The Role of Heterovalent P+5/Si+4 Substitution on the Microhardness of Ag6+x(P1-xSix)S5I Single Crystals

Editorial Board PCSS Journal; I.O. Shender; M.J. Filep; O.P. Kokhan; V.S. Bilanych; A.I. Pogodin; T.O. Malakhovska

doi:10.15330/pcss.27.2.449-455

Authors

I.O. Shender Uzhhorod National University
M.J. Filep Ferenc Rákóczi II Transcarpathian Hungarian University, Beregovo, Ukraine
O.P. Kokhan Uzhhorod National University
V.S. Bilanych Uzhhorod National University
A.I. Pogodin Uzhhorod National University
T.O. Malakhovska Uzhhorod National University, Uzhhorod, Ukraine

DOI:

https://doi.org/10.15330/pcss.27.2.449-455

Keywords:

argyrodite, single crystal, microhardness, heterovalent substitution

Abstract

The dependence of the microhardness of Ag_6+x(P_1-xSi_x)S₅I (х = 0.25; 0.5; 0.75) single crystals on load and composition was investigated using the Vickers method. The investigation was performed in wide range of the applied loads 0.05…2 N at room temperature. It has been established that an increase in the load on the indenter leads to a nonlinear decrease in the microhardness values for all studied crystals. Observed dependences indicates a normal indentation size effect. The behavior of microhardness of Ag_6+x(P_1-xSi_x)S₅I single crystals were described using the geometrically necessary dislocations model. The corresponding parameters of the used model were determined. The influence of ionic radii and electronegativity on microhardness change were discussed. Using Meyer's law, the occurrence of a normal indentation size effect has been confirmed.

References

A. Machín, C. Morant, F. Márquez, Batteries, Advancements and Challenges in Solid-State Battery Technology: An In-Depth Review of Solid Electrolytes and Anode Innovations 10(1), 29 (2024); https://doi.org/10.3390/batteries10010029.

Z. Moradi, A. Lanjan, R. Tyagi, S. Srinivasan, Journal of Energy Storage, Review on current state, challenges, and potential solutions in solid-state batteries research 73, 109048 (2023); https://doi.org/10.1016/j.est.2023.109048.

C. Li, Z. Wang, Z. He, Y. Li, J. Mao, K. Dai, C. Yan, J. Zheng, Sustainable Materials and Technologies, An advance review of solid-state battery: challenges, progress and prospects 29, e00297 (2021); https://doi.org/10.1016/j.susmat.2021.e00297.

J. Sung, J. Heo, D.-H. Kim, S. Jo, Y.-C. Ha, D. Kim, S. Ahn, J.-W. Park, Materials Chemistry Frontiers, Recent advances in all-solid-state batteries for commercialization 8, 1861 (2024); https://doi.org/10.1039/D3QM01171B.

Z. Zhang, W.Q. Han, Nano-Micro Letters, From Liquid to Solid-State Lithium Metal Batteries: Fundamental Issues and Recent Developments 16, 24 (2024); https://doi.org/10.1007/s40820-023-01234-y.

Z. Zhang, L. Zhang, Y. Liu, C. Yu, X. Yan, B. Xu, L. Wang, Journal of Alloys and Compounds, Synthesis and characterization of argyrodite solid electrolytes for all-solid-state li-ion batteries 747, 227 (2018); https://doi.org/10.1016/j.jallcom.2018.03.027.

T. Tao, Z. Zheng, Y. Gao, B. Yu, Y. Fan, Y. Chen, S. Huang, S. Lu, Energy Materials, Understanding the role of interfaces in solid-state lithium-sulfur batteries 2, 200036 (2022); https://doi.org/10.20517/energymater.2022.46.

M. Laqibi, B. Cros, S. Peytavin, M. Ribes, Solid State Ionics, New silver superionic conductors Ag7XY5Z (X = Si, Ge, Sn; Y = S, Se; Z = Cl, Br, I)-synthesis and electrical studies 23 (1-2), 21 (1987); https://doi.org/10.1016/0167-2738(87)90077-4.

R.B. Beeken, J.J. Garbe, J.M. Gillis, N.R. Petersen, B.W. Podoll, M.R. Stoneman, Journal of Physics and Chemistry of Solids, Electrical conductivities of the Ag6PS5X and the Cu6PSe5X (X=Br, I) argyrodites 66 (5), 882 (2005); https://doi.org/10.1016/j.jpcs.2004.10.010.

A.I. Pogodin, I.P. Studenyak, I.A. Shender, M.M. Pop, M.J. Filep, T.O. Malakhovska, O.P.Kokhan, P. Kopčanský, T.Y. Babuka, J Journal of Materials Science, Crystal structure, ion transport and optical properties of new high-conductivity Ag7(Si1−xGex)S5I solid solutions 57, 6706 (2022); https://doi.org/10.1007/s10853-022-07059-1.

I.P. Studenyak, A.I. Pogodin, M.J. Filep, O.I. Symkanych, T.Y. Babuka, O.P. Kokhan, P. Kúš, Journal of Alloys and Compounds, Influence of heterovalent cationic substitution on electrical properties of Ag6+x(P1−xGex)S5I solid solutions 873, 159784 (2021); https://doi.org/10.1016/j.jallcom.2021.159784.

I.O. Shender, A.I. Pogodin, M.J. Filep, T.O. Malakhovska, O.P. Kokhan, V.S. Bilanych, K.V. Skubenych, O.I. Symkanych, V.Yu. Izai, L.M. Suslikov, Semiconductor Physics, Quantum Electronics & Optoelectronics, Influence of cation Si4+↔Ge4+ and P5+↔Ge4+ substitution on the mechanical parameters of single crystals Ag7(Si1–xGex)S5I and Ag6+x(P1–xGex)S5I 26(4), 408 (2023); https://doi.org/10.15407/spqeo26.04.408.

I.O. Shender, A.I. Pogodin, M.J. Filep, T.O. Malakhovska, O.P. Kokhan, Semiconductor Physics, Quantum Electronics & Optoelectronics, Microhardness of single-crystal samples of Ag7+x(P1–xGex)S6 solid solutions . 27 (2), 169 (2024); https://doi.org/10.15407/spqeo27.02.169.

I.O. Shender, A.I. Pogodin, M.J. Filep, T.O. Malakhovska, O.P. Kokhan, L.M. Suslikov, V.S. Bilanych, R. Mariychuk, Semiconductor Physics, Quantum Electronics & Optoelectronics, The effect of heterovalent P+5-Si+4 substitution on the microhardness of Ag7+x(P1–xSix)S6 single crystals 28 (1), 26 (2024); https://doi.org/10.15407/spqeo28.01.026.

A.I. Pogodin, M.M. Pop, I.O. Shender, M.J. Filep, T.O. Malakhovska, O.P. Kokhan, K.V. Skubenych, V. Izai, Semiconductor Physics, Quantum Electronics & Optoelectronics, Ellipsometric study of Ag6+x(P1–xSix)S5I single crystals. 28 (2), 215 (2025); https://doi.org/10.15407/spqeo28.02.215.

P.P. Filho, M.R. Mitchell, R.E. Link, T.D. Cavalcante, V.H. de Albuquerque, J.M.R.C Tavares, Journal of Testing and Evaluation, Brinell and Vickers hardness measurement using image processing and analysis techniques 38(1), 102220 (2010); https://doi.org/10.1520/jte102220.

F.R. Nabarro, S. Shrivastava, S.B. Luyckx, Philosophical Magazine, The size effect in microindentation 86 (25-26), 4173 (2006); https://doi.org/10.1080/14786430600577910.

J. Benet Charles, F.D. Gnanam, Journal of Materials Science Letters, Vickers micromechanical indentation of NaSb2F7and Na3Sb4F15 single crystals 9(2), 165 (1990); https://doi.org/10.1007/bf00727704.

L.C. Allen, Journal of the American Chemical Society, Electronegativity is the average one-electron energy of the valence-shell electrons in ground-state free atoms 111(25), 9003 (1989); https://doi.org/10.1021/ja00207a003.

R.D. Shannon, Acta Crystallographica Section A, Revised effective ionic radii and sys-tematic studies of interatomic distances in halides and chalcogenides 32, 751 (1976); https://doi.org/10.1107/S0567739476001551.

W.D. Nix, H. Gao, Journal of the Mechanics and Physics of Solids, Indentation size effects in crystalline materials: A law for strain gradient plasticity 46(3), 411 (1998); https://doi.org/10.1016/S0022-5096(97)00086-0.

P. Song, K. Yabuuchi, P. Spaetig, Acta Materialia, Insights into hardening, plastically deformed zone and geometrically necessary dislocations of two ion-irradiated FeCrAl(Zr)-ODS ferritic steels: A combined experimental and simulation study 234, 117991 (2022); https://doi.org/10.1016/j.actamat.2022.117991.

H.G. Chuah, Z.M. Ripin, Journal of Materials Science, Quantifying the surface roughness effect in microindentation using a proportional specimen resistance model 48, 6293 (2013); https://doi.org/10.1007/s10853-013-7429-z.

V. Saraswati, Bulletin of Materials Science, Microhardness measurement in nonmetallic materials 9, 287 (1987); https://doi.org/10.1007/BF02743978.

P. Kathiravan, T. Balakrishnan, C. Srinath, K. Ramamurthi, S. Thamotharan, Karbala International Journal of Modern Science, Growth and characterization of α-nickel sulphate hexahydrate single crystal 2(4), 226 (2016); https://doi.org/10.1016/j.kijoms.2016.08.002.