Phase subsolidus separation of the Ge–P–Sn ternary system
Abstract
2D materials are becoming increasingly attractive for use in modern electronic devices due to new properties that can arise from reduced dimensionality and the quantum confinement of charge carriers. Many studies are aimed at the search for materials characterized by a layered structure, which allows obtaining chemically stable atomic layers without surface broken bonds. Binary compounds of elements of IV (Si, Ge, Sn) and V (P, As) groups form layered structures in which two-dimensional layers with covalent bonds are bound by weak van der Waals forces, and from this point of view they can be considered as being promising 2D materials. However, it should be noted, that obtaining crystals of compounds of this class is associated with significant difficulties due to the high vapor pressure of phosphorus. Attempts have been made to obtain the GeP samples from tin melt solutions, which can significantly soften the synthesis conditions. The study of phase equilibria and the construction of a phase diagram of the Ge–P–Sn ternary system would allow approaching the production of both bulk and two-dimensional samples of germanium phosphide, as well as determining the possibility of alloying them with tin.
In this study, based on the investigation of several alloys of the Ge–P–Sn ternary system using the X-ray phase analysis, it was established that the phase subsolidus separation of the state diagram is carried out by the Sn4P3–Ge, Sn4P3–GeP, Sn3P4–GeP and SnP3–GeP sections. The composition of the alloys corresponded to the figurative points of the intersecting sections. A scheme of phase equilibria in the Ge–P–Sn system was proposed. This scheme assumes the existence of a nonvariant peritectic equilibrium L+Ge ↔ Sn4P3+GeP and eutectic processes L ↔ Ge+Sn+Sn4P3 and L ↔ Sn4P3+GeP+SnP3.
The study of alloys using the differential thermal analysis method allowed determining the temperatures of these processes, equal to 795 K, 504 K, and 790 K, respectively. The T-x diagram of the Sn–GeP polythermal cross section, which experimentally confirms the proposed scheme, was constructed
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References
Goncharov E. G. Semiconductor phosphides and arsenides of silicon and germanium*. Voronezh: VSU Publ.; 1989. 208 p. (In Russ.)
Semenova G. V., Goncharov E. G. Solid solutions with the participation of elements of the fifth group*. Moscow: MFTI Publ.; 2000. 160 p. (In Russ.). Available at: https://www.elibrary.ru/item.asp?id=25882424
Khan K., Tareen A. K., Khan Q. U., Iqbal M., Zhang H. and Guo Z. Novel synthesis, properties and applications of emerging group VA two-dimensional monoelemental materials (2D-Xenes). Materials Chemistry Frontiers. 2021;5: 6333-6391. https://doi.org/10.1039/D1QM00629K
Yu X., Liang W., Xing Ch., … Zhang H. Emerging 2D pnictogens for catalytic applications: status and challenges. Journal of Materials Chemistry A. 2020;8: 12887–12927. https://doi.org/10.1039/D0TA04068A
Tao W., Kong N., Ji X., … Kim J. S. Emerging two-dimensional monoelemental materials (Xenes) for biomedical applications. Chemical Society Reviews. 2019;48: 2891-2912. https://doi.org/10.1039/C8CS00823J
Carrasco J. A., Congost-Escoin P., Assebban M., Abellán G. Antimonene: a tuneable post-graphene material for advanced applications in optoelectronics, catalysis, energy and biomedicine. Chemical Society Reviews. 2023;52: 1288–1330. https://doi.org/10.1039/D2CS00570K
Pang J., Bachmatiuk A., Yin Y., … Rümmeli M. H. Applications of phosphorene and black phosphorus in energy conversion and storage devices. Advanced Energy Materials. 2018;8(8): 1702093. https://doi.org/10.1002/aenm.201702093
Niu T. New properties with old materials: layered black phosphorous. Nano Today. 2017;12: 7–9. https://doi.org/10.1016/j.nantod.2016.08.013
Goswami A., Gawande M. B. Phosphorene: current status, challenges and opportunities. Frontiers of Chemical Science and Engineering. 2019;13(2): 296–309. https://doi.org/10.1007/s11705-018-1783-y
Lee K., Synnestvedt S., Bellard M., Kovnir K. GeP and (Ge1-xSnx)(P1-yGey) (x~0.12, y~0.05): synthesis, structure, and properties of two-dimensional layered tetrel phosphides. Journal of Solid State Chemistry. 2015;224: 62–70. https://doi.org/10.1016/j.jssc.2014.04.021
Barreteau C., Michon B., Besnard C., Giannini E. High-pressure melt growth and transport properties of SiP, SiAs, GeP, and GeAs 2D layered semiconductors. Journal of Crystal Growth. 2016;443(1): 75–80. https://doi.org/10.1016/j.jcrysgro.2016.03.019
Cheng A-Q., He Z., Zhao J., Zeng H., Chen R-Sh. Monolayered silicon and germanium monopnictide semiconductors: excellent stability, high absorbance, and strain engineering of electronic properties. ACS Applied Materials & Interfaces. 2018;10(6): 5133–5139. https://doi.org/10.1021/acsami.7b17560
Zhou L., Guo Y., Zhao J. GeAs and SiAs monolayers: novel 2D semiconductors with suitable band structures. Physica E: Low-dimensional Systems and Nanostructures. 2018;95: 149–153. https://doi.org/10.1016/j.physe.2017. 08.016
Ramzan M. S., Bacic V., Jing Y., Kuc A. Electronic properties of a new family of layered materials from groups 14 and 15: first-principles simulations. The Journal of Physical Chemistry C. 2019;123(41): 25470–25476. https://doi.org/10.1021/acs.jpcc.9b07068
Olesinski R. W., Abbaschian G. J. The Ge−Sn (Germanium−Tin) system. Bulletin of Alloy Phase Diagrams. 1984;5(3): 265–271. https://doi.org/10.1007/bf02868550
Ugai Ya. A., Sokolov L. I., Goncharov E. G., Pshestanchik V. R. P-T-x diagram of the state of the Ge-P system and the thermodynamics of the interaction of the components. Russian Journal of Inorganic Chemistry. 1978;23(7): 1907–1911. (In Russ.). Available at: https://www.elibrary.ru/item.asp?id=29096578
Olofsson O. X-ray investigation of the tin-phosphorus system. Acta Chemica Scandinavica. 1970;24: 1153 -1162. https://doi.org/10.3891/acta.chem.scand.24-1153
Donohue P. C. The synthesis, structure and superconducting properties of new high-pressure forms of tin phosphide. Inorganic Chemistry. 1970;9(2): 335–348. https://doi.org/10.1021/ic50084a032
Katz G., Kohn Y. A., Broder Y. D. Crystallographic data for tin monophosphide. Acta Crystallographica. 1957;9: 607–609. https://doi.org/10.1107/s0365110x57002170
Vivian A. C. The tin-arsenic system. Journal of the Institute of Metals. 1920;23: 325–336.
Gullman J. The crystal structure of SnP. Journal of Solid State Chemistry. 1990;87: 202–207. https://doi.org/10.1016/0022-4596(90)90083-a
Sushkova T. P., Kononova E. U., Savinova Y. A., Dorokhina E. S., Semenova G. V. Intermediate phases in Sn-P system. Condensed Matter and Interphases. 2014;16(2): 210–214. Available at: https://www.elibrary.ru/item.asp?edn=sitfep
Ritcher A. Pressure dependence of the tin-phosphorus phase diagram. Monatshefte für Chemie – Chemical Monthly. 2012;143(12): 1593–1602. https://doi.org/10.1007/s00706-012-0861-y
Proskurina E. Yu., Semenova G. V., Zavrazhnov A. Yu., Kosyakov A. V. P-T-x diagram of Sn - P system. Condensed Matter and Interphases. 2015;17(4): 498–509. (In Russ., abstract in Eng.). Available at: https://www.elibrary.ru/item.asp?id=25946590
Zavrazhnov A. Yu., Semenova G. V., Proskurina E. Yu., Sushkova T. P. Phase diagram of the Sn - P system. Journal of Thermal Analysis and Calorimetry. 2018;134(1): 475–481. https://doi.org/10.1007/s10973-018-7123-0
Semenova G. V., Leont’eva T. A., Sushkova T. P. Analysis of phase equilibria in the Ge–P–Sn ternary system. Condensed Matter and Interphases. 2019;21(2): 249–261. (In Russ., abstract in Eng.). https://doi.org/10.17308/kcmf.2019.21/763
Khaldoyanidi K. A. Phase diagrams of heterogeneous systems with transformations*. F. А. Kuznetsov (ed.). Novosibirsk: INKh RAN Publ.; 2004. 382 с. (In Russ.)
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