Direct single-molecule dynamic detection of chemical reactions.

Single-molecule detection can reveal time trajectories and reaction pathways of individual intermediates/transition states in chemical reactions and biological processes, which is of fundamental importance to elucidate their intrinsic mechanisms. We present a reliable, label-free single-molecule approach that allows us to directly explore the dynamic process of basic chemical reactions at the single-event level by using stable graphene-molecule single-molecule junctions. These junctions are constructed by covalently connecting a single molecule with a 9-fluorenone center to nanogapped graphene electrodes. For the first time, real-time single-molecule electrical measurements unambiguously show reproducible large-amplitude two-level fluctuations that are highly dependent on solvent environments in a nucleophilic addition reaction of hydroxylamine to a carbonyl group. Both theoretical simulations and ensemble experiments prove that this observation originates from the reversible transition between the reactant and a new intermediate state within a time scale of a few microseconds. These investigations open up a new route that is able to be immediately applied to probe fast single-molecule physics or biophysics with high time resolution, making an important contribution to broad fields beyond reaction chemistry

Interface-engineered hole doping in Sr2IrO4/LaNiO3 heterostructure

The relativistic Mott insulator Sr2IrO4 driven by large spin-orbit interaction is known for the Jeff = 1/2 antiferromagnetic state which closely resembles the electronic structure of parent compounds of superconducting cuprates. Here, we report the realization of hole-doped Sr2IrO4 by means of interfacial charge transfer in Sr2IrO4/LaNiO3 heterostructures. X-ray photoelectron spectroscopy on Ir 4f edge along with the X-ray absorption spectroscopy at Ni L2 edge confirmed that 5d electrons from Ir sites are transferred onto Ni sites, leading to markedly electronic reconstruction at the interface. Although the Sr2IrO4/LaNiO3 heterostructure remains non-metallic, we reveal that the transport behavior is no longer described by the Mott variable range hopping mode, but by the Efros-Shklovskii model. These findings highlight a powerful utility of interfaces to realize emerging electronic states of the Ruddlesden-Popper phases of Ir-based oxides.Comment: 9 pages including 3 figures and reference

Direct Determination of Electron-Phonon Coupling Matrix Element in a Correlated System

High-resolution electron energy loss spectroscopy measurements have been carried out on an optimally doped cuprate Bi2Sr2CaCu2O8+{\delta}. The momentum-dependent linewidth and the dispersion of an A1 optical phonon are obtained. Based on these data as well as the detailed knowledge of the electronic structure from angle-resolved photoemission spectroscopy, we develop a scheme to determine the full structure of electron-phonon coupling for a specific phonon mode, thus providing a general method for directly resolving the EPC matrix element in systems with anisotropic electronic structures

Strengthened proximity effect at grain boundaries to enhance inter-grain supercurrent in Ba1-xKxFe2As2 superconductors

Iron-based superconductors have great potential for high-power applications due to their prominent high-field properties. One of the central issues in enhancing the critical current density of iron-based superconducting wires is to reveal the roles and limitations of grain boundaries in supercurrent transport. Here, we finely tuned the electronic properties of grain boundaries by doping Ba1-xKxFe2As2 superconductors in a wide range (0.25<x<0.598). It is found that the intra-grain Jcintra peaks near x~0.287, while the inter-grain Jcinter has a maximum at about x~0.458. Remarkably, the grain boundary transparency parameter defined as Jcinter/Jcintra rises monotonically with doping. Through detailed microscopic analysis, we suggest that the FeAs segregation phase commonly existing at grain boundaries and the adjacent grains constitute superconductor-normal metal-superconductor (SNS) Josephson junctions which play a key role in transporting supercurrent. A sandwich model based on the proximity effect and the SNS junction is proposed to well interpret our data. It is found that overdoping in superconducting grains largely strengthens the proximity effect and consequently enhances the intergrain supercurrent. Our results will shed new insights and inspirations for improving the application parameters of iron-based superconductors by grain boundary engineering.Comment: 22 pages, 6 figure

Cove‐Edged Nanographenes with Localized Double Bonds

The efficient synthesis and electronic properties of two large‐size cove‐edged nanographenes (NGs), CN1 and CN2, are presented. X‐ray crystallographic analysis reveals a contorted backbone for both molecules owing to the steric repulsion at the inner cove position. Noticeably, the dominant structures of these molecules contain four (for CN1) or six (for CN2) localized C=C double bonds embedded in nine (for CN1) or twelve (for CN2) aromatic sextet rings according to Clar's formula, which is supported by bond length analysis and theoretical (NICS, ACID) calculations. Furthermore, Raman spectra exhibit a band associated with the longitudinal CC stretching mode of olefinic double bonds. Owing to the existence of the additional olefinic bonds, both compounds show a small band gap (1.84 eV for CN1 and 1.37 eV for CN2). They also display moderate fluorescence quantum yield (35 % for CN1 and 50 % for CN2) owing to the contorted geometry, which can suppress aggregation in solution.J.W. acknowleges financial support from the MOE Tier 3 programme (MOE2014-T3-1-004) and NRF Investigatorship (NRF-NRFI05-2019-0005). J.C. acknowledges MINECO and Junta de Andalucía of Spain projects (PGC2018-098533-BI00 and UMA18FEDERJA057). M.A.D.-G. and R.M.-M. thank support from MINECO through the research project MAT2015-66586-R and the FPI fellowship (no. BES-2016-077681), respectively

Flexible but Refractory Single-Crystalline Hyperbolic Metamaterials

The fabrication of flexible single-crystalline plasmonic or photonic components in a scalable way is fundamentally important to flexible electronic and photonic devices with high speed, high energy efficiency, and high reliability. However, it remains to be a big challenge so far. Here, we have successfully synthesized flexible single-crystalline optical hyperbolic metamaterials by directly depositing refractory nitride superlattices on flexible fluoro phlogopite-mica substrates with magnetron sputtering. Interestingly, these flexible hyperbolic metamaterials show dual-band hyperbolic dispersion of dielectric constants with low dielectric losses and high figure-of-merit in the visible to near-infrared ranges. More importantly, the optical properties of these nitride-based flexible hyperbolic metamaterials show remarkable stability under either heating or bending. Therefore, the strategy developed in this work offers an easy and scalable route to fabricate flexible, high-performance, and refractory plasmonic or photonic components, which can significantly expand the applications of current electronic and photonic devices.Comment: 15 page