The High Throughput Experimentation (HTE) project of the Joint Center for Artificial Photosynthesis (JCAP, http://solarfuelshub.org/) performs accelerated discovery of new earth-abundant photoabsorbers and electrocatalysts. Through collaboration within the DOE solar fuels hub and with the broader research community, the new materials will be utilized in devices that efficiently convert solar energy, water and carbon dioxide into transportation fuels. JCAP-HTE builds high-throughput pipelines for the synthesis, screening and characterization of photoelectrochemical materials. In addition to a summary of these pipelines, we will describe several new screening instruments for high throughput (photo-)electrochemical measurements. These instruments are not only optimized for screening against solar fuels requirements, but also provide new tools for the broader combinatorial materials science community. We will also describe the high throughput discovery, follow-on verification, and device implementation of a new quaternary metal oxide catalyst. This rapid technology development from discovery to device implementation is a hallmark of the multi-faceted JCAP research effort.

Considerable research and development efforts are being devoted to the efficient generation of solar fuels. A solar fuels device couples a solar photoabsorber with catalysts to convert solar energy to chemical energy via reactions such as oxygen evolution (water splitting). Widespread deployment of this technology hinges upon discovery of new materials through efforts such as the high throughput screening of oxygen evolution catalysts, as discussed in this manuscript. We derive an expression for the efficiency of the oxygen evolution catalyst that combines catalytic and optical properties. Using this hybrid efficiency, we screen 5456 samples in a (Fe-Co-Ni-Ti)O x pseudo-quaternary catalyst library using automated, high throughput electrochemistry and optical experiments. The observed compositional trends in this catalyst efficiency lead to the discovery of a new high performance composition region.

M. Tsukahara, S. Mitrovic, V. Gajdosik, G. Margaritondo, L. Pournin, M. Ramaioli, D. Sage, Y.Hwu, M. Unser, and Th. M. Liebling Mathematics Institute, École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland Institut de Physique de la Matiere Complexe, École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland Biomedical Imaging Group, École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland Institute of Physics, Academia Sinica, Nankang, Taipei 115, Taiwan (Dated: April 21, 2008)

We describe an approach for exploring microscopic properties of granular media that couples x-ray microtomography and distinct-element-method (DEM) simulations through image analysis. We illustrate it via the study of the intriguing phenomenon of instant arching in an hourglass (in our case a cylinder filled with a polydisperse mixture of glass beads that has a small circular shutter in the bottom). X-ray tomography provides three-dimensional snapshots of the microscopic conditions of the system both prior to opening the shutter, and thereafter, once jamming is completed. The process time in between is bridged using DEM simulation, which settles to positions in remarkably good agreement with the x-ray images. Specifically designed image analysis procedures accurately extract the geometrical information, i.e., the positions and sizes of the beads, from the raw x-ray tomographs, and compress the data representation from initially 5 gigabytes to a few tens of kilobytes per tomograph. The scope of the approach is explored through a sensitivity analysis to input data perturbations in both bead sizes and positions. We establish that accuracy of size--much more than position--estimates is critical, thus explaining the difficulty in considering a mixture of beads of different sizes. We further point to limits in the replication ability of granular flows away from equilibrium; i.e., the difficulty of numerically reproducing chaotic motion.

The correlated 3d sulphide BaVS_3 is a most interesting compound because of the apparent coexistence of one-dimensional and three-dimensional properties. Our experiments explain this puzzle and shed new light on its electronic structure. High-resolution angle-resolved photoemission measurements in a 4eV wide range below the Fermi level explored the coexistence of weakly correlated a_1g wide-band and strongly correlated e_g narrow-band d-electrons that is responsible for the complicated behavior of this material. The most relevant result is the evidence for a_1g--e_g inter-band nesting condition.

BaVS3 is a moderately correlated d-electron system with a rich phase diagram. To construct the corresponding minimal electronic model, one has to decide which d-states are occupied, and to which extent. The ARPES experiment presented here shows that the behavior of BaVS3 is governed by the coexistence of wide-band (A_1g) and narrow-band (twofold degenerate E) d-electrons. We sketch a lattice fermion model which may serve as a minimal model of BaVS3. This serves foremost for the understanding of the metal-insulator in pure BaVS3 and its absence in some related compounds. The nature of the low temperature magnetic order differs for several systems which may be described in terms of the same electron model. We describe several recent experiments which give information about magnetic order at high pressures. In particular, we discuss field-induced insulator-to-metal transition at slightly subcritical pressures, and an evidence for magnetic order in the high-pressure metallic phase. The phase diagram of Sr-doped BaVS3 is also discussed. The complexity of the phases of BaVS3 arises from the fact that it is simultaneously unstable against several kinds of instabilities.

The electronic band structure probed by angle-resolved photoemission spectroscopy on thin epitaxial La2-xSrxCuO4 films under extreme tensile strain shows anomalous features compatible with c-axis dispersion. This result is in striking contrast with the usual quasi-two-dimensional (2D) dispersion observed up to now in most superconducting cuprates, including relaxed and compressively strained La2-xSrxCuO4 films grown under the same conditions. The data were analyzed using a 3D tight-binding dispersion for a body-centered-tetragonal lattice. We relate the enhancement of the c-axis dispersion to the significant displacement of the apical oxygen induced by epitaxial strain.

We systematically study the structural and electronic properties of very thin cuprate films. Our direct angle resolved photoemission spectroscopy (ARPES) measurements on the low binding energy electronic structure of La2-xSrxCuO4 (LSCO) films confirmed that the Fermi surface evolves with doping, but changes even more significantly with growth-induced compressive strain. For a given doping, the in-plane compressive strain enhances TC's and modifies the 2-dimensional hole-like Fermi surface as to appear more electron-like. In contrast, the in-plane tensile strain reduces TC (suppressing superconductivity for huge tensile strain) and shows 3-dimensional ARPES dispersion with a corresponding 3-dimensional Fermi surface. To account for these striking changes in electronic structure and superconductivity, the out-of-plane states should be taken into account, as well as some subtle changes in the associated atomic distances.

High-resolution angle-resolved photoemission (ARPES) displays quasi-one dimensional (1D) electronic states in the insulating molybdenum red bronze K0.33MoO3, in good qualitative agreement with band structure calculations. Combined ARPES, optical conductivity, and electrical resistivity data underline the importance of defects which pin the Fermi level within the gap. The ARPES line shape exhibits the same strong-coupling features observed in the blue bronze K0.3MoO3, a related 1D Peierls conductor. We speculate that a similar mechanism could be at the origin of the gaps in both materials.

A Reply to the Comment by Ivana Mrkonjic and Slaven Barisic.Received 15 September 2003DOI:https://doi.org/10.1103/PhysRevLett.92.129702©2004 American Physical Society

TaSe3 belongs to a class of low-dimensional materials characterized by the interplay and competition between dimensionality crossover and broken symmetry ground states. A comprehensive study by dc-transport, optical, and angle-resolved photoemission (ARPES) experiments shows that the electronic properties of this compound are strongly anisotropic between the chain and the transverse crystallographic direction. Even though TaSe3 fails to undergo a charge-density-wave (CDW) phase transition, we found evidence for short range order CDW segments, which progressively disappear with decreasing temperature.

Angle-resolved photoemission spectroscopy reveals very surprising strain-induced effects on the electronic band dispersion of epitaxial La2-xSrxCuO4-delta thin films. In strained films we measure a band that crosses the Fermi level (E-F) well before the Brillouin zone boundary. This is in contrast to the flat band reported in unstrained single crystals and in our unstrained films, as well as in contrast to the band flattening predicted by band structure calculations for in-plane compressive strain. In spite of the density of states reduction near E-F, the critical temperature increases in strained films with respect to unstrained samples. These results require a radical departure from commonly accepted notions about strain effects on high temperature superconductors, with possible general repercussions on superconductivity theory.

High-resolution angle-resolved photoemission data show that a metal-insulator Mott transition occurs at the surface of the quasi-two-dimensional compound 1T-TaSe2. The transition is driven by the narrowing of the Ta 5d band induced by a temperature-dependent modulation of the atomic positions. A dynamical mean-field theory calculation of the spectral function of the half-filled Hubbard model captures the main qualitative feature of the data, namely, the rapid transfer of spectral weight from the observed quasiparticle peak at the Fermi surface to the Hubbard bands, as the correlation gap opens up.

High-resolution angle-resolved photoemission spectroscopy (ARPES) on the quasi-one-dimensional Peierls system K0.3MoO3 reveals a "hidden" open Fermi surface and band features displaying the symmetry properties of the underlying lattice. However, the ARPES line shapes and optical data suggest that the corresponding quasiparticles are heavily renormalized by strong electron-phonon interactions. The temperature dependence of the leading edge of the mostly incoherent spectrum bears signatures of the Peierls transition at T-P=180 K and of pretransitional fluctuations.

High-resolution angle-resolved (ARPES) photoemission in the quasi-one dimensional (1D) Peierls systems (TaSe 4 ) 2 I and K 0.3 MoO 3 reveals spectral features with clear 1D character. Their dispersion and polarization dependence is consistent with open Fermi surfaces and with the symmetry properties of the lattice, However the measured spectral lineshapes are unusual in various respects, as shown also by a comparison with the quasiparticle spectra of a `good' metal. A consistent description of the normal metallic phase and of the low-temperature insulating phases is possible within a polaronic scenario, where the carriers are strongly renormalized by the interaction with the lattice and the spectrum is largely incoherent. The quasiparticle signatures are hidden at the spectral leading edge.

We exploited angle-resolved photoemission (ARPES) to investigate the nature of the elementary quasiparticle (QP) excitations in selected low-dimensional compounds. In the model quasi two-dimensional conductor TiTe2 we observe spectral lineshapes which are consistent with a Fermi liquid (FL) scenario, and the usual QP scattering mechanisms. In contrast, in typical quasi one-dimensional Peierls systems like TTF–TCNQ, (TaSe4)2I and K0.3MoO3, we find clear non-FL lineshapes. We briefly discuss the possible origins of these unusual properties.