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  Theoretical and experimental study of metastable solid solutions and phase stability within the immiscible Ag–Mo binary system

Sarakinos, K., Greczynski, G., Elofsson, V., Magnfält, D., Högberg, H., & Alling, B. (2016). Theoretical and experimental study of metastable solid solutions and phase stability within the immiscible Ag–Mo binary system. Journal of Applied Physics, 119(9): 095303. doi:10.1063/1.4942840.

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Sarakinos, Kostas1, Author           
Greczynski, Grzegorz2, Author           
Elofsson, Viktor1, Author           
Magnfält, D.1, Author           
Högberg, Hans3, Author           
Alling, Björn4, 5, Author           
Affiliations:
1Nanoscale Engineering Division, Department of Physics, Chemistry, and Biology (IFM), Linköping University, Linköping, Sweden, persistent22              
2Thin Film Physics Division, Department of Physics (IFM), Linköping University, SE-581 83 Linköping, Sweden, ou_persistent22              
3Thin Film Physics Division, Department of Physics, Chemistry, and Biology (IFM), Linköping University, Linköping, Sweden, persistent22              
4Adaptive Structural Materials (Simulation), Computational Materials Design, Max-Planck-Institut für Eisenforschung GmbH, Max Planck Society, ou_1863339              
5Department of Physics, Chemistry and Biology (IFM), Thin Film Physics Division, Linköping University, Linköping, Sweden, ou_persistent22              

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Free keywords: Bins; Carbides; Ceramic materials; Chemical bonds; Chemical stability; Crystal structure; Density functional theory; Dissolution; Electronic properties; Lattice theory; Magnetrons; Metastable phases; Molybdenum; Nitrides; Phase stability; Phase transitions; Silver alloys; Solid solutions; Stability; Structure (composition); System stability; Thin films; Transition metal alloys; Transition metals, Chemical interactions; Composition ranges; Effect of chemicals; Energy differences; Magnetron co-sputtering; Metastable solid solution; Thermodynamic equilibria; Thin film systems, Silver
 Abstract: Metastable solid solutions are phases that are synthesized far from thermodynamic equilibrium and offer a versatile route to design materials with tailor-made functionalities. One of the most investigated classes of metastable solid solutions with widespread technological implications is vapor deposited ternary transition metal ceramic thin films (i.e., nitrides, carbides, and borides). The vapor-based synthesis of these ceramic phases involves complex and difficult to control chemical interactions of the vapor species with the growing film surface, which often makes the fundamental understanding of the composition-properties relations a challenging task. Hence, in the present study, we investigate the phase stability within an immiscible binary thin film system that offers a simpler synthesis chemistry, i.e., the Ag-Mo system. We employ magnetron co-sputtering to grow Ag1-xMox thin films over the entire composition range along with x-ray probes to investigate the films structure and bonding properties. Concurrently, we use density functional theory calculations to predict phase stability and determine the effect of chemical composition on the lattice volume and the electronic properties of Ag-Mo solid solutions. Our combined theoretical and experimental data show that Mo-rich films (x ≥ ∼0.54) form bcc Mo-Ag metastable solid solutions. Furthermore, for Ag-rich compositions (x ≤ ∼0.21), our data can be interpreted as Mo not being dissolved in the Ag fcc lattice. All in all, our data show an asymmetry with regards to the mutual solubility of Ag and Mo in the two crystal structures, i.e., Ag has a larger propensity for dissolving in the bcc-Mo lattice as compared to Mo in the fcc-Ag lattice. We explain these findings in light of isostructural short-range clustering that induces energy difference between the two (fcc and bcc) metastable phases. We also suggest that the phase stability can be explained by the larger atomic mobility of Ag atoms as compared to that of Mo. The mechanisms suggested herein may be of relevance for explaining phase stability data in a number of metastable alloys, such as ternary transition metal-aluminum-nitride systems. © 2016 AIP Publishing LLC.

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Language(s): eng - English
 Dates: 2016-03-07
 Publication Status: Issued
 Pages: -
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1063/1.4942840
BibTex Citekey: Sarakinos2016
 Degree: -

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Title: Journal of Applied Physics
  Abbreviation : J. Appl. Phys.
Source Genre: Journal
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Publ. Info: New York, NY : AIP Publishing
Pages: - Volume / Issue: 119 (9) Sequence Number: 095303 Start / End Page: - Identifier: ISSN: 0021-8979
CoNE: https://pure.mpg.de/cone/journals/resource/991042723401880