RESUMO
CaMn1-x Nb x O3 (x = 0, 0.5, 0.6, 0.7 and 0.10) thin films have been grown by a two-step sputtering/annealing method. First, rock-salt-structured (Ca,Mn1-x ,Nb x )O thin films were deposited on 11Ì00 sapphire using reactive RF magnetron co-sputtering from elemental targets of Ca, Mn and Nb. The CaMn1-x Nb x O3 films were then obtained by thermally induced phase transformation from rock-salt-structured (Ca,Mn1-x Nb x )O to orthorhombic during post-deposition annealing at 700 °C for 3 h in oxygen flow. The X-ray diffraction patterns of pure CaMnO3 showed mixed orientation, while Nb-containing films were epitaxially grown in [101] out of-plane-direction. Scanning transmission electron microscopy showed a Ruddlesden-Popper (R-P) secondary phase in the films, which results in reduction of the electrical and thermal conductivity of CaMn1-x Nb x O3. The electrical resistivity and Seebeck coefficient of the pure CaMnO3 film were measured to 2.7 Ω cm and -270 µV K-1 at room temperature, respectively. The electrical resistivity and Seebeck coefficient were reduced by alloying with Nb and was measured to 0.09 Ω cm and -145 µV K-1 for x = 0.05. Yielding a power factor of 21.5 µW K-2 m-1 near room temperature, nearly eight times higher than for pure CaMnO3 (2.8 µW K-2 m-1). The power factors for alloyed samples are low compared to other studies on phase-pure material. This is due to high electrical resistivity originating from the secondary R-P phase. The thermal conductivity of the CaMn1-x Nb x O3 films is low for all samples and is the lowest for x = 0.07 and 0.10, determined to 1.6 W m-1 K-1. The low thermal conductivity is attributed to grain boundary scattering and the secondary R-P phase.
RESUMO
Recent theoretical investigations [A. B. Belonoshko et al. Nat. Geosci. 10, 312 (2017)1752-089410.1038/ngeo2892] revealed the occurrence of the concerted migration of several atoms in bcc Fe at inner-core temperatures and pressures. Here, we combine first-principles and semiempirical atomistic simulations to show that a diffusion mechanism analogous to the one predicted for bcc iron at extreme conditions is also operative and of relevance for the high-temperature bcc phase of pure Ti at ambient pressure. The mechanism entails a rapid collective movement of numerous (from two to dozens) neighbors along tangled closed-loop paths in defect-free crystal regions. We argue that this phenomenon closely resembles the diffusion behavior of superionics and liquid metals. Furthermore, we suggest that concerted migration is the atomistic manifestation of vanishingly small ω-mode phonon frequencies previously detected via neutron scattering and the mechanism underlying anomalously large and markedly non-Arrhenius self-diffusivities characteristic of bcc Ti.
