Highly Efficient Determination of Complex NMR Multiplet Structures in Inhomogeneous Magnetic Fields.

Proton-proton scalar (J) coupling plays an important role in disentangling molecular structures and spatial conformations. But it is challenging to extract J coupling networks from congested 1H NMR spectra, especially in inhomogeneous magnetic fields. Herein, we propose a general liquid NMR protocol, named HR-G-SERF, to implement highly efficient determination of individual J couplings and corresponding coupling networks via simultaneously suppressing effects of spectral congestions and magnetic field inhomogeneity. This method records full-resolved 2D absorption-mode spectra to deliver great convenience for multipet analyses on complex samples. More meaningfully, it is capable of disentangling multiplet structures of biological samples, that is, grape sarcocarp, despite of its heterogeneous semisolid state and extensive compositions. In addition, a modification, named AH-G-SERF, is developed to compress experimental acquisition and subsequently improve unit-time SNR, while maintaining satisfactory spectral performance. This accelerated variant may further boost the applicability for rapid NMR detections and afford the possibility of adopting hyperpolarized substances to enhance the overall sensitivity. Therefore, this study provides a promising tool for molecular structure elucidations and composition analyses in chemistry, biochemistry, and metabonomics among others.

Quasi-Bragg plasmon modes for highly efficient plasmon-enhanced second-harmonic generation at near-ultraviolet frequencies.

Boosting nonlinear frequency conversions with plasmonic nanostructures at near-ultraviolet (UV) frequencies remains a great challenge in nano-optics. Here we experimentally design and fabricate a plasmon-enhanced second-harmonic generation (PESHG) platform suitable for near-UV frequencies by integrating aluminum materials with grating configurations involved in structural heterogeneity. The SHG emission on the proposed platform can be amplified by up to three orders of magnitude with respect to unpatterned systems. Furthermore, the mechanism governing this amplification is identified as the occurrence of quasi-Bragg plasmon modes near second-harmonic wavelengths, such that a well-defined coherent interplay can be attained within the hot spot region and facilitate the efficient out-coupling of local second-harmonic lights to the far-field. Our work sheds light into the understanding of the role of grating-coupled surface plasmon resonances played in PESHG processes, and should pave an avenue toward UV nanosource and nonlinear metasurface applications.

Controlled growth of MoS2 via surface-energy alterations.

Monolayer MoS2 in triangular configurations with rich edges or high-quality uniform films are either catalytically active for the hydrogen evolution reaction or flexible for functional electronic and optoelectronic devices. Here, we have experimentally discovered that these two types of MoS2 products can be selectively synthesized on graphene or sapphire substrates, which are associated with both different adsorption energy and diffusion-energy barrier for vapor precursors during growth. Our study not only provides insights into the on-surface synthesis of high-quality MoS2 monolayers, but also can be applied to the growth of vertically-stacked and large-scale in-plane lateral MoS2-graphene heterostructures.

Multiband enhanced second-harmonic generation via plasmon hybridization.

Boosting nonlinear frequency-conversion efficiencies in hybrid metal-dielectric nanostructures generally requires the enhancement of optical fields that interact constructively with nonlinear dielectrics. Inevitably for localized surface plasmons, spectra subject to this enhancement tend to span narrowly. As a result, because of the spectral mismatch of resonant modes at frequencies participating in nonlinear optical processes, strong nonlinear signal generations endure the disadvantage of rapid degradations. Here, we experimentally design a multiband enhanced second-harmonic generation platform of three-dimensional metal-dielectric-metal nanocavities that consist of thin ZnO films integrated with silver mushroom arrays. Varying geometric parameters, we demonstrate that the introduction of ZnO materials in intracavity regions enables us to modulate fundamental-frequency-related resonant modes, resulting in strong coupling induced plasmon hybridization between localized and propagating surface plasmons. Meanwhile, ZnO materials can also serve as an efficient nonlinear dielectric, which provides a potential to obtain a well-defined coherent interplay between hybridized resonant modes and nonlinear susceptibilities of dielectric materials at multi-frequency. Finally, not only is the conversion efficiency of ZnO materials increased by almost two orders of magnitude with respect to hybrid un-pattered systems at several wavelengths over a 100-nm spectral range but also a hybrid plasmon-light coupling scheme in three-dimensional nanostructures can be developed.

Plasmon-Induced Magnetic Resonance Enhanced Raman Spectroscopy.

Plasmon-induced magnetic resonance has shown great potentials in optical metamaterials, chemical (bio)-sensing, and surface-enhanced spectroscopies. Here, we have theoretically and experimentally revealed (1) a correspondence of the strongest near-field response to the far-field scattering valley and (2) a significant improvement in Raman signals of probing molecules by the plasmon-induced magnetic resonance. These revelations are accomplished by designing a simple and practical metallic nanoparticle-film plasmonic system that generates magnetic resonances at visible-near-infrared frequencies. Our work may provide new insights for understanding the enhancement mechanism of various plasmon-enhanced spectroscopies and also helps further explore light-matter interactions at the nanoscale.

Critical Annealing Temperature for Stacking Orientation of Bilayer Graphene.

It is rarely reported that stacking orientations of bilayer graphene (BLG) can be manipulated by the annealing process. Most investigators have painstakingly fabricated this BLG by chemical vapor deposition growth or mechanical means. Here, it is discovered that, at ≈600 °C, called the critical annealing temperature (CAT), most stacking orientations collapse into strongly coupled or AB-stacked states. This phenomenon is governed (i) macroscopically by the stress generation and release in top graphene domains, evolving from mild ripples to sharp billows in certain local areas, and (ii) microscopically by the principle of minimal potential obeyed by carbon atoms that have acquired sufficient thermal energy at CAT. Conspicuously, evolutions of stacking orientations in Raman mappings under various annealing temperatures are observed. Furthermore, MoS2 synthesized on BLG is used to directly observe crystal orientations of top and bottom graphene layers. The finding of CAT provides a guide for the fabrication of strongly coupled or AB-stacked BLG, and can be applied to aligning other 2D heterostructures.

Analyses of multi-color plant-growth light sources in achieving maximum photosynthesis efficiencies with enhanced color qualities.

An optimal design of light-emitting diode (LED) lighting that benefits both the photosynthesis performance for plants and the visional health for human eyes has drawn considerable attention. In the present study, we have developed a multi-color driving algorithm that serves as a liaison between desired spectral power distributions and pulse-width-modulation duty cycles. With the aid of this algorithm, our multi-color plant-growth light sources can optimize correlated-color temperature (CCT) and color rendering index (CRI) such that photosynthetic luminous efficacy of radiation (PLER) is maximized regardless of the number of LEDs and the type of photosynthetic action spectrum (PAS). In order to illustrate the accuracies of the proposed algorithm and the practicalities of our plant-growth light sources, we choose six color LEDs and German PAS for experiments. Finally, our study can help provide a useful guide to improve light qualities in plant factories, in which long-term co-inhabitance of plants and human beings is required.

Improvements of mesopic luminance for light-emitting-diode-based outdoor light sources via tuning scotopic/photopic ratios.

Outdoor light sources must guarantee excellent mesopic luminance (Lmes) for traffic safety at night. Here, we propose a solution to improve mesopic-related parameters, which include especially the scotopic/photopic ratio and the Lmes, of multi-chip light-emitting diode (LED) light sources. Generally, these sources are driven by pulse-width-modulation currents, and possess readily-controlled spectral power distributions (SPDs). An updated version of the optical power ratio algorithm developed in this article can select suitable overall SPDs and yield corresponding duty cycles to drive individual chips at different correlated-color temperatures and operating temperatures. Its accuracy and practicality are proven by experimental results. In addition, our study introduces a temperature-feedback technique that can instantly adjust duty cycles for each chip according to real-time operating temperatures in order to avoid undesirable color drifts at different operating temperatures. It can also be regarded as a model for practitioners who desire to improve the quality of outdoor light sources.

A visualization method for probing grain boundaries of single layer graphene via molecular beam epitaxy.

Graphene, a member of layered two-dimensional (2D) materials, possesses high carrier mobility, mechanical flexibility, and optical transparency, as well as enjoying a wide range of promising applications in electronics. Adopting the chemical vaporization deposition method, the majority of investigators have ubiquitously grown single layer graphene (SLG), which inevitably involves polycrystalline properties. Here we demonstrate a simple method for the direct visualization of arbitrarily large-size SLG domains by synthesizing one-hundred-nm-scale MoS2 single crystals via a high-vacuum molecular beam epitaxy process. The present study based on epitaxial growth provides a guide for probing the grain boundaries of various 2D materials and implements higher potentials for the next-generation electronic devices.

Graphene-Based Fluorescence-Quenching-Related Fermi Level Elevation and Electron-Concentration Surge.

Intermolecular p-orbital overlaps in unsaturated π-conjugated systems, such as graphene and fluorescent molecules with aromatic structure, serve as the electron-exchanged path. Using Raman-mapping measurements, we observe that the fluorescence intensity of fluorescein isothiocyanate (FITC) is quenched by graphene, whereas it persists in graphene-absent substrates (SiO2). After identifying a mechanism related to photon-induced electron transfer (PET) that contributes to this fluorescence quenching phenomenon, we validate this mechanism by conducting analyses on Dirac point shifts of FITC-coated graphene. From these shifts, Fermi level elevation and the electron-concentration surge in graphene upon visible-light impingements are acquired. Finally, according to this mechanism, graphene-based biosensors are fabricated to show the sensing capability of measuring fluorescently labeled-biomolecule concentrations.

Multi-function indoor light sources based on light-emitting diodes-a solution for healthy lighting.

A solution for multi-functional indoor light sources is proposed to achieve the new concept of healthy lighting. A remotely controllable light source that embodies a quadruple-chip light-emitting diode and driven by pulse-width-modulation currents is designed. Therefore, spectral power distributions (SPDs) of the light source can be readily controlled. An algorithm, namely the optical power ratio algorithm, is developed to select all suitable SPDs adapted for various applications. Principles of selection are based on those traditional visual indices, as well as on some non-visual parameters such as circadian action factor, circadian efficacy of radiation and circadian illuminance. We investigate in detail the correlation among these parameters and provide SPDs with both decent visual and non-visual performances for three typical cases. The study suggests some fundamental principles for designing healthy light sources, and can be regarded as a guide for designing indoor light sources of the next generation.

Plasmon-Enhanced Second-Harmonic Generation Nanorulers with Ultrahigh Sensitivities.

Attainment of spatial resolutions far below diffraction limits by means of optical methods constitutes a challenging task. Here, we design nonlinear nanorulers that are capable of accomplishing approximately 1 nm resolutions by utilizing the mechanism of plasmon-enhanced second-harmonic generation (PESHG). Through introducing Au@SiO2 (core@shell) shell-isolated nanoparticles, we strive to maneuver electric-field-related gap modes such that a reliable relationship between PESHG responses and gap sizes, represented by "PESHG nanoruler equation", can be obtained. Additionally validated by both experiments and simulations, we have transferred "hot spots" to the film-nanoparticle-gap region, ensuring that retrieved PESHG emissions nearly exclusively originate from this region and are significantly amplified. The PESHG nanoruler can be potentially developed as an ultrasensitive optical method for measuring nanoscale distances with higher spectral accuracies and signal-to-noise ratios.

Shape Stability of Metallic Nanoplates: A Molecular Dynamics Study.

Metallic nanoplates have attracted widespread interests owing to their functional versatility, which relies heavily on their morphologies. In this study, the shape stability of several metallic nanoplates with body-centered-cubic (bcc) lattices is investigated by employing molecular dynamics simulations. It is found that the nanoplate with (110) surface planes is the most stable compared to the ones with (111) and (001) surfaces, and their shapes evolve with different patterns as the temperature increases. The formation of differently orientated facets is observed in the (001) nanoplates, which leads to the accumulation of shear stress and thus results in the subsequent formation of saddle shape. The associated shape evolution is quantitatively characterized. Further simulations suggest that the shape stability could be tuned by facet orientations, nanoplate sizes (including diameter and thickness), and components.

Hydrogen Induced Etching Features of Wrinkled Graphene Domains.

Wrinkles are observed commonly in CVD (chemical vapor deposition)-grown graphene on Cu and hydrogen etching is of significant interest to understand the growth details, as well as a practical tool for fabricating functional graphene nanostructures. Here, we demonstrate a special hydrogen etching phenomenon of wrinkled graphene domains. We investigated the wrinkling of graphene domains under fast cooling conditions and the results indicated that wrinkles in the monolayer area formed more easily compared to the multilayer area (≥two layers), and the boundary of the multilayer area tended to be a high density wrinkle zone in those graphene domains, with a small portion of multilayer area in the center. Due to the site-selective adsorption of atomic hydrogen on wrinkled regions, the boundary of the multilayer area became a new initial point for the etching process, aside from the domain edge and random defect sites, as reported before, leading to the separation of the monolayer and multilayer area over time. A schematic model was drawn to illustrate how the etching of wrinkled graphene was generated and propagated. This work may provide valuable guidance for the design and growth of nanostructures based on wrinkled graphene.

Construction of three-dimensional temperature distribution using a network of ultrasonic transducers.

Although the ultrasonic technique for measuring temperature distributions has drawn much attention in recent years, most studies that adopt this technique focus on two-dimensional (2D) systems. Mathematically, extending from 2D to 3D requires higher construction-performing algorithms, as well as more complicated, but extremely crucial, designs of ultrasonic transducer layouts. Otherwise the ill condition of governing-equation matrices will become more serious. Here, we aim at constructing 3D temperature distributions by using a network of properly-installed ultrasonic transducers that can be controlled to transmit and receive ultrasound. In addition, the proposed method is capable of performing this construction procedure in real time, thus monitoring transient temperature distributions and guarantee the safety of operations related to heating or burning. Numerical simulations include constructions for four kinds of temperature distributions, as well as corresponding qualitative and quantitative analyses. Finally, our study offers a guide in developing non-intrusive experimental methods that measure 3D temperature distributions in real time.

Tunable surface plasmon polaritons and ultrafast dynamics in 2D nanohole arrays.

High-quality and unique surface plasmon resonance (SPR) with a narrow linewidth and controllable resonance energy plays a key role in wide applications including ultrahigh-resolution spectroscopy, on-chip sensing, optical modulation, and solar cell technology. In this work, the response of surface plasmon polariton (SPP) modes in Au nanohole arrays has been effectively tuned by properly adjusting the sample orientation without changing the geometrical parameters, and a very narrow linewidth down to 8 nm is achieved via the strong interference of two (0, -1) and (-1, 0) SPP modes in the Γ-M direction under transverse magnetic polarization. These results have been validated excellently by finite-element-method numerical simulations. More importantly, we have quantitatively investigated the contribution of conduction-band electron distribution to the SPP intensity of the array within a 20 ps timescale with ultrahigh sensitivity by utilizing home-built femtosecond transient absorption spectroscopy, and observed the minimum SPP intensity at ∼700 fs following excitation with a 0.2 µJ pulse. This study may help enhance the understanding toward the intrinsic micromechanism of SPR, thus offering opportunities for potential applications in strong coupling and new-style optical wave manipulations.

Capabilities of transition metals in retarding the bonding of carbon atoms to minimize dendritic graphene.

The avoidance of growing dendritic graphene on the copper substrate during the chemical vapor deposition process is greatly desired. Here we have identified a mechanism, in which (1) transition metal plates placed inside the copper pockets reduce the majority of active carbon atoms to eventually suppress the graphene growth rate, and (2) transition metals etch graphene C-C bonds along defective edges to grow into zigzag-edge ending domains with higher priorities. Via isotopic labeling of the methane method, we have observed bright-dark-alternating hexagonal-shaped rings, which are shown in Raman mapping images. Under a hydrogen atmosphere, we are capable of acquiring hexagonal openings within graphene domains by means of transition-metal-driven catalytic etching. This methodology may work as a simple and convenient way to determine graphene size and crystal orientation, and may enable the etching of graphene into smooth and ordered zigzag edge nanoribbons without compromising the quality of graphene.

Thermal electron-tunneling devices as coolers and amplifiers.

Nanoscale thermal systems that are associated with a pair of electron reservoirs have been previously studied. In particular, devices that adjust electron tunnels relatively to reservoirs' chemical potentials enjoy the novelty and the potential. Since only two reservoirs and one tunnel exist, however, designers need external aids to complete a cycle, rendering their models non-spontaneous. Here we design thermal conversion devices that are operated among three electron reservoirs connected by energy-filtering tunnels and also referred to as thermal electron-tunneling devices. They are driven by one of electron reservoirs rather than the external power input, and are equivalent to those coupling systems consisting of forward and reverse Carnot cycles with energy selective electron functions. These previously-unreported electronic devices can be used as coolers and thermal amplifiers and may be called as thermal transistors. The electron and energy fluxes of devices are capable of being manipulated in the same or oppsite directions at our disposal. The proposed model can open a new field in the application of nano-devices.

Maximal rectification ratios for idealized bi-segment thermal rectifiers.

Thermal rectifiers whose forward heat fluxes are greater than reverse counterparts have been extensively studied. Here we have discovered, idealized, and derived the ultimate limit of such rectification ratios, which are partially validated by numerical simulations, experiments, and micro-scale Hamiltonian-oscillator analyses. For rectifiers whose thermal conductivities (κ) are linear with the temperature, this limit is simply a numerical value of 3. For those whose conductivities are nonlinear with temperatures, the maxima equal κmax/κmin, where two extremes denote values of the solid segment materials that can be possibly found or fabricated within a reasonable temperature range. Recommendations for manufacturing high-ratio rectifiers are also given with examples. Under idealized assumptions, these proposed rectification limits cannot be defied by any bi-segment thermal rectifiers.