SIMES Publications

Abstract

Superionic materials are multi-component solids with simultaneous characteristics of both a solid and a liquid. Above a critical temperature associated with a structural phase transition, they exhibit liquid-like ionic conductivities and dynamic disorder within a rigid crystalline structure. Broad applications as electrochemical storage materials and resistive switching devices follow from this abrupt change in ionic mobility, but the microscopic pathways and speed limits associated with this switching process are largely unknown. Here we use ultrafast X-ray spectroscopy and scattering techniques to obtain an atomic-level, real-time view of the transition state in copper sulphide nanocrystals. We observe the transformation to occur on a twenty picosecond timescale and show that this is determined by the ionic hopping time.

Abstract

Sulphur is an attractive cathode material with a high specific capacity of 1,673 mAh g⁻¹, but its rapid capacity decay owing to polysulphide dissolution presents a significant technical challenge. Despite much efforts in encapsulating sulphur particles with conducting materials to limit polysulphide dissolution, relatively little emphasis has been placed on dealing with the volumetric expansion of sulphur during lithiation, which will lead to cracking and fracture of the protective shell. Here, we demonstrate the design of a sulphur–TiO₂ yolk–shell nanoarchitecture with internal void space to accommodate the volume expansion of sulphur, resulting in an intact TiO₂ shell to minimize polysulphide dissolution. An initial specific capacity of 1,030 mAh g⁻¹ at 0.5 C and Coulombic efficiency of 98.4% over 1,000 cycles are achieved. Most importantly, the capacity decay after 1,000 cycles is as small as 0.033% per cycle, which represents the best performance for long-cycle lithium–sulphur batteries so far.

Abstract

Charge and spin density waves, periodic modulations of the electron, and magnetization densities, respectively, are among the most abundant and nontrivial low-temperature ordered phases in condensed matter. The ordering direction is widely believed to result from the Fermi surface topology. However, several recent studies indicate that this common view needs to be supplemented. Here, we show how an enhanced electron–lattice interaction can contribute to or even determine the selection of the ordering vector in the model charge density wave system ErTe₃. Our joint experimental and theoretical study allows us to establish a relation between the selection rules of the electronic light scattering spectra and the enhanced electron–phonon coupling in the vicinity of band degeneracy points. This alternative proposal for charge density wave formation may be of general relevance for driving phase transitions into other broken-symmetry ground states, particularly in multiband systems, such as the iron-based superconductors.

Abstract

We present a determinant quantum Monte Carlo study of the competition between instantaneous on-site
Coulomb repulsion and retarded phonon-mediated attraction between electrons, as described by the
two-dimensional Hubbard-Holstein model. At half filling, we find a strong competition between
antiferromagnetism (AFM) and charge-density-wave (CDW) order. We demonstrate that a simple picture
of AFM-CDW competition that incorporates the phonon-mediated attraction into an effective-U Hubbard
model requires significant refinement. Specifically, retardation effects slow the onset of charge order so
that CDWorder remains absent even when the effective U is negative. This delay opens a window where
neither AFM nor CDW order is well established and where there are signatures of a possible metallic
phase.

Abstract

A detailed phenomenology of low energy excitations is a crucial starting point for microscopic understanding of complex materials, such as the cuprate high-temperature superconductors. Because of its unique momentum-space discrimination, angle-resolved photoemission spectroscopy (ARPES) is ideally suited for this task in the cuprates, where emergent phases, particularly superconductivity and the pseudogap, have anisotropic gap structure in momentum space. We present a comprehensive doping- and temperature-dependence ARPES study of spectral gaps in Bi₂Sr₂CaCu₂O_8+δ, covering much of the superconducting portion of the phase diagram. In the ground state, abrupt changes in near-nodal gap phenomenology give spectroscopic evidence for two potential quantum critical points, p = 0.19 for the pseudogap phase and p = 0.076 for another competing phase. Temperature dependence reveals that the pseudogap is not static below T_c and exists p > 0.19 at higher temperatures. Our data imply a revised phase diagram that reconciles conflicting reports about the endpoint of the pseudogap in the literature, incorporates phase competition between the superconducting gap and pseudogap, and highlights distinct physics at the edge of the superconducting dome.

Abstract

Light absorption in a photovoltaic device becomes critical as the thickness of an absorber layer is decreased to reduce cost. To enhance light absorption, photon management at the nanoscale has been studied because conventional methods, which are based on micrometer-sized structure, do not work well for thinner solar cells. This article reviews recent progress in photon management on the nanoscale for increasing light absorption in Si solar cells. The methodology for the absorption enhancement will be discussed, followed by advances in nanofabrication techniques that make the methodology a scalable and viable solution. The authors conclude with a discussion of the challenge of photon management schemes and future directions for light trapping in ultra-thin Si solar cells.

Abstract

Diamondoids are unique molecular nano-materials with diamond structure and fascinating properties such as negative electron affinity and short electron mean free paths. A thin layer of diamondoids deposited on a cathode is able to act as an electron monochromator, reducing the energy spread of photo-emitted electrons from a surface. This property can be applied effectively to improve the spatial resolution in x-ray photoemission electron microscopy (X-PEEM), which is limited by chromatic aberration of the electron optics. In this paper, we present X-PEEM measurements reaching the technological relevant spatial resolution of 10 nm without the need of expensive and complex corrective optics. Our results provide a simple approach to image surface chemical and magnetic information at nanometer scales by employing diamondoids.

Abstract

Diamondoids are unique molecular nano-materials with diamond structure and fascinating properties such as negative electron affinity and short electron mean free paths. A thin layer of diamondoids deposited on a cathode is able to act as an electron monochromator, reducing the energy spread of photo-emitted electrons from a surface. This property can be applied effectively to improve the spatial resolution in x-ray photoemission electron microscopy (X-PEEM), which is limited by chromatic aberration of the electron optics. In this paper, we present X-PEEM measurements reaching the technological relevant spatial resolution of 10 nm without the need of expensive and complex corrective optics. Our results provide a simple approach to image surface chemical and magnetic information at nanometer scales by employing diamondoids.

Abstract

Vertically aligned nanopillars can serve as excellent electrical, optical and mechanical platforms for biological studies. However, revealing the nature of the interface between the cell and the nanopillar is very challenging. In particular, a matter of debate is whether the cell membrane remains intact around the nanopillar. Here we present a detailed characterization of the cell-nanopillar interface by transmission electron microscopy. We examined cortical neurons growing on nanopillars with diameter 50–500 nm and heights 0.5–2 μm. We found that on nanopillars less than 300 nm in diameter, the cell membrane wraps around the entirety of the nanopillar without the nanopillar penetrating into the interior of the cell. On the other hand, the cell sits on top of arrays of larger, closely spaced nanopillars. We also observed that the membrane-surface gap of both cell bodies and neurites is smaller for nanopillars than for a flat substrate. These results support a tight interaction between the cell membrane and the nanopillars and previous findings of excellent sealing in electrophysiology recordings using nanopillar electrodes.

Abstract

High-energy-resolution fluorescence-detected x-ray absorption spectroscopy (HERFD-XAS) has been applied to study the chemical state of ~1.2 nm size-selected Pt nanoparticles (NPs) in an electrochemical environment under potential control. Spectral features due to chemisorbed hydrogen, chemisorbed O/OH, and platinum oxides can be distinguished with increasing potential. Pt electro-oxidation follows two competitive pathways involving both oxide formation and Pt dissolution.