown in Table 12 below. Additionally, bulk glass formation evaluation, thermal stability evaluation, refractive index calculation, and Vickers hardness measurement were performed in the same manner as in Experimental Examples 1 to 4 above, and the results are shown in Table 12 below.
TABLE-US-00012 TABLE 12 Calculated Glass Thermal refractive Quality transition stability Vickers index at 10 Si Ga Te Sb of glass temperature T hardness m (at %) (at %) (at %) (at %) formation ( C.) ( C.) (GPa) n.sub.10(cal) EXAMPLE 11.5 7.5 80 1 Good 175.9 139 1.23 3.18 10-1 EXAMPLE 9.5 7.5 80 3 Good 141. 2 56.3 1.13 3.50 10-2 EXAMPLE 9 15 75 1 Good 182.9 69.97 1.27 3.35 10-3 EXAMPLE 7 15 75 3 Good 171.9 105.8 1.33 3.44 10-4 EXAMPLE 14 10 75 1 Good 182.1 51 1.05 3.31 10-5 EXAMPLE 12 10 75 3 Good 167.8 68 1.05 3.37 10-6 EXAMPLE 10 10 75 5 Good 156.3 73.5 1.04 3.48 10-7 EXAMPLE 8 10 75 7 Moderate 147.1 67.8 1.01 3.52 10-8 Comparative 4 15 80 1 Bad Example 10-1 Comparative 2 15 80 3 Bad Example 10-2 Comparative 0 15 80 5 Bad Example 10-3 Comparative 7.5 7.5 80 5 Bad Example 10-4 Comparative 5.5 7.5 80 7 Bad Example 10-5 Comparative 5 15 75 5 Bad Example 10-6 Comparative 3 15 75 7 Bad Example 10-7 Comparative 6.5 10 82.5 1 Bad Example 10-8
[0085] Referring to Table 12, it can be seen that when the content of the antimony element is 1.0 at % or more and 7.0 at % or less and the silicon content is 8.0 at % or more and 14.0 at % or less, with respect to the total element, the chalcogenide glass composition further including antimony of the present disclosure can form a stable bulk glass with excellent thermal stability, hardness and refractive index at a wavelength of 10 m.
Examples 11-1 and 11-2
[0086] A glass specimen further including aluminum (Al) in addition to silicon (Si), gallium (Ga), and tellurium (Te) was manufactured. Specifically, Examples 11-1 and 11-2 were manufactured in the same manner as the glass specimen manufacturing method of Example 1-1 above, with the exception that the starting materials were adjusted to the composition of silicon (Si), gallium (Ga), tellurium (Te), and aluminum (Al) shown in Table 13 below. Additionally, bulk glass formation evaluation, thermal stability evaluation, refractive index calculation, Vickers hardness measurement, and transmission spectrum measurement were performed in the same manner as in Experimental Examples 1 to 5 above, and the results are shown in Table 13 and
TABLE-US-00013 TABLE 13 Glass Thermal Quality transition stability Vickers Si Ga Te Al of glass temperature T hardness (at %) (at %) (at %) (at %) formation ( C.) ( C.) (GPa) EXAMPLE 15 7 75 3 Good 186.3 49.3 1.25 11-1 EXAMPLE 15 4 75 6 Good 182.8 53.5 1.08 11-2
[0087] Referring to Table 13, it can be seen that when the content of the aluminum element is 3.0 at % or more and 6.0 at % or less with respect to the total elements, the chalcogenide glass composition further including aluminum of the present disclosure can form a stable bulk glass with excellent thermal stability, hardness and refractive index at a wavelength of 10 m.
[0088] Additionally, referring to
Examples 12-1 to 12-3
[0089] A glass specimen further including iodine (I) in addition to silicon (Si), gallium (Ga), and tellurium (Te) was manufactured. Specifically, Examples 12-1 to 12-3 were manufactured in the same manner as the glass specimen manufacturing method of Example 1-1 above, with the exception that the starting materials were adjusted to the composition of silicon (Si), gallium (Ga), tellurium (Te), and iodine (I) shown in Table 14 below. Additionally, bulk glass formation evaluation, transmission spectrum measurement were performed in the same manner as in Experimental Examples 1 to 5 above, and the results are shown in Table 14 and
TABLE-US-00014 TABLE 14 Si Ga Te I Quality of glass (at %) (at %) (at %) (at %) formation EXAMPLE 12-1 10 14 75 1 Moderate EXAMPLE 12-2 10 12 75 3 Moderate EXAMPLE 12-3 10 15 65 10 Good
[0090] Referring to Table 14, it can be seen that when the content of the iodine element is 1.0 at % or more and 10.0 at % or less with respect to the total elements, the chalcogenide glass composition further including iodine of the present disclosure can form a stable bulk glass.
[0091] Additionally, referring to