Doping-Induced Spectral Shifts in Two Dimensional Metal Oxides

Doping of strongly layered ionic oxides is an established paradigm for creating novel electronic behavior. This is nowhere more apparent than in superconductivity, where doping gives rise to high temperature superconductivity in cuprates (hole-doped) and to surprisingly high Tc in HfNCl (Tc=25.5K, electron-doped). First principles calculations of hole-doping of the layered delafossite CuAlO2 reveal unexpectedly large doping-induced shifts in spectral density, strongly in opposition to the rigid band picture that is widely used as an accepted guideline. These spectral shifts, of similar origin as the charge transfer used to produce negative electron affinity surfaces and adjust Schottky barrier heights, drastically alter the character of the Fermi level carriers, leading in this material to an O-Cu-O molecule-based carrier (or polaron, at low doping) rather than a nearly pure-Cu hole as in a rigid band picture. First principles linear response electron-phonon coupling (EPC) calculations reveal, as a consequence, net weak EPC and no superconductivity rather than the high Tc obtained previously using rigid band expectations. These specifically two-dimensional dipole-layer driven spectral shifts provides new insights into materials design in layered materials foe functionalities besides superconductivity.Comment: 6 pages, 8 figures,1 tabl

Charge and Spin Ordering in Insulating Na0.5_{0.5}CoO2_2: Effects of Correlation and Symmetry

Ab initio band theory including correlations due to intra-atomic repulsion is applied to study charge disproportionation and charge- and spin-ordering in insulating Na$_{0.5}$CoO$_2$. Various ordering patterns (zigzag and two striped) for four-Co supercells are analyzed before focusing on the observed "out-of-phase stripe" pattern of antiferromagnetic Co$^{4+}$ spins along charge-ordered stripes. This pattern relieves frustration and shows distinct analogies with the cuprate layers: a bipartite lattice of antialigned spins, with axes at 90 degree angles. Substantial distinctions with cuprates are also discussed, including the tiny gap of a new variant of "charge transfer" type within the Co 3d system.Comment: 5 pages, 3 figure

Compensated Half-metallicity in the Trigonally Distorted Perovskite-type NiCrO3_3

Using first principles calculations, we investigate the electronic and magnetic properties of the trigonally distorted (R-3c) perovskite-derived NiCrO$_3$. Within the local spin density approximation (LSDA), our calculations show that this system is an exactly compensated half-metal (CHM). The local spin moments of Cr 2.04, and antialigned Ni -1.41 and three oxygens -0.63 (in the units of $\mu_B$), indicate high spin S=3/2 Cr$^{3+}$ and S=3/2 (NiO$_3$)$^{3-}$ units. Considering reasonable values of the on-site Coulomb repulsion U on both Ni and Cr ions with LDA+U approach, this system becomes an insulator (as reported by Chamberland and Cloud) having a narrow gap in the spin-up channel, whereas the other channel has a large gap of ~3 eV. Although inclusion of U seemingly leads to the transition Ni$^{2+} --> high spin S=3/2 Ni$^{3+}$, consistent with the experimentally observed effective moment, the zero net moment remains unchanged due to either reduction of oxygen local moments or enhancement of Cr local moment. Compression of volume by 10to CHM even when correlation effects are included.These results suggest the possibility of a CHM state in NiCrO$_3$ and provide another route to search for CHM, which is a property sought by many.Comment: 5 pages, 5 embedded figures, (To be published in PRB rapid Commun.

Half Semimetallic Antiferromagnetism in the Sr2_2CrTO6_6 System, T=Os, Ru

Double perovskite Sr$_2$CrOsO$_6$ is (or is very close to) a realization of a spin-asymmetric semimetallic compensated ferrimagnet, according to first principles calculations. This type of near-half metallic antiferromagnet is an unusual occurrence, and more so in this compound because the zero gap is accidental rather than being symmetry determined. The large spin-orbit coupling (SOC) of osmium upsets the spin balance (no net spin moment without SOC): it reduces the Os spin moment by 0.27 $\mu_B$ and induces an Os orbital moment of 0.17 $\mu_B$ in the opposite direction. The effects combine (with small oxygen contributions) to give a net total moment of 0.54 $\mu_B$ per cell in \scoo, reflecting a large impact of SOC in this compound. This value is in moderately good agreement with the measured saturation moment of 0.75 $\mu_B$. The value of the net moment on the Os ion obtained from neutron diffraction (0.73 $\mu_B$ at low temperature) differs from the calculated value (1.14 $\mu_B$). Rather surprisingly, in isovalent Sr$_2$CrRuO$_6$ the smaller SOC-induced spin changes and orbital moments (mostly on Ru) almost exactly cancel. This makes Sr$_2$CrRuO$_6$ a "half (semi)metallic antiferromagnet" (practically vanishing net total moment) even when SOC is included, with the metallic channel being a small-band-overlap semimetal. Fixed spin moment (FSM) calculations are presented for each compound, illustrating how they provide different information than in the case of a nonmagnetic material. These FSM results indicate that the Cr moment is an order of magnitude stiffer against longitudinal fluctuations than is the Os moment.Comment: 6 page