Ukrainian Journal of Physical Optics


2026 Volume 27, Issue 4


ISSN 1816-2002 (Online), ISSN 1609-1833 (Print)

ANNEALING-INDUCED CRYSTALLIZATION OF SILVER THIOARSENITES AND SILVER MIGRATION IN Agx(As2S3)1-X GLASSES

Yu. Azhniuk, A. Pogodin, M. Filep, V. Lopushansky, V. Izai, V. Kryshenik, I. Voynarovych, and A.V. Gomonnai

Author Information
1Azhniuk, Yu. ORCID logo SCOPUS logo, 2Pogodin, A. ORCID logo SCOPUS logo, 1,3Filep, M. ORCID logo SCOPUS logo, 1Lopushansky, V. ORCID logo SCOPUS logo, 4Izai, V. ORCID logo SCOPUS logo, 1Kryshenik, V. ORCID logo SCOPUS logo, 1Voynarovych, I. ORCID logo SCOPUS logo, 1*Gomonnai A.V. ORCID logo SCOPUS logo,
1Institute of Electron Physics, Nat. Acad. Sci. Ukr., 21 Universytetska Str., 88017, Uzhhorod, Ukraine
2Uzhhorod National University, 3 Narodna Sq., 88000, Uzhhorod, Ukraine
3Ferenc Rákóczi II Transcarpathian Hungarian University, 6 Kossuth Sq., Berehovo 90200, Ukraine
4Center for Nanotechnology and Advanced Materials, Faculty of Mathematics, Physics and Informatics, Comenius University Bratislava, Mlynská Dolina F1, 84248, Bratislava, Slovakia
*Corresponding author: gomonnai@ukr.net

ABSTRACT

X-ray diffraction (XRD) and Raman scattering studies showed that the amorphous structure of Agx(As2S3)1-x samples with x≤0.15 is preserved upon annealing at 250°C for up to 4 h. Meanwhile, XRD patterns of the annealed x = 0.3 sample show the presence of three kinds of silver thioarsenite nanocrystals formed in the samples upon annealing: AgAsS2 (smithite and trechmannite) as well as Ag3AsS3 (proustite). The average nanocrystal size, estimated from the Scherrer equation, is about 20 nm. Raman spectroscopy also shows the formation of thioarsenite nanocrystals in Agx(As2S3)1-x glasses upon annealing, with dependence on the silver content and annealing duration. Raman spectroscopy and energy-dispersive X-ray spectroscopy show thermally induced migration of silver atoms toward the sample surface upon annealing.

Keywords: amorphous chalcogenides, phase separation, nanocrystals, X-ray diffraction, Raman spectroscopy, photoinduced effects

UDC: 543.424.2

    1. Frumar, M. & Wagner, T. (2003). Ag doped chalcogenide glasses and their applications. Curr. Opin. Solid State Mater. Sci. 7. 117-126.
      doi:10.1016/S1359-0286(03)00044-5
    2. Pradel, A., Kuwata, N., & Ribes, M. (2003). Ion transport and structure in chalcogenide glasses. J. Phys.: Condens. Matter. 15. S1561-S1571.
      doi:10.1088/0953-8984/15/16/306
    3. Stratan, I., Tsiulyanu, D., & Eisele, I. (2006). A programmable metallization cell based on Ag-As2S3. J. Optoelectron. Adv. Mater. 8. 2117-2119.
    4. Holbrook, C., Chen, P., Novita, D. I., & Boolchand P. (2007). Origin of Conductivity Threshold in the Solid Electrolyte Glass System: (Ag2S)x(As2S3)1-x. IEEE Transactions on Nanotechnology. 6. 530-535.
      doi:10.1109/TNANO.2007.905540
    5. Kaban, I., Jóvári, P., Wágner, T., Bartoš, M., Frumar, M., Beuneu, B., Hoyer, W., Mattern, N., & Eckert, J. (2011). Structural study of AsS2-Ag glasses over a wide concentration range. J. Non-Cryst. Solids. 357. 3430-3434.
      doi:10.1016/j.jnoncrysol.2011.06.015
    6. Stehlik, S., Kolar, J., Bartos, M., Vlcek, Mil., Frumar M., Zima, V. & Wagner, T. (2010). Conductivity in Ag-As-S(Se, Te) chalcogenide glasses. Solid State Ionics. 181. 1625-1630.
      doi:10.1016/j.ssi.2010.09.016
    7. Gotoh, T. & Tanaka, K. (2001), Photoinduced surface deformations in ion-conducting Ag-As-S glasses. II. Anisotropic deformation produced by large light spots. J. Appl. Phys. 89. 4703-4706.
      doi:10.1063/1.1357472
    8. Kyriazis, F., Chrissanthopoulos, A., Dracopoulos, V., Krbal, M., Wagner, T., Frumar, M., & Yannopoulos, S. N. (2009). Effect of silver doping on the structure and phase separation of sulfur-rich As-S glasses: Raman and SEM studies. J. Non-Cryst. Solids. 355. 2010-2014.
      doi:10.1016/j.jnoncrysol.2009.04.070
    9. Andrikopoulos, K. S., Arvanitidis, J., Dracopoulos, V., Christofilos, D., Wagner, T., & Yannopoulos, S. N. (2011). Nanoindentation and Raman studies of phase-separated Ag-As-S glasses, Appl. Phys. Lett. 99. 171911.
      doi:10.1063/1.3651494
    10. Douaud, A., Messaddeq, S. H., & Messaddeq, Y. (2019). Photo-induced birefringence and surface ripples structures in As-S-Ag chalcogenide thin-films. J. Non-Cryst. Solids. 519. 119446.
      doi:10.1016/j.jnoncrysol.2019.05.022
    11. Ohta, M., Tsutsumi, M., Izumi, F. & Ueno, S. (1982). Phase separation and structural change accompanying the introduction of silver to arsenic trisulphide glass. J. Mater. Sci. 17. 2431-2434.
      doi:10.1007/BF00543755
    12. Yaji, T. & Kurita, S. Photodoping sensitivityof Ag into amorphous As2S3 films. (1983). J. Appl. Phys. 54. 647-651.
      doi:10.1063/1.332029
    13. Indutnyi, I. Z., Dan'ko, V. A., Kudryavtsev, A. A., Michailovskaya, E. V., & Min'ko, V. I. (1995). Photodoping in As2S3-Ag structures. J. Non-Cryst. Solids. 185. 176-182.
      doi:10.1016/0022-3093(94)00660-1
    14. Tasseva, J., Todorov, R., Babeva, Tz., & Petkov, K. (2010). Structural and optical characterization of Ag photo-doped thin As40S60−xSex films for non-linear applications. J. Opt. 12. 065601.
      doi:10.1088/2040-8978/12/6/065601
    15. Stronski, A., Revutska, L., Meshalkin, A., Paiuk, O., Achimova, E., Korchovyi, A., Shportko, K., Gudymenko, O., Prisacar, A., Gubanova, A., & Triduh, G. (2019). Structural properties of Ag-As-S chalcogenide glasses in phase separation region and their application in holographic grating recording. Opt. Mater. 94. 393-397.
      doi:10.1016/j.optmat.2019.06.016
    16. Okuno, M., Sugaya, H., & Matsumoto, T. (1992). An EXAFS study of Ag3AsS3 glass, J. Non-Cryst. Solids. 150. 356-360.
      doi:10.1016/0022-3093(92)90152-A
    17. Studenyak, I. P., Neimet, Yu. Yu., Kranjčec, M., Solomon, A. M., Orliukas, A. F., Kežionis, A., Kazakevičius, E., & Šalkus, T. (2014). Electrical conductivity studies in (Ag3AsS3)x(As2S3)1-x superionic glasses and composites. J. Appl. Phys. 115. 033702.
      doi:10.1063/1.4861624
    18. Studenyak, I., P., Neimet, Yu.,Yu., Rati, Y., Y., Stanko, D., Kranjčec, M., Kökényesi, Daróci, S., L., & Bohdan, R. (2014.) Structural and optical properties of annealed and illuminated (Ag3AsS3)0.6(As2S3)0.4 thin films. Opt. Mater. 37. 718-723.
      doi:10.1016/j.optmat.2014.08.019
    19. Studenyak, I. P., Molnar, Z. R., Kutsyk, M. M., Izai, V. Yu., Kranjčec, M., & Kökényesi, S. (2018). Temperature studies of optical absorption in the sandwich structure based on (Ag3AsS3)0.6(As2S3)0.4 thin film and gold nanoparticles. Semicond. Phys., Quantum Electron. & Optoelectron. 21. 89-94.
      doi:10.15407/spqeo21.01.089
    20. Wágner, T., Vlček, Mir., Kasap, S. O., Vlček, Mil., & Frumar, M. (2001), Changing the composition of Ag-As-S amorphous films using photo-induced solid state reaction. J. Non-Cryst. Solids. 284. 168-173.
      doi:10.1016/S0022-3093(01)00397-0
    21. Piarristeguy, A., Ramonda, M., Kuwata, N., Pradel, A., & Ribes, M. (2006). Microstructure of Ag2S-As2S3 glasses. Solid State Ionics. 177. 3157-3160.
      doi:10.1016/j.ssi.2006.07.054
    22. Almeida, J. M. P., Lu, C., Mendonça, C. R., & Arnold, C. B. (2015), Single-step synthesis of silver sulfide nanocrystals in arsenic trisulfide. Opt. Mater. Expr. 5. 1815-1821.
      doi:10.1364/OME.5.001815
    23. Almeida, J. M. P., Barbano, E. C., Arnold, C. B., Misoguti, L., & Mendonça, C. R. (2017). Nonlinear optical waveguides in As2S3-Ag2S chalcogenide glass thin films. Opt. Mater. Expr. 7. 93-99.
      doi:10.1364/OME.7.000093
    24. Azhniuk, Y., Pogodin, A., Izai, V., Filep, M., Lopushansky, V., Satrapinskyy, L., Yukhymchuk, V., Kryshenik, V., Voynarovych, I., & Gomonnai, A. V. (2025). Phase separation and photoinduced migration of silver in Agx(As2S3)1-x glasses. Mater. Res. Expr. 12. 095201.
      doi:10.1088/2053-1591/ae0782
    25. Hellner, E., & Burzlaff, H. (1964). Die Struktur des Smithits AgAsS2. Naturwissenschaften. 51. 35-36.
      doi:10.1007/BF00622577
    26. Matsumoto, T., & Nowacki, W. (1969). The crystal structure of trechmannite, AgAsS2. Zeitschrift für Kristallographie. 129. 163-177.
      doi:10.1524/zkri.1969.129.1-4.163
    27. Allen, S. (1985). Phase transitions in proustite I. Structural studies. Phase Transitions. 6. 1-24.
      doi:10.1080/01411598508219887
    28. Smitiukh, O. V., Marchuk, O. V., Kogut, Y. M., Yukhymchuk, V. O., Mazur, N. V., Myronchuk, G. L., Ponedelnyk, S. M., Cherniushok, O. I., Parashchuk, T. O., Khyzhun, O. Y., Wojciechowski, К. T., & Fedorchuk, A. O. (2022). Effect of rare-earth doping on the structural and optical properties of the Ag3AsS3 crystals. Opt Quant Electron. 54. 224.
      doi:10.1007/s11082-022-03542-w
    29. Scherrer, P. (1918). Bestimmung der Größe und der inneren Struktur von Kolloidteilchen Mittels Röntgenstrahlen. Nachr. Ges. Wiss. Göttingen, Math. - Phys. Klasse. 1918. 98.
    30. Tanaka, K. (2014). Photoinduced deformations in chalcogenide glasses, in: R.P. Wang (Ed.), Amorphous Chalcogenides: Advances and Applications, Pan Stanford Publishing. 59-96.
    31. Tanaka K., & Shimakawa K. (2021). Amorphous Chalcogenide Semiconductors and Related Materials. Springer Nature Switzerland AG.Cham.
      doi:10.1007/978-3-030-69598-9
    32. Yannopoulos, S., N. (2021). Athermal photoelectronic effects in non-crystalline chalcogenides: Current status and beyond, in: A.V. Kolobov and K. Shimakawa (Ed.). The World Scientific Reference of Amorphous Materials: Structure, Properties, Modeling and Applications (Volume 1: Chalcogenide Glasses). World Scientific Publishing. Singapore. 251-311.
      doi:10.1142/9789811215575_0009
    33. Kovalskiy, A., Ganjoo, A., Khalid, S., & Jain, H. (2010). Combined high-resolution XPS and EXAFS study of Ag photodissolution in a-As2S3 thin film. J. Non-Cryst. Solids. 356. 2332-2336.
      doi:10.1016/j.jnoncrysol.2010.02.021
    34. Lőrinczi, A., Popescu, M., Sava, F., Velea, A., & Şimăndan, I.-D. (2011). Silver doped As2S3 chalcogenide films: A diffusion study. Phys. Status Solidi C. 8. 2617-2620.
      doi:10.1002/pssc.201084096
    35. Indutnyi, I. Z., Mynko, V. I., Sopinskyy, M. V., & Mamykin, S. V. (2025). Surface plasmon-polariton study of photoinduced diffusion in light-sensitive Ag-As2S3 thin-film structure. Thin Solid Films. 824. 140705.
      doi:10.1016/j.tsf.2025.140705
    36. Chen, P., Holbrook, C., Boolchand, P., Georgiev, D. G., Jackson, K. A., & Micoulaut, M. (2008). Intermediate phase, network demixing, boson and floppy modes, and compositional trends in glass transition temperatures of binary AsxS1−x system. Phys. Rev. B. 78. 224208.
      doi:10.1103/PhysRevB.78.224208
    37. Yannopoulos, S. N., Andrikopoulos, K. S., Kastrissios, D. Th., & Papatheodorou, G. N. (2012). Origin of photoinduced defects in glassy As2S3 under band gap illumination studied by Raman scattering: A revisory approach. Phys. Status Solidi B. 249. 2005-2012.
      doi:10.1002/pssb.201200385
    38. Frumar, M., Jedelský, J., Frumarová, B., Wágner, T., & Hrdlička, M. (2003), Optically and thermally induced changes of structure, linear and non-linear optical properties of chalcogenides thin films. J. Non-Cryst. Solids. 326-327. 399-404.
      doi:10.1016/S0022-3093(03)00446-0
    39. Yannopoulos, S. N. (2003). Intramolecular structural model for photoinduced plasticity in chalcogenide glasses. Phys. Rev. B. 68. 064206.
      doi:10.1103/PhysRevB.68.064206
    40. Firth, A., Owen A., & Ewen, P. (1981). Laser-Raman study of the structure of silver doped As40S60 glass. Journal de Physique Colloques 42. C4-903-C4-906.
      doi:10.1051/jphyscol:19814196
    41. Kharbish, S. (2017). Spectral-structural characteristics of the extremely scarce silver arsenic sulfosalts, proustite, smithite, trechmannite and xanthoconite: μ-Raman spectroscopy evidence. Spectrochim. Acta A Mol. Biomol. Spectrosc. 177. 104-110.
      doi:10.1016/j.saa.2017.01.038
    42. Makreski, P., Jovanovski, G., Minceva-Sukarova, B., Soptrajanov, B., Green, A., Engelen, B., & Grzetic, I. (2004). Vibrational spectra of MI3MIIIS3 type synthetic minerals (MI = Tl or Ag and MIII = As or Sb). Vibrational Spectroscopy. 35. 59-65.
      doi:10.1016/j.vibspec.2003.11.007
    43. Forneris, R. (1969). The infrared and Raman spectra of realgar and orpiment. Amer. Mineralog. 54. 1062-1074.
    44. Zallen, R., Slade, M. L., & Ward, A. T. (1971). Lattice vibrations and interlayer interactions in crystalline As2S3 and As2Se3. Phys. Rev. B. 3. 4257-4273.
      doi:10.1103/PhysRevB.3.4257
    45. Černošek, Z., Černošková, E., & Beneš, L. (1999) Crystalline arsenic trisulfide: preparation, differential scanning calorimetry and Raman scattering measurements. Mater. Lett. 38. 336-340.
      doi:10.1016/S0167-577X(98)00185-2
    46. Liu, K., Dai, L., Li, H., Hu, H., Yang, L., Pu, C., Hong, M., & Liu, P. (2019). Phase transition and metallization of orpiment by Raman spectroscopy, electrical conductivity and theoretical calculation under high pressure. Materials. 12. 784-796.
      doi:10.3390/ma12050784
    47. Kolev, K., & Wautelet, M. (1990). Kinetics of CW laser-induced crystallization and oxidation of thin Sb, Se, and Sb2Se3 films in air. Appl. Phys. A. 50. 192-196.
      doi:10.1007/BF00324417
    48. Azhniuk, Yu. M., Stoyka, V., Petryshynets, I., Rubish, V. M., Guranich, O. G., Gomonnai, A. V., & Zahn, D. R. T. (2012). SbSI nanocrystal formation in As-Sb-S-I glass under laser beam. Mater. Res. Bull. 47. 1520-1522.
      doi:10.1016/j.materresbull.2012.02.036
    49. Makreski, P., Petruševski, G., Ugarković, S., & Jovanovski, G. (2013). Laser-induced transformation of stibnite (Sb2S3) and other structurally related salts. Vibr. Spectrosc. 68. 177-182.
      doi:10.1016/j.vibspec.2013.07.007
    50. Azhniuk, Yu. M., Gomonnai, A. V., Rubish, V. M., Rigan, M. Yu., Solomon, A. M., Gomonnai, O. O., Guranich, O. G., Petryshynets, I., & Zahn, D. R. T. (2013). In situ Raman observation of laser-induced formation of TlInSe2 crystallites in Tl-In-As-Se glass. J. Phys. Chem. Solids. 74. 1452-1458.
      doi:10.1016/j.jpcs.2013.05.005
    51. Azhniuk, Y. M., Gomonnai, A. V., Lopushansky, V. V., Gomonnai, O. O., Babuka, T., Loya, V. Y., & Voynarovych, I. M. (2023). Laser-induced transformations in thermally evaporated thin TlInSe2 films studied by Raman spectroscopy. Ukr. J. Phys. 68. 816-821.
      doi:10.15407/ujpe68.12.816
    52. Azhniuk, Y., Hasynets, S., Lopushansky, V., Kryshenik, V., Solomon, A. M., & Gomonnai, A. V. (2023). Raman study of photoinduced crystallization of SnS2 in As2S3:Sn glasses. Vibr. Spectrosc. 128. 103583.
      doi:10.1016/j.vibspec.2023.103583
    53. Azhniuk, Y. M., Lopushansky, V. V., Loya, V. Y., Hasynets, S. M., Kryshenik, V. M., & Gomonnai, A. V. (2026). Formation of SnS2 nanocrystals in amorphous (As2S3)1 x(SnS2)x films studied by Raman spectroscopy. Molecular Cryst. Liquid Cryst. 770. 907 - 919.
      doi:10.1080/15421406.2026.2627640
    54. Fernandes, Th., Hans, P., Texier, M., Comby-Dassonneville, S., Mariette, C., Mignerot, F., Jeannot, S., le Friec, Y., Simola, R., & Thomas, O. (2025), Laser-induced crystallization and amorphization of Ge-Rich GST thin films monitored in situ with synchrotron X-ray diffraction. Phys. Stat. Solidi RRL. 19. 2400392.
      doi:10.1002/pssr.202400392
    55. Azhniuk, Yu. M., Dzhagan, V. M., Solonenko, D., Mukherjee, A., Loya, V. Yu., Grytsyshche, I. V., Lopushansky, V. V., Gomonnai, A. V., & Zahn, D. R. T. (2019). Laser annealing-induced formation of CdS nanocrystals in Cd-doped amorphous As2S3 thin films. Phys. Status Solidi B. 256. 1800298.
      doi:10.1002/pssb.201800298
    56. Azhniuk, Y. M., Lopushansky, V. V., Loya, V. Yu., Kryshenik, V. M., Dzhagan, V. M., Gomonnai, A. V., & Zahn, D. R. T. (2020). Raman study of laser-induced formation of II-VI nanocrystals in zinc-doped As-S(Se) films. Appl. Nanosci. 10. 4831-4837.
      doi:10.1007/s13204-020-01269-2
    57. Azhniuk, Y. M., Dzhagan, V. M., Solonenko, D. Lopushansky, V. V., Loya, V. Y., Kryshenik, V. M., Voynarovych, I. M., Gomonnai, A. V., & Zahn, D. R. T. (2021). Ternary CdS1-xSex nanocrystals formed in Cd-doped As-Se-S films due to photoenhanced diffusion during micro-Raman measurement. J. Raman Spectrosc. 52. 821-832.
      doi:10.1002/jrs.6063
    58. Stehlik, S., Kolar, J., Frumar, M., Wagner, T., Haneda, H., & Sakaguchi, I. (2011). Phase separation in chalcogenide glasses: the system AgAsSSe. Int. J. Appl. Glass Sci. 2. 301-307.
      doi:10.1111/j.2041-1294.2011.00065.x
    59. Correr, W., Messaddeq, S. H., Douaud, A., & Messaddeq, Y. (2021). Vibrational and conductive microscopic investigation of thermal dewetting in Ag-As-S chalcogenide thin films. Appl. Surf. Sci. 554. 149621.
      doi:10.1016/j.apsusc.2021.149621

    Дослідження дифракції рентгенівських променів і раманівської спектроскопії показали, що при відпалі при 250 °C тривалістю до 4 год зберігається аморфна структура зразків Agx(As2S3)1-x з x ≤ 0.15. Водночас дифрактограми зразка з x = 0.3 вказують на утво¬рення при відпалі нанокристалів тіоарсенатів срібла трьох типів: AgAsS2 (смітит і трехманіт) та Ag3AsS3 (прустит). Середній розмір утворених нанокристалів, оцінений за формулою Шерера, становить близько 20 нм. Утворення нанокристалів тіоарсенітів у склах Agx(As2S3)1-x при відпалі також підтверджується даними раманівської спектроскопії, яка показує залежність цього явища від вмісту срібла у склі та тривалості відпалу. Методами раманівської спектроскопії та енергодисперсійної рентгенівської спектроскопії показано термоіндуковану міграцію срібла з об'єму до поверхні зразків.

    Ключові слова: аморфні халькогеніди; розділення фаз; нанокристали; дифракція рентгенівських променів; раманівська спектроскопія; фотоіндуковані ефекти

Free download this article 

This work is licensed under CC BY 4.0