Optical manipulation of Rashba-split 2-dimensional electron gas.

In spintronics, the two main approaches to actively control the electrons' spin involve static magnetic or electric fields. An alternative avenue relies on the use of optical fields to generate spin currents, which can bolster spin-device performance, allowing for faster and more efficient logic. To date, research has mainly focused on the optical injection of spin currents through the photogalvanic effect, and little is known about the direct optical control of the intrinsic spin-splitting. To explore the optical manipulation of a material's spin properties, we consider the Rashba effect. Using time- and angle-resolved photoemission spectroscopy (TR-ARPES), we demonstrate that an optical excitation can tune the Rashba-induced spin splitting of a two-dimensional electron gas at the surface of Bi2Se3. We establish that light-induced photovoltage and charge carrier redistribution - which in concert modulate the Rashba spin-orbit coupling strength on a sub-picosecond timescale - can offer an unprecedented platform for achieving optically-driven spin logic devices.

Observation of chiral surface excitons in a topological insulator Bi2Se3.

The protected electron states at the boundaries or on the surfaces of topological insulators (TIs) have been the subject of intense theoretical and experimental investigations. Such states are enforced by very strong spin-orbit interaction in solids composed of heavy elements. Here, we study the composite particles-chiral excitons-formed by the Coulomb attraction between electrons and holes residing on the surface of an archetypical 3D TI, [Formula: see text] Photoluminescence (PL) emission arising due to recombination of excitons in conventional semiconductors is usually unpolarized because of scattering by phonons and other degrees of freedom during exciton thermalization. On the contrary, we observe almost perfectly polarization-preserving PL emission from chiral excitons. We demonstrate that the chiral excitons can be optically oriented with circularly polarized light in a broad range of excitation energies, even when the latter deviate from the (apparent) optical band gap by hundreds of millielectronvolts, and that the orientation remains preserved even at room temperature. Based on the dependences of the PL spectra on the energy and polarization of incident photons, we propose that chiral excitons are made from massive holes and massless (Dirac) electrons, both with chiral spin textures enforced by strong spin-orbit coupling. A theoretical model based on this proposal describes quantitatively the experimental observations. The optical orientation of composite particles, the chiral excitons, emerges as a general result of strong spin-orbit coupling in a 2D electron system. Our findings can potentially expand applications of TIs in photonics and optoelectronics.

Chiral Spin Mode on the Surface of a Topological Insulator.

Using polarization-resolved resonant Raman spectroscopy, we explore collective spin excitations of the chiral surface states in a three dimensional topological insulator, Bi_{2}Se_{3}. We observe a sharp peak at 150 meV in the pseudovector A_{2} symmetry channel of the Raman spectra. By comparing the data with calculations, we identify this peak as the transverse collective spin mode of surface Dirac fermions. This mode, unlike a Dirac plasmon or a surface plasmon in the charge sector of excitations, is analogous to a spin wave in a partially polarized Fermi liquid, with spin-orbit coupling playing the role of an effective magnetic field.

Analogy Between the "Hidden Order" and the Orbital Antiferromagnetism in URu_{2-x}Fe_{x}Si_{2}.

We study URu_{2-x}Fe_{x}Si_{2}, in which two types of staggered phases compete at low temperature as the iron concentration x is varied: the nonmagnetic "hidden order" (HO) phase below the critical concentration x_{c}, and unconventional antiferromagnetic (AFM) phase above x_{c}. By using polarization resolved Raman spectroscopy, we detect a collective mode of pseudovectorlike A_{2g} symmetry whose energy continuously evolves with increasing x; it monotonically decreases in the HO phase until it vanishes at x=x_{c}, and then reappears with increasing energy in the AFM phase. The mode's evolution provides direct evidence for a unified order parameter for both nonmagnetic and magnetic phases arising from the orbital degrees-of-freedom of the uranium-5f electrons.

Discovery of an Unconventional Charge Density Wave at the Surface of K_{0.9}Mo_{6}O_{17}.

We use angle resolved photoemission spectroscopy, Raman spectroscopy, low energy electron diffraction, and x-ray scattering to reveal an unusual electronically mediated charge density wave (CDW) in K_{0.9}Mo_{6}O_{17}. Not only does K_{0.9}Mo_{6}O_{17} lack signatures of electron-phonon coupling, but it also hosts an extraordinary surface CDW, with T_{S_CDW}=220 K nearly twice that of the bulk CDW, T_{B_CDW}=115 K. While the bulk CDW has a BCS-like gap of 12 meV, the surface gap is 10 times larger and well in the strong coupling regime. Strong coupling behavior combined with the absence of signatures of strong electron-phonon coupling indicates that the CDW is likely mediated by electronic interactions enhanced by low dimensionality.

Heavy fermions. Chirality density wave of the "hidden order" phase in URu2Si2.

A second-order phase transition in a physical system is associated with the emergence of an "order parameter" and a spontaneous symmetry breaking. The heavy fermion superconductor URu2Si2 has a "hidden order" (HO) phase below the temperature of 17.5 kelvin; the symmetry of the associated order parameter has remained ambiguous. Here we use polarization-resolved Raman spectroscopy to specify the symmetry of the low-energy excitations above and below the HO transition. We determine that the HO parameter breaks local vertical and diagonal reflection symmetries at the uranium sites, resulting in crystal field states with distinct chiral properties, which order to a commensurate chirality density wave ground state.

Microchannel technologies for artificial lungs: (2) screen-filled wide rectangular channels.

Artificial lungs with blood-side channels on a 10-40 microm scale would be characterized, similar to the natural lungs, by tens of thousands to hundreds of millions parallel blood channels, short blood paths, low pressure drops, and low blood primes. A major challenge for developing such devices is the requirement that the multitude of channels must be uniform from channel to channel and along each channel. One possible strategy for developing microchannel artificial lungs is to fill broad rectangular channels with micro scale screens that can provide uniform support and stability. The present work explores the effectiveness of 40 microm screen-filled blood-side channels and, as a comparison, 82 microm screen-filled channels. Small concept-devices, consisting of a single 69 mm wide and 3 or 6 mm long channel, were tested using 30% hematocrit blood and oxygen or air on the gas side. The measured oxygen fluxes in the devices were in the range of 4 to 9 x 10(-7) moles/(min x cm(2)), with the latter close to the theoretical membrane limit. The pressure drop was in the range of 1-6 mm Hg. Extrapolating the data to a device designed to process 4 L/min suggests a required blood prime of only 35 ml.

Microchannel technologies for artificial lungs: (1) theory.

The feasibility of developing micro channel artificial lungs is calculated for eight possible strategies: 12 and 25 microm circular channels imbedded in gas-permeable sheets, 12 and 25 microm high open rectangular channels with gas-permeable walls, 12 and 25 microm high broad open channels with support posts and gas-permeable walls, and two 40 microm high screen-filled rectangular channels with gas-permeable walls. Each strategy is considered by imposing a pressure drop maximum of 10 mm Hg and limiting the possibility of shear-induced blood trauma. The pressure drop limit determines the acceptable channel length and required size to oxygenate 4 L/min of venous blood. Circular channels imbedded in open-pore, gas-permeable materials are especially attractive. With 12 microm channels, such a device would require 140 million, 0.8 mm long channels, but the total size of the gas-exchange section would be only 57 ml and a blood prime of only 13 ml. Also attractive are 12 mum high broad open channels with support posts and 40 mum screen-filled rectangular channels. The total size of the former would be 250 ml with a blood prime of 13 ml, and the total size of the latter would be 270 ml with a blood prime of 27 ml.

Microchannel technologies for artificial lungs: (3) open rectangular channels.

Lithographic techniques were used to develop patterned silicone rubber membranes that provide 15 microm high microchannels for artificial lungs. Two types of devices were fabricated as a proof-of-concept: one has a series of parallel, straight, open rectangular channels that are each 300 microm wide, separated by 200-microm walls, and 3-mm long and the other is a wide rectangular channel with support posts, also 3- mm long. Experiments with 30% hematocrit, venous, bovine blood showed average oxygen fluxes ranging from 11 x 10(-7) moles/(min x cm(2)) at a residence time of 0.04 sec to 6.5 x 10(-7) moles/(min x cm(2)) at a residence time of 0.20 sec. The average oxygen flux vs. residence time, which is due to transverse molecular diffusion, follows the same relation for all membranes tested. The corresponding increase in hemoglobin saturation ranged from 9% at the residence time of 0.04 sec to 24% at the residence time of 0.20 sec. The support-post channel membranes are attractive for designers because they can be arbitrarily wide and would be less prone to blockage.

Direct evidence of oxidized gold on supported gold catalysts.

Supported gold catalysts have drawn worldwide interest due to the novel properties and potential applications in industries. However, the origin of the catalytic activity in gold nanoparticles is still not well understood. In this study, time-of-flight secondary ion mass spectroscopy (TOF-SIMS) has been applied to investigate the nature of gold in Au (1.3 wt %)/gamma-Al2O3 and Au (2.8 wt %)/TiO2 catalysts prepared by the deposition-precipitation method. The SIMS spectrum of the supported gold catalysts presented AuO-, AuO2-, and AuOH- ion clusters. These measurements show direct evidence for oxidized gold on supported gold catalysts and may be helpful to gaining better understanding of the origin of the catalytic activity.

Catalysis research of relevance to carbon management: progress, challenges, and opportunities.

The goal of the "Opportunities for Catalysis Research in Carbon Management" workshop was to review within the context of greenhouse gas/carbon issues the current state of knowledge, barriers to further scientific and technological progress, and basic scientific research needs in the areas of H2 generation and utilization, light hydrocarbon activation and utilization, carbon dioxide activation, utilization, and sequestration, emerging techniques and research directions in relevant catalysis research, and in catalysis for more efficient transportation engines. Several overarching themes emerge from this review. First and foremost, there is a pressing need to better understand in detail the catalytic mechanisms involved in almost every process area mentioned above. This includes the structures, energetics, lifetimes, and reactivities of the species thought to be important in the key catalytic cycles. As much of this type of information as is possible to acquire would also greatly aid in better understanding perplexing, incomplete/inefficient catalytic cycles and in inventing new, efficient ones. The most productive way to attack such problems must include long-term, in-depth fundamental studies of both commercial and model processes, by conventional research techniques and, importantly, by applying various promising new physicochemical and computational approaches which would allow incisive, in situ elucidation of reaction pathways. There is also a consensus that more exploratory experiments, especially high-risk, unconventional catalytic and model studies, should be undertaken. Such an effort will likely require specialized equipment, instrumentation, and computational facilities. The most expeditious and cost-effective means to carry out this research would be by close coupling of academic, industrial, and national laboratory catalysis efforts worldwide. Completely new research approaches should be vigorously explored, ranging from novel compositions, fabrication techniques, reactors, and reaction conditions for heterogeneous catalysts, to novel ligands and ligation geometries (e.g., biomimetic), reaction media, and activation methods for homogeneous ones. The interplay between these two areas involving various hybrid and single-site supported catalyst systems should also be productive. Finally, new combinatorial and semicombinatorial means to rapidly create and screen catalyst systems are now available. As a complement to the approaches noted above, these techniques promise to greatly accelerate catalyst discovery, evaluation, and understanding. They should be incorporated in the vigorous international research effort needed in this field.