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Register a new userMonatomic Co, CoO$_2$, and CoO$_3$ Nanowires on Ir(100) and Pt(100) surfaces: Formation, Structure, and Energetics
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In this study we investigate the structural and chemical changes of monatomic CoO$_2$ chains grown self-organized on the Ir(100) surface [P. Ferstl et al., PRL 117, 2016, 046101] and on Pt(100) under reducing and oxidizing conditions. By a combination of quantitative low-energy electron diffraction, scanning tunnelling microscopy, and density functional theory we show that the cobalt oxide wires are completely reduced by H$_2$ at temperatures above 320 K and a 3x1 ordered Ir$_2$Co or Pt$_2$Co surface alloy is formed. Depending on temperature the surface alloy on Ir(100) is either hydrogen covered (T < 400 K) or clean and eventually undergoes an irreversible order-disorder transition at about 570 K. The Pt$_2$Co surface alloy disorders with the desorption of hydrogen, whereby Co submerges into subsurface sites. Vice versa, applying stronger oxidants than O$_2$ such as NO$_2$ leads to the formation of CoO3 chains on Ir(100) in a 3x1 superstructure. On Pt(100) such a CoO$_3$ phase could not be prepared so far, which however, is due to the UHV conditions of our experiments. As revealed by theory this phase will become stable in a regime of higher pressure. In general, the structures can be reversibly switched on both surfaces using the respective agents O$_2$, NO$_2$ and H$_2$.
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We have investigated the magnetic ordering in the ultrathin c(10$times$2) CoO(111) film supported on Ir(100) on the basis of ab-initio calculations. We find a close relationship between the local structural properties of the oxide film and the induced magnetic order, leading to alternating ferromagnetically and anti-ferromagnetically ordered segments. While the local magnetic order is directly related to the geometric position of the Co atoms, the mismatch between the CoO film and the Ir substrate leads to a complex long-range order of the oxide.
[Ca$_2$CoO$_3$]$_{0.62}$[CoO$_2$], a two dimensional misfit metallic compound, is famous for its rich phases accessed by temperature, $i.e.$ high temperature spin-state transition, metal-insulator transition (MIT) at intermediate temperature ($sim$ 100 K) and low temperature spin density wave (SDW). It enters into SDW phase below T$_{MIT}$ which becomes long range at 27 K. Information on the independent role of misfit layers (rocksalt/Ca$_2$CoO$_3$ & triangular/CoO$_2$) in these phases is scarce. By combining a set of complementary macroscopic (DC magnetization and resistivity) and microscopic (neutron diffraction and X-ray absorption fine structure spectroscopy) measurements on pure (CCO) and Tb substituted in the rocksalt layer of CCO (CCO1), magnetic correlations in both subsystems of this misfit compound are unraveled. CCO is found to exhibit glassiness, as well as exchange bias (EB) effects, while CCO1 does not exhibit glassiness, albeit it shows weaker EB effect. By combining local structure investigations from extended X-ray absorption fine structure (EXAFS) spectroscopy and neutron diffraction results on CCO, we confirm that the SDW arises in the CoO$_2$ layer. Our results show that the magnetocrystalline anisotropy associated with the rocksalt layer acts as a source of pinning, which is responsible for EB effect. Ferromagnetic clusters in the Ca$_2$CoO$_3$ affects SDW in CoO$_2$ and ultimately glassiness arises.
The structure and dynamics of atomic oxygen adsorbed on Ag(410) and Ag(210) surfaces have been investigated using density functional theory. Our results show that the adsorption configuration in which O adatoms decorate the upper side of the (110) steps forming O--Ag--O rows is particularly stable for both surfaces. On Ag(210), this arrangement is more stable than other configurations at all the investigated coverages. On Ag(410), adsorption on the terrace and at the step edge are almost degenerate, the former being slightly preferred at low coverage while the latter is stabilized by increasing the coverage. These findings are substantiated by a comparison between the vibrational modes, calculated within density-functional perturbation theory, and the HREEL spectrum which has been recently measured in these systems.
The electric, magnetic, and thermal properties of three perovskite cobaltites with the same 30% hole doping and ferromagnetic ground state were investigated down to very low temperatures. With decreasing size of large cations, the ferromagnetic Curie temperature and spontaneous moments of cobalt are gradually suppressed - $T_C=130$ K, 55 K and 25 K and $m = 0.68 mu_B$, 0.34 $mu_B$ and 0.23 $mu_B$ for Nd$_{0.7}$Sr$_{0.3}$CoO$_3$, Pr$_{0.7}$Ca$_{0.3}$CoO$_3$ and Nd$_{0.7}$Ca$_{0.3}$CoO$_3$, respectively. The moment reduction with respect to moment of the conventional ferromagnet La$_{0.7}$Sr$_{0.3}$CoO$_3$ ($T_C=230$ K, $m = 1.71 mu_B$) in so-called IS/LS state for Co$^{3+}$/Co$^{4+}$, was originally interpreted using phase-separation scenario. Based on the present results, mainly the analysis of Schottky peak originating in Zeeman splitting of the ground state Kramers doublet of Nd$^{3+}$, we find, however, that ferromagnetic phase in Nd$_{0.7}$Ca$_{0.3}$CoO$_3$ and likely also Pr$_{0.7}$Ca$_{0.3}$CoO$_3$ is uniformly distributed over all sample volume, despite the severe drop of moments. The ground state of these compounds is identified with the LS/LS-related phase derived theoretically by Sboychakov textit{et al.} [Phys. Rev. B textbf{80}, 024423 (2009)]. The ground state of Nd$_{0.7}$Sr$_{0.3}$CoO$_3$ with an intermediate cobalt moment is inhomogeneous due to competing of LS/LS and IS/LS phases. In the theoretical part of the study, the crystal field split levels for $4f^3$ (Nd$^{3+}$), $4f^2$ (Pr$^{3+}$) and $4f^1$ (Ce$^{3+}$ or Pr$^{4+}$) are calculated and their magnetic characteristics are presented.
The structure and strain of ultrathin CoO films grown on a Pt(001) substrate and on a ferromagnetic PtFe pseudomorphic layer on Pt(001) have been determined with insitu and real time surface x-ray diffraction. The films grow epitaxially on both surfaces with an in-plane hexagonal pattern that yields a pseudo-cubic CoO(111) surface. A refined x-ray diffraction analysis reveals a slight monoclinic distortion at RT induced by the anisotropic stress at the interface. The tetragonal contribution to the distortion results in a ratio c/a > 1, opposite to that found in the low temperature bulk CoO phase. This distortion leads to a stable Co2+ spin configuration within the plane of the film.
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