Delafossite structured ternary nitrides, ABN 2 , have been of recent experimental investigation for applications such as tandem solar and photoelectrochemical cells. We present a thorough first principles computational investigation of their stability, electronic structure, and optical properties. Nine compounds, where A = Cu, Ag, Au and B = V, Nb, Ta, were studied. For three of these compounds, CuTaN 2 , CuNbN 2 , and AgTaN 2 , our computations agree well with experimental results. Optimized lattice parameters, formation energies, and mechanical properties have been computed using the generalized gradient approximation (GGA). Phonon density of states computed at zero-temperature shows that all compounds are dynamically unstable at low temperatures. Including finite-temperature anharmonic effects stabilizes all compounds at 300 K, with the exception of AgVN 2 . Analysis of Crystal Orbital Hamiltonian Populations (COHP) provides insight into the bonding and antibonding characters of A–N and B–N pairs. Instability at low temperatures can be attributed to strong A–N antibonding character near the Fermi energy. B–N bonding is found to be crucial in maintaining stability of the structure. AgVN 2 is the only compound to display significant B–N antibonding below the Fermi energy, as well as the strongest degree of A–N antibonding, both of which provide explanation for the sustained instability of this compound up to 900 K. Hybrid functional calculations of electronic and optical properties show that real static dielectric constants in the semiconductors are related to corresponding band gaps through the Moss relation. CuTaN 2 , CuNbN 2 , AgTaN 2 , AgNbN 2 , AgVN 2 , AuTaN 2 , and AuNbN 2 exhibit indirect electronic band gaps while CuVN 2 and AuVN 2 are metallic. Imaginary parts of the dielectric function are characterized by d–d interband transitions in the semiconductors and d–d intraband transitions in the metals. Four compounds, CuTaN 2 , CuNbN 2 , AgTaN 2 , and AgNbN 2 , are predicted to exhibit large light absorption in the range of 1.0 to 1.7 eV, therefore making these materials good candidates for solar-energy conversion applications. Two compounds, AuTaN 2 and AuNbN 2 , have band gaps and absorption onsets near the ideal range for obtaining high solar-cell conversion efficiency, suggesting that these compounds could become potential candidates as absorber materials in tandem solar cells or for band-gap engineering by alloying.
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Identification of high-dielectric constant compounds from statistical design
The discovery of high-dielectric materials is crucial to increasing the efficiency of electronic devices and batteries. Here, we report three previously unexplored materials with very high dielectric constants (69 <
- NSF-PAR ID:
- 10368772
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- npj Computational Materials
- Volume:
- 8
- Issue:
- 1
- ISSN:
- 2057-3960
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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