The one-dimensional cobaltate Ca3Co2O6 is an intriguing material having an unconventional magnetic structure, displaying quantum tunneling phenomena in its magnetization. Using a newly developed experimental method, s-core-level non-resonant inelasti
c x-ray scattering (s-NIXS), we were able to image the atomic Co 3d orbital that is responsible for the Ising magnetism in this system. We show that we can directly observe that it is the complex d2 orbital occupied by the sixth electron at the high-spin Co-trig{3+} (d6) sites that generates this behavior. This is extremely rare in the research field of transition metal compounds, and is only made possible by the delicately balanced prismatic trigonal coordination. The ability to directly relate the orbital occupation with the local crystal structure is essential to model the magnetic properties of this system.
Unknown changes in the crystalline order of regular TiO$_2$ result in the formation of black titania, which has garnered significant interest as a photocatalytic material due to the accompanying electronic changes. Herein, we determine the nature of
the lattice distortion caused by an oxygen vacancy that in turn results in the formation of mid-band gap states found in previous studies of black titania. We introduce an innovative technique using a state-of-the-art silicon drift detector, which can be used in conjunction with extended x-ray absorption fine structure (EXAFS) to measure bulk interatomic distances. We illustrate how the energy dispersive nature of such a detector can allow us an unimpeded signal, indefinitely in energy space, thereby sidestepping the hurdles of more conventional EXAFS, which is often impeded by other absorption edges.
The implementation and control of room temperature ferromagnetism (RTFM) by adding magnetic atoms to a semiconductors lattice has been one of the most important problems in solid state state physics in the last decade. Herein we report for the first
time, to our knowledge, on the mechanism that allows RTFM to be tuned by the inclusion of emph{non-magnetic} aluminum in nickel ferrite. This material, NiFe$_{2-x}$Al$_x$O$_4$ (x=0, 0.5, 1.5), has already shown much promise for magnetic semiconductor technologies, and we are able to add to its versatility technological viability with our results. The site occupancies and valencies of Fe atoms (Fe$^{3+}$ T$_d$, Fe$^{2+}$ O$_h$, and Fe$^{3+}$ O$_h$) can be methodically controlled by including aluminum. Using the fact that aluminum strongly prefers a 3+ octahedral environment, we can selectively fill iron sites with aluminum atoms, and hence specifically tune the magnetic contributions for each of the iron sites, and therefore the bulk material as well. Interestingly, the influence of the aluminum is weak on the electronic structure (supplemental material), allowing one to retain the desirable electronic properties while achieving desirable magnetic properties.
