Long-term radiation-induced optical darkening effects in chalcogenide glasses

In this work, it is reported that the γ-irradiated (2.41 MGy accumulated dose) glasses As₂S₃ (∼2 mm thick) and Ge₁₅.₈As₂₁S₆₃.₂ (∼1 mm thick), both measured ∼10 years after γ-irradiation, exhibit radiation-induced optical darkening effect (i.e., long-wave shift of fundamental optical absorption edge)...

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Veröffentlicht in:Semiconductor Physics Quantum Electronics & Optoelectronics
Datum:2016
1. Verfasser: Kavetskyy, T.S.
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Sprache:English
Veröffentlicht: Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України 2016
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Zitieren:Long-term radiation-induced optical darkening effects in chalcogenide glasses / T.S. Kavetskyy // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2016. — Т. 19, № 4. — С. 395-398. — Бібліогр.: 20 назв. — англ.

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spelling Kavetskyy, T.S.
2017-06-15T09:25:27Z
2017-06-15T09:25:27Z
2016
Long-term radiation-induced optical darkening effects in chalcogenide glasses / T.S. Kavetskyy // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2016. — Т. 19, № 4. — С. 395-398. — Бібліогр.: 20 назв. — англ.
1560-8034
DOI: 10.15407/spqeo19.04.395
PACS 61.43.Fs, 61.80.Ed, 78.40.Fy, 78.40.Pg
https://nasplib.isofts.kiev.ua/handle/123456789/121681
In this work, it is reported that the γ-irradiated (2.41 MGy accumulated dose) glasses As₂S₃ (∼2 mm thick) and Ge₁₅.₈As₂₁S₆₃.₂ (∼1 mm thick), both measured ∼10 years after γ-irradiation, exhibit radiation-induced optical darkening effect (i.e., long-wave shift of fundamental optical absorption edge). In the case of As₂S₃ glass, the observed longterm radiation-induced optical darkening effect is well comparable with that reported in literature for γ-irradiated (∼3 MGy accumulated dose) glass As₂S₃ (1.5 mm thick), measured directly after γ-irradiation. In view of practical application, this finding demonstrates the possibilities for development of innovative chalcogenide glass based long-term dosimeter systems with stable and controlled parameters. A possible general criterion for mechanisms of long-term radiation-induced structural changes in chalcogenide glasses has been also considered.
The investigated samples used for measurements were prepared within joint research projects (#0106U007386 and #0109U007446c) between DSPU (Drohobych, Ukraine) and SRC “Carat” (Lviv, Ukraine) supported by the MES of Ukraine (#0106U007385 and #0109U007445). Support of DAAD (Germany) and MES of Ukraine (projects #0111U001021 and #0114U002616) is also gratefully acknowledged.
en
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
Semiconductor Physics Quantum Electronics & Optoelectronics
Long-term radiation-induced optical darkening effects in chalcogenide glasses
Article
published earlier
institution Digital Library of Periodicals of National Academy of Sciences of Ukraine
collection DSpace DC
title Long-term radiation-induced optical darkening effects in chalcogenide glasses
spellingShingle Long-term radiation-induced optical darkening effects in chalcogenide glasses
Kavetskyy, T.S.
title_short Long-term radiation-induced optical darkening effects in chalcogenide glasses
title_full Long-term radiation-induced optical darkening effects in chalcogenide glasses
title_fullStr Long-term radiation-induced optical darkening effects in chalcogenide glasses
title_full_unstemmed Long-term radiation-induced optical darkening effects in chalcogenide glasses
title_sort long-term radiation-induced optical darkening effects in chalcogenide glasses
author Kavetskyy, T.S.
author_facet Kavetskyy, T.S.
publishDate 2016
language English
container_title Semiconductor Physics Quantum Electronics & Optoelectronics
publisher Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
format Article
description In this work, it is reported that the γ-irradiated (2.41 MGy accumulated dose) glasses As₂S₃ (∼2 mm thick) and Ge₁₅.₈As₂₁S₆₃.₂ (∼1 mm thick), both measured ∼10 years after γ-irradiation, exhibit radiation-induced optical darkening effect (i.e., long-wave shift of fundamental optical absorption edge). In the case of As₂S₃ glass, the observed longterm radiation-induced optical darkening effect is well comparable with that reported in literature for γ-irradiated (∼3 MGy accumulated dose) glass As₂S₃ (1.5 mm thick), measured directly after γ-irradiation. In view of practical application, this finding demonstrates the possibilities for development of innovative chalcogenide glass based long-term dosimeter systems with stable and controlled parameters. A possible general criterion for mechanisms of long-term radiation-induced structural changes in chalcogenide glasses has been also considered.
issn 1560-8034
url https://nasplib.isofts.kiev.ua/handle/123456789/121681
citation_txt Long-term radiation-induced optical darkening effects in chalcogenide glasses / T.S. Kavetskyy // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2016. — Т. 19, № 4. — С. 395-398. — Бібліогр.: 20 назв. — англ.
work_keys_str_mv AT kavetskyyts longtermradiationinducedopticaldarkeningeffectsinchalcogenideglasses
first_indexed 2025-11-24T06:16:35Z
last_indexed 2025-11-24T06:16:35Z
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fulltext Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 4. P. 395-398. doi: https://doi.org/10.15407/spqeo19.04.395 © 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine 395 PACS 61.43.Fs, 61.80.Ed, 78.40.Fy, 78.40.Pg Long-term radiation-induced optical darkening effects in chalcogenide glasses T.S. Kavetskyy Drohobych Ivan Franko State Pedagogical University, 24, I. Franko str., 82100 Drohobych, Ukraine The John Paul II Catholic University of Lublin, 14, Al. Racławickie, 20-950 Lublin, Poland Abstract. In this work, it is reported that the γ-irradiated (2.41 MGy accumulated dose) glasses As2S3 (∼2 mm thick) and Ge15.8As21S63.2 (∼1 mm thick), both measured ∼10 years after γ-irradiation, exhibit radiation-induced optical darkening effect (i.e., long-wave shift of fundamental optical absorption edge). In the case of As2S3 glass, the observed long- term radiation-induced optical darkening effect is well comparable with that reported in literature for γ-irradiated (∼3 MGy accumulated dose) glass As2S3 (1.5 mm thick), measured directly after γ-irradiation. In view of practical application, this finding demonstrates the possibilities for development of innovative chalcogenide glass based long-term dosimeter systems with stable and controlled parameters. A possible general criterion for mechanisms of long-term radiation-induced structural changes in chalcogenide glasses has been also considered. Keywords: chalcogenide glasses, optical properties, radiation modification. Manuscript received 20.06.16; revised version received 05.09.16; accepted for publication 16.11.16; published online 05.12.16. 1. Introduction Radiation-induced optical effects (RIOEs) caused by 60Co γ-irradiation in chalcogenide glasses (ChGs) are well-known to be used for dosimetric applications [1, 2]. RIOEs could be also considered as the main control parameter of radiation sensitivity of ChGs. It has been established on the example of Ge-As-S [3] and Ge-Sb-S [4] systems that the total RIOEs consist of two components: the dynamic component that relaxes for 2-3 months after γ-irradiation and static one that remains stable for a long period of time after γ-irradiation. Recently, analyzing the radiation-induced effects in chalcogenide glasses the authors [5] made assumption that a long-term period (more than 7 years) after 60Co γ- irradiation does not give an argument for observation of radiation-induced effects caused by timing relaxation of post-radiation changes or dynamic component of RIOE. But, as mentioned above, it has been experimentally established [3, 4] that the RIOE’s dynamic component is only 2 to 3 months and RIOE’s static component takes place for a long period after γ-irradiation. However, the question “how long RIOE’s static component would be existed?” was not examined yet. In this Letter, the results of optical transmission measurements of As2S3 (∼2 mm thick) and Ge15.8As21S63.2 (∼1 mm thick) glasses in unirradiated and γ-irradiated (2.41 MGy accumulated dose) states in the range of fundamental optical absorption edge are reported for the samples measured ∼10 years after γ-irradiation. Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 4. P. 395-398. doi: https://doi.org/10.15407/spqeo19.04.395 © 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine 396 The investigated samples of As2S3 and Ge15.8As21S63.2 compositions were prepared from elements of 99.9999% purity in evacuated silica ampoules using the standard melt-quenching procedure [6], polished to a high optical quality and annealed at about 20…30 K below the corresponding glass transition temperature before their radiation treatment. Both samples were subjected to radiation treatment with 60Co γ-quanta with the average energy E = 1.25 MeV and accumulated dose Φ = 2.41 MGy, details of which are described elsewhere [7-9]. Optical transmission spectra of the samples were measured in the visible spectral range at room temperature using an Evolution 220 UV- visible spectrophotometer. Fig. 1 shows the optical transmission spectra, τ(λ), of g-As2S3 and g-Ge15.8As21S63.2 samples in the unirradiated and γ-irradiated states, measured ∼10 years after γ-irradiation. Clearly, the long-wave shift of fundamental optical absorption edge is detected, signifying the existence of long-term radiation-induced optical darkening effect. The decrease in the sample’s transparency in the saturation region for g-As2S3 is due to the radiation-induced oxidation processes occurring on the sample surface [9]. The observed long-term radiation- induced optical darkening effect is found to be practically the same as that reported for γ-irradiated (∼3 MGy accumulated dose) g-As2S3 (1.5 mm thick), measured directly after γ-irradiation [10]. To quantify this similarity, as an example, one may compare Δτ ∼15% at λ = 675 nm in this study (see Fig. 1) with Δτ ∼20% at λ = 675 nm in the work [10] (see Fig. 1, curves 1 and 2). Taking into account the dynamic RIOE component on the level of ∼5% [3, 4], it means that the RIOE’s static component may exist for a long period, perhaps more than 10 years. It may also indicate that a backward measuring chronology mentioned by the authors [10], it is not necessary to be performed, being although useful to make in situ experiment, as the radiation-induced optical darkening effects in chalcogenide glasses are stable in time, and corresponding radiation-induced structural changes can be correctly investigated with a long-time interval. In this respect, the long-term radiation-induced structural changes examined in the works [2, 11-14] are very important in view of practical applications of chalcogenide glasses. In particular, the long-term radiation-induced effects demonstrate the possibilities for development of innovative chalcogenide glass based long- term dosimeter systems with stable and controlled parameters. In spite of the long-term radiation-induced optical darkening effects detected in this study for both investigated g-As2S3 and g-Ge15.8As21S63.2, the mechanisms of long-term radiation-induced structural changes in these compounds are found to be different [2, 11, 13, 14]. It is concluded from the recent positron annihilation spectroscopy measurements with the Doppler broadening of annihilation line (DBAL) technique [11, 14]. Namely, it has been ascertained using the DBAL data that the defect structures of radiation-modified g-As2S3 and g-Ge15.8As21S63.2 are different probably as a result of different mechanisms of radiation-induced defect formation. It has been suggested that the non-defective mechanism within the distortion model for g-As2S3 and the defective mechanism within the coordination topological defects (CTDs) model for g-Ge15.8As21S63.2 took place [11, 14], since the latter CTD model has been evidently verified using Raman spectroscopy studies, employing the differential representation of depolarized Raman spectra [13]. The CTD approach used for g-Ge15.8As21S63.2 or (As2S3)0.4(GeS2)0.6 alloy with the dominant Ge-S sub- system seems to be valid for major Ge-S based chalcogenides (see, for example, [15-17]). Therefore, the positron annihilation spectroscopy DBAL method should be reported as a highly sensitive and unique experimental tool to compensate impossibilities (if any) of optical and structural techniques to directly identify the radiation-induced changes in defect structure of glassy materials on the nanoscale level. Moreover, analyzing the DBAL experimental results obtained in the context with XRD and Raman data, some regularity could be observed that may be applied to estimate a possible general criterion for mechanisms of long-term radiation-induced structural changes in ChGs. Fig. 1. Optical transmission spectra, τ(λ), of (a) g-As2S3 (d ≅ 2.0 mm, Φ = 2.41 MGy) and (b) g-Ge15.8As21S63.2 (d ≅ 1.0 mm, Φ = 2.41 MGy) samples in unirradiated (unirrad.) and γ- irradiated (irrad.) states, measured ∼10 years after γ-irradiation. Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 4. P. 395-398. doi: https://doi.org/10.15407/spqeo19.04.395 © 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine 397 Indeed, on the one hand, the established for As-S based glasses the long-term radiation-induced structural changes in DBAL data [2, 11, 14], when the first sharp diffraction peak (FSDP) becomes weaker and broader after γ-irradiation [2, 12], have been interpreted within the non-defective distortion model. Since the FSDP originates as a signature of the medium-range order (MRO) structure within the range 5…20 Å in covalent glasses (for review, see [18]), which is commonly accepted by many researchers in literature, the FSDP weakening and broadening means the decrease in the MRO structural correlation length and, consequently, the rise of disordering on the MRO scale. Note, that no changes or possible ordering on the short-range order (SRO) structure within the range 2 to 5 Å [18] should be happened as a result of radiation-induced decreasing the size or void concentration due to relaxation processes within the distortion model [14]. Thus, when the radiation-induced structural changes in ChGs occur towards the disordering on the MRO scale and no changes or ordering on the SRO scale, the non-defective mechanism in the frame of the distortion model and any other models (if exist), resulting in a final structural configuration without charged defects, is dominant. On the other hand, the established for Ge-S based glasses the long-term radiation-induced structural changes in DBAL data [2, 11, 14], when the FSDP remains practically unchanged [2] or its intensity can be something higher [16] and peak is probably something narrower upon γ- irradiation, have been interpreted within the defective CTD model, involving atomic rearrangements directly in the first coordination shells (first-nearest-neighbor atomic correlations), that is, on the SRO scale. The unobservable changes in the FSDP and/or the FSDP sharping and narrowing means that no changes or increasing the MRO structural correlation length and, consequently, a stable MRO structure and/or rise of ordering on the MRO scale take place. Thus, when the radiation-induced structural changes in ChGs occur towards the no changes or ordering on the MRO scale and disordering on the SRO scale, the defective mechanism in the frame of the coordination topological defects and any other models (if exist), resulting in a final structural configuration with charged defects, is dominant. The above mentioned DBAL data versus FSDP- XRD data, interpreted within CTD model for g- Ge15.8As21S63.2, are also found to be consistent with Raman data, showing clear confirmation for CTD model applied [13]. In view of the above analysis, the degree of disorder, exemplified by the ratio of Ibos/Imol in Raman spectrum, illustrating the essential increase of the degree of disorder after γ-irradiation for g-Ge15.8As21S63.2 [13], should be related to the increase in the disorder on the SRO scale in agreement again with CTD approach. Thus, the origin of Ibos/Imol seems to be related with the degree of disorder of SRO structure in covalent glasses. It is also some signature that the first sharp diffraction peak and the low frequency dynamics (the boson peak) are not related directly to each other on the MRO scale, which is in contrast to assumption made by the authors [19] and in agreement with observations of the authors [20]. Let us summarize the possible general criterion for mechanisms of long-term radiation-induced structural changes in chalcogenide glasses that involves “ordering- disordering” on the nanoscale as follows: when the radiation-induced structural changes in chalcogenide glasses occur towards disordering on the medium-range order scale and no changes or ordering on the short- range order scale, the non-defective mechanism, resulting in a final structural configuration without charged defects, is dominant; and, vice versa, when the radiation- induced structural changes in chalcogenide glasses occur towards no changes or ordering on the medium-range order scale and disordering on the short-range order scale, the defective mechanism, resulting in a final structural configuration with charged defects, is dominant. In conclusion, the long-term radiation-induced optical darkening effects have been detected for g-As2S3 (d ≅ 2.0 mm, Φ = 2.41 MGy) and g-Ge15.8As21S63.2 (d ≅ 1.0 mm, Φ = 2.41 MGy), measured ∼10 years after γ- irradiation. In the case of g-As2S3, the observed long- term radiation-induced optical darkening effect is well comparable with that reported in literature for γ- irradiated (∼3 MGy accumulated dose) g-As2S3 (1.5 mm thick) measured directly after γ-irradiation [10]. In view of practical applications, this finding demonstrates the possibilities for development of innovative chalcogenide glass based long-term dosimeter systems with stable and controlled parameters. Previous investigations of both these samples with the positron annihilation spectroscopy DBAL method and analysis performed in respect to XRD and Raman data allow also suggestion on the possible general criterion for mechanisms of long- term radiation-induced structural changes in ChGs. Acknowledgments The investigated samples used for measurements were prepared within joint research projects (#0106U007386 and #0109U007446c) between DSPU (Drohobych, Ukraine) and SRC “Carat” (Lviv, Ukraine) supported by the MES of Ukraine (#0106U007385 and #0109U007445). Support of DAAD (Germany) and MES of Ukraine (projects #0111U001021 and #0114U002616) is also gratefully acknowledged. References 1. O.I. Shpotyuk, Radiation-induced effects in chalcogenide vitreous semiconductors. Chapter 6 // In: Semiconducting Chalcogenide Glass I: Glass Formation, Structure, and Stimulated Transformations in Chalcogenide Glasses: Semiconductors and Semimetals, Vol. 78 Semiconductor Physics, Quantum Electronics & Optoelectronics, 2016. V. 19, N 4. P. 395-398. doi: https://doi.org/10.15407/spqeo19.04.395 © 2016, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine 398 (R. Fairman and B. Ushkov, eds.). Elsevier Academic Press, 2004, p. 215-260. 2. T.S. Kavetskyy, A.L. Stepanov, Effects of gamma- irradiation and ion implantation in chalcogenide glasses. Chapter 14 // In: Glass Nanocomposites: Synthesis, Properties and Applications (B. Karmakar, K. Rademann, A.L. Stepanov, eds.). Elsevier Academic Press, 2016, p. 341-358. 3. O.I. Shpotyuk, E.R. Skordeva, R.Ya. Golovchak, V.D. Pamukchieva, A.P. Kovalskii, Radiation- stimulated changes in transmission of chalcogenide glasses of As2S3-Ge2S3 // J. Appl. Spectr. 66(5), p. 749-753 (1999). 4. O.I. Shpotyuk, T.S. Kavetskyy, A.P. Kovalskiy, R.V. Lutziv, V. Pamukchieva, Radiation-induced changes in optical transmission in vitreous semiconductors of the GexSb40-xS60 system // Ukr. J. Phys. 46(4), p. 495-498 (2001). 5. O. Shpotyuk, S.A. Kozyukhin, M. Shpotyuk, A. Ingram, R. Szatanik, Positronics of radiation- induced effects in chalcogenide glassy semiconductors // Semiconductors, 49(3), p. 298- 304 (2015). 6. A. Feltz, Amorphous and Vitreous Inorganic Solids. Moscow, Mir, 1986 (in Russian). 7. 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Shpotyuk, A study of reversible γ-induced structural transformations in vitreous Ge23.5Sb11.8S64.7 by high-resolution X-ray photoelectron spectroscopy // J. Phys. Chem. B, 110, p. 22930-22934 (2006). 16. T. Kavetskyy, O. Shpotyuk, I. Kaban, W. Hoyer, Radiation-modified structure of Ge25Sb15S60 and Ge35Sb5S60 glasses // J. Сhem. Phys. 128(24), p. 244514-1-244514-8 (2008). 17. T. Kavetskyy, O. Shpotyuk, V. Balitska, G. Dovbeshko, I. Blonskyy, I. Kaban, W. Hoyer, M. Iovu, A. Andriesh, Vibrational and structural properties of unmodified and radiation-modified chalcogenide glasses for advanced optical applications // Proc. SPIE, 7142, p. 71420B-1- 71420B-8 (2008). 18. S.R. Elliott, Medium-range structural order in covalent amorphous solids // Nature, 354, p. 445- 452 (1991). 19. A.P. Sokolov, A. Kisliuk, M. Soltwisch, D. Quitmann, Medium-range order in glasses: Comparison of Raman and diffraction measurements // Phys. Rev. Lett. 69(10), p. 1540- 1543 (1992). 20. L. Börjesson, A.K. Hassan, J. Swenson, L.M. Torell, A. Fontana, Is there a correlation between the first sharp diffraction peak and the low frequency vibrational behavior of glasses? // Phys. Rev. Lett. 70(9), p. 1275-1278 (1993).