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Microstructural evolution and thermal stability of HfN/ScN, ZrN/ScN, and Hf0.5Zr0.5N/ScN metal/semiconductor superlattices

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Abstract

Nitride-based metal/semiconductor superlattices for possible applications as thermoelectric, plasmonic, and hard coating materials have been grown by magnetron sputtering. Since long-time thermal stability of the superlattices is crucial for these applications, the atomic scale microstructure and its evolution under annealing to working temperatures were investigated with high-resolution transmission electron microscopy methods. We report on epitaxial growth of three cubic superlattice systems (HfN/ScN, ZrN/ScN, and Hf0.5Zr0.5N/ScN) that show long-time thermal stability (annealing up to 120 h at 950 °C) as monitored by scanning transmission electron microscopy-based energy-dispersive X-ray spectroscopy. No interdiffusion between the metal and semiconductor layers could be observed for any of the present systems under long-time annealing, which is in contrast to earlier attempts on similar superlattice structures based on TiN as the metallic compound. Atomically resolved high-resolution transmission electron microscopy imaging revealed that even though the superlattice curves towards the substrate at regular interval column boundaries originating from threading dislocations close to the substrate interface, the cubic lattice continues coherently across the boundaries. It is found that the boundaries themselves are alloyed along the entire growth direction, while in their vicinity nanometer-size inclusions of metallic phases are observed that could be identified as the zinc blende phase of same stoichiometry as the parent rock salt transition metal nitride phase. Our results demonstrate the long-time thermal stability of metal/semiconductor superlattices based on Zr and Hf nitrides.

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Acknowledgements

The Knut and Alice Wallenberg (KAW) Foundation is acknowledged for the Electron Microscope Laboratory in Linköping. M.G., L.H., J.L.S., and J.B. acknowledge the financial support from the Swedish Research Council [RÅC Frame Program (2011-6505), Project Grant 2013-4018, and Linnaeus Grant (LiLi-NFM)] as well as the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU 2009-00971). B.S. and T.D.S. acknowledge the financial support from the National Science Foundation and the U.S. Department of Energy (Award No. CBET-1048616).

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The manuscript was written through contributions of all authors. All authors have provided approval to the final version of the manuscript.

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Authors and Affiliations

  1. Thin Film Physics Division, Department of Physics, Chemistry and Biology, Linköping University, 581 83, Linköping, Sweden

    Magnus Garbrecht, Jeremy L. Schroeder, Lars Hultman & Jens Birch

  2. Department of Materials Science and Engineering, University of California, Berkeley, CA, 94720, USA

    Bivas Saha

  3. Bradley Department of Electrical and Computer Engineering, Virginia Tech, Blacksburg, VA, 24061, USA

    Timothy D. Sands

  4. Department of Materials Science and Engineering, Virginia Tech, Blacksburg, VA, 24061, USA

    Timothy D. Sands

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  1. Magnus Garbrecht
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  2. Jeremy L. Schroeder
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  3. Lars Hultman
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  4. Jens Birch
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  5. Bivas Saha
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  6. Timothy D. Sands
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Correspondence to Magnus Garbrecht.

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Garbrecht, M., Schroeder, J.L., Hultman, L. et al. Microstructural evolution and thermal stability of HfN/ScN, ZrN/ScN, and Hf0.5Zr0.5N/ScN metal/semiconductor superlattices. J Mater Sci 51, 8250–8258 (2016). https://doi.org/10.1007/s10853-016-0102-6

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  • DOI: https://doi.org/10.1007/s10853-016-0102-6

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