SIMES Publications

Abstract

Electron emission is critical for a host of modern fabrication and analysis applications including mass spectrometry, electron imaging and nanopatterning. Here, we report that monolayers of diamondoids effectively confer dramatically enhanced field emission properties to metal surfaces. We attribute the improved emission to a significant reduction of the work function rather than a geometric enhancement. This effect depends on the particular diamondoid isomer, with [121]tetramantane-2-thiol reducing gold’s work function from ∼5.1 eV to 1.60 ± 0.3 eV, corresponding to an increase in current by a factor of over 13,000. This reduction in work function is the largest reported for any organic species and also the largest for any air-stable compound^{1, 2, 3}. This effect was not observed for sp³-hybridized alkanes, nor for smaller diamondoid molecules. The magnitude of the enhancement, molecule specificity and elimination of gold metal rearrangement precludes geometric factors as the dominant contribution. Instead, we attribute this effect to the stable radical cation of diamondoids. Our computed enhancement due to a positively charged radical cation was in agreement with the measured work functions to within ±0.3 eV, suggesting a new paradigm for low-work-function coatings based on the design of nanoparticles with stable radical cations.

Abstract

High ionic conductivity solid polymer electrolyte (SPE) has long been desired for the next generation high energy and safe rechargeable lithium batteries. Among all of the SPEs, composite polymer electrolyte (CPE) with ceramic fillers has garnered great interest due to the enhancement of ionic conductivity. However, the high degree of polymer crystallinity, agglomeration of ceramic fillers, and weak polymer–ceramic interaction limit the further improvement of ionic conductivity. Different from the existing methods of blending preformed ceramic particles with polymers, here we introduce an in situ synthesis of ceramic filler particles in polymer electrolyte. Much stronger chemical/mechanical interactions between monodispersed 12 nm diameter SiO₂ nanospheres and poly(ethylene oxide) (PEO) chains were produced by in situ hydrolysis, which significantly suppresses the crystallization of PEO and thus facilitates polymer segmental motion for ionic conduction. In addition, an improved degree of LiClO₄ dissociation can also be achieved. All of these lead to good ionic conductivity (1.2 × 10^–3 S cm^–1 at 60 °C, 4.4 × 10^–5 S cm^–1 at 30 °C). At the same time, largely extended electrochemical stability window up to 5.5 V can be observed. We further demonstrated all-solid-state lithium batteries showing excellent rate capability as well as good cycling performance.

Abstract

The observed magnetoresistance (MR) in three-terminal (3T) ferromagnet-nonmagnet (FM-NM) tunnel junctions has historically been assigned to ensemble dephasing (Hanle effect) of a spin accumulation, thus offering a powerful approach for characterizing the spin lifetime of candidate materials for spintronics applications. However, due to crucial discrepancies of the extracted spin parameters with known materials properties, this interpretation has come under intense scrutiny. By employing epitaxial artificial dipoles as the tunnel barrier in oxide heterostructures, the band alignments between the FM and NM channels can be controllably engineered, providing an experimental platform for testing the predictions of the various spin accumulation models. Using this approach, we have been able to definitively rule out spin accumulation as the origin of the 3T MR. Instead, we assign the origin of the magnetoresistance to spin-dependent hopping through defect states in the barrier, a fundamental phenomenon seen across diverse systems. A theoretical framework is developed that can account for the signal amplitude, linewidth, and anisotropy.

Abstract

As a promising non-precious catalyst for the hydrogen evolution reaction (HER; refs 1,2,3,4,5), molybdenum disulphide (MoS₂) is known to contain active edge sites and an inert basal plane^{1, 6, 7, 8}. Activating the MoS₂ basal plane could further enhance its HER activity but is not often a strategy for doing so. Herein, we report the first activation and optimization of the basal plane of monolayer 2H-MoS₂ for HER by introducing sulphur (S) vacancies and strain. Our theoretical and experimental results show that the S-vacancies are new catalytic sites in the basal plane, where gap states around the Fermi level allow hydrogen to bind directly to exposed Mo atoms. The hydrogen adsorption free energy (ΔG_H) can be further manipulated by straining the surface with S-vacancies, which fine-tunes the catalytic activity. Proper combinations of S-vacancy and strain yield the optimal ΔG_H = 0 eV, which allows us to achieve the highest intrinsic HER activity among molybdenum-sulphide-based catalysts.

Abstract

Charge density wave (CDW) correlations have been shown to universally exist in cuprate superconductors. However, their nature at high fields inferred from nuclear magnetic resonance is distinct from that measured by x-ray scattering at zero and low fields. Here we combine a pulsed magnet with an x-ray free electron laser to characterize the CDW in YBa₂Cu₃O_6.67 via x-ray scattering in fields up to 28 Tesla. While the zero-field CDW order, which develops below T ~ 150 K, is essentially two-dimensional, at lower temperature and beyond 15 Tesla, another three-dimensionally ordered CDW emerges. The field-induced CDW appears around the zero-field superconducting transition temperature; in contrast, the incommensurate in-plane ordering vector is field-independent. This implies that the two forms of CDW and high-temperature superconductivity are intimately linked.

Abstract

To shed light on how electronic correlations vary across the phase diagram of the cuprate superconductors, we examine the doping evolution of spin and charge excitations in the single-band Hubbard model using determinant quantum Monte Carlo (DQMC). In the single-particle response, we observe that the effects of correlations weaken rapidly with doping, such that one may expect the random phase approximation (RPA) to provide an adequate description of the two-particle response. In contrast, when compared to RPA, we find that significant residual correlations in the two-particle excitations persist up to 40% hole and 15% electron doping (the range of dopings achieved in the cuprates). These fundamental differences between the doping evolution of single- and multiparticle renormalizations show that conclusions drawn from single-particle processes cannot necessarily be applied to multiparticle excitations. Eventually, the system smoothly transitions via a momentum-dependent crossover into a weakly correlated metallic state where the spin and charge excitation spectra exhibit similar behavior and where RPA provides an adequate description.

Abstract

Owing to its low cost and high natural abundance, sodium metal is among the most promising anode materials for energy storage technologies beyond lithium ion batteries. However, room-temperature sodium metal anodes suffer from poor reversibility during long-term plating and stripping, mainly due to formation of nonuniform solid electrolyte interphase as well as dendritic growth of sodium metal. Herein we report for the first time that a simple liquid electrolyte, sodium hexafluorophosphate in glymes (mono-, di-, and tetraglyme), can enable highly reversible and nondendritic plating–stripping of sodium metal anodes at room temperature. High average Coulombic efficiencies of 99.9% were achieved over 300 plating–stripping cycles at 0.5 mA cm^–2. The long-term reversibility was found to arise from the formation of a uniform, inorganic solid electrolyte interphase made of sodium oxide and sodium fluoride, which is highly impermeable to electrolyte solvent and conducive to nondendritic growth. As a proof of concept, we also demonstrate a room-temperature sodium–sulfur battery using this class of electrolytes, paving the way for the development of next-generation, sodium-based energy storage technologies.

Abstract

The coexistence of ferromagnetic and antiferromagnetic phases and their role in the photoinduced insulator-to-metal transition in Pr_1−x Ca_x MnO₃ are revealed via ultrafast resonant x-ray diffraction and broadband optical reflectivity measurements. The antiferromagnetic scattering signal and ferromagnetically sensitive reflectivity measurements show similar, strongly temperature dependent time scales. We attribute the common dynamics to an activation barrier between the equilibrium insulating phase and the photoinduced metallic phase related to interactions between the phase-separated ferromagnetic and antiferromagnetic insulating phases.

Abstract

Engineered optoelectronic surfaces must control both the flow of light and the flow of electrons at an interface; however, nanostructures for photon and electron management have typically been studied and optimized separately. In this work, we unify these concepts in a new hybrid metal–semiconductor surface that offers both strong light absorption and high electrical conductivity. We use metal-assisted chemical etching to nanostructure the surface of a silicon wafer, creating an array of silicon nanopillars protruding through holes in a gold film. When coated with a silicon nitride anti-reflection layer, we observe broad-band absorption of up to 97% in this structure, which is remarkable considering that metal covers 60% of the top surface. We use optical simulations to show that Mie-like resonances in the nanopillars funnel light around the metal layer and into the substrate, rendering the metal nearly transparent to the incoming light. Our results show that, across a wide parameter space, hybrid metal–semiconductor surfaces with absorption above 90% and sheet resistance below 20 Ω/□ are realizable, suggesting a new paradigm wherein transparent electrodes and photon management textures are designed and fabricated together to create high-performance optoelectronic interfaces.

Abstract

High-resolution X-ray microscopy is used to investigate the sequence of lithiation in LiFePO₄porous electrodes. For electrodes with homogeneous interparticle electronic connectivity via the carbon black network, the smaller particles lithiate first. For electrodes with heterogeneous connectivity, the better-connected particles preferentially lithiate. Correlative electron and X-ray microscopy also reveal the presence of incoherent nanodomains that lithiate as if they are separate particles.