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Most cubic semiconductors have threefold degenerate p-bonding valence bands and nondegenerate s-antibonding conduction bands. This allows strong interband transitions from the valence to the conduction bands. On the other hand, intervalence band transitions within p-bonding orbitals in conventional p-type semiconductors are forbidden at k=0 and, therefore, weak, but observable. In gapless semiconductors, however, the s-antibonding band moves down between the split-off hole band and the valence band maximum due to the Darwin shift. This band arrangement makes them three-dimensional topological insulators. It also allows strong interband transitions from the s-antibonding valence band to the p-bonding bands, which have been observed in α-tin with Fourier-transform infrared spectroscopic ellipsometry [Carrasco et al., Appl. Phys. Lett. 113, 232104 (2018)]. This manuscript presents a theoretical description of such transitions applicable to many gapless semiconductors. This model is based on k→⋅p→ theory, degenerate carrier statistics, the excitonic Sommerfeld enhancement, and screening of the transitions by many-body effects. The impact of nonparabolic bands is approximated within Kane’s 8×8k→⋅p→-model by adjustments of the effective masses. This achieves agreement with experiments.
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Dynamical stabilization in delafossite nitrides for solar energy conversion
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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- Award ID(s):
- 1629230
- PAR ID:
- 10089431
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 6
- Issue:
- 42
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 20852 to 20860
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c8ta07536k
