Pressure-Stabilized Semiconducting Electrides in Alkaline-Earth-Metal Subnitrides.

High pressure is able to modify profoundly the chemical bonding and generate new phase structures of materials with chemical and physical properties not accessible at ambient conditions. We here report an unprecedented phenomenon on the pressure-induced formation of semiconducting electrides via com...

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Publicado en:Journal of the American Chemical Society Vol. 139; no. 39; pp. 13798 - 13804
Autores principales: Yunwei Zhang, Weikang Wu, Yanchao Wang, Yang, Shengyuan A., Yanming Ma
Formato: Artículo
Publicado: American Chemical Society 10/4/2017
Materias:
Acceso en línea:Ver este registro en EBSCOhost
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      dt: 10/4/2017
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      pub: American Chemical Society
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        10.1021/jacs.7b07016
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        atl: Pressure-Stabilized Semiconducting Electrides in Alkaline-Earth-Metal Subnitrides.
      aug:
        au:
          Yunwei Zhang
          Weikang Wu
          Yanchao Wang
          Yang, Shengyuan A.
          Yanming Ma
        affil:
          State Key Lab of Superhard Materials, College of Physics, Jilin University, Changchun 130012, China
          Beijing Computational Science Research Center, Beijing 100084, China
          Research Laboratory for Quantum Materials, Singapore University of Technology and Design, Singapore 487372, Singapore
          International Center of Future Science, Jilin University, Changchun 130012, China
      su:
        High pressure chemistry
        Chemical bonds
        Semiconductor nanoparticles
        X-ray diffraction
      sug:
        subj:
          High pressure chemistry
          Chemical bonds
          Semiconductor nanoparticles
          X-ray diffraction
      ab: High pressure is able to modify profoundly the chemical bonding and generate new phase structures of materials with chemical and physical properties not accessible at ambient conditions. We here report an unprecedented phenomenon on the pressure-induced formation of semiconducting electrides via compression of layered alkaline-earth subnitrides CaN, SrN, and Ba2N that are conducting electrides with loosely confined electrons in the interlayer voids at ambient pressure. Our extensive first-principles swarm structure searches identified the high-pressure semiconducting electride phases of a tetragonal ... structure for CaN and a monoclinic Cc structure shared by SrN and BaN, both of which contain atomic-size cavities with paring electrons distributed within. These electride structures are validated by the excellent agreement between the simulated X-ray diffraction patterns and the experimental data available. We attribute the emergence of the semiconducting electride phases to the p-d hybridization on alkaline-earth-metal atoms under compression as well as the filling of the p-d hybridized band due to the interaction between Ca and N. Our work provides a unique example of pressure-induced metal-to-semiconductor transition in compound materials and reveals unambiguously the electron-confinement topology change between different types of electrides.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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