Flat Au Research Articles

Advanced 3D Micro‐Electrodes for On‐Chip Zinc‐Ion Micro‐Batteries

AbstractThe development of high‐performance planar micro‐batteries featuring safer, cost‐effective systems is crucial for powering smart devices such as medical implants, micro‐robots, micro‐sensors, and the Internet of Things (IoT). However, current on‐chip micro‐batteries suffer from limited energy density within constrained device footprints due to challenges in effectively loading high‐capacity active materials onto micro‐electrodes. Innovative designs for advanced micro‐electrodes are needed for on‐chip micro‐batteries. This work introduces advanced, highly porous 3D gold (Au) scaffold‐based interdigitated electrodes (IDEs) as current collectors, which enable effective loading of active materials (Zn and polyaniline) without compromising overall conductivity and significantly increase active mass loading. These 3D Au scaffold‐based micro‐batteries (3D P‐ZIMB) offer substantially higher energy storage performance (≈135% enhancement) compared to conventional micro‐batteries (C‐ZIMB) when materials loaded onto flat Au IDEs. Furthermore, the 3D P‐ZIMB demonstrates higher areal capacities (≈35 µAh cm−2) and areal energy (≈31.05 µWh cm−2) than most high‐performance on‐chip micro‐batteries, and it delivers a much higher areal power (≈3584.35 µW cm−2) than high‐performance on‐chip micro‐supercapacitors. In‐depth postmortem investigations reveal that the 3D P‐ZIMB avoids issues like material peeling, sluggish electrolyte ion diffusion, and dendrite formation on the anode, while maintaining identical material morphologies and structural characteristics. Therefore, this study presents a smart strategy to enhance the electrochemical performance of planar micro‐batteries and advance the field of on‐chip micro‐battery research.

Selective Oxidation of Methanol to Methyl Formate on Gold: The Role of Low-Coordinated Sites Revealed by Isothermal Pulsed Molecular Beam Experiments and AIMD Simulations.

To elucidate the role of low-coordinated sites in the partial methanol oxidation to methyl formate (MeFo), the isothermal reactivity of flat Au(111) and stepped Au(332) in pulsed molecular beam experiments was compared for a broad range of reaction conditions. Low-coordinated step sites were found to enhance MeFo selectivity, especially at low coverage conditions, as found at higher temperatures. The analysis of the transient kinetics provides evidence for the essential role of Au x O y phases for MeFo formation and the complex interplay of different oxygen species for the observed selectivity. Ab initio molecular dynamic simulations yielded microscopic insights in the formation of Au x O y phases on flat and stepped gold surfaces emphasizing the role of low-coordinated sites in their formation. Moreover, associated surface restructuring provides atomic-scale insights which align with the experimentally observed transient kinetics in MeFo formation.

Advanced Porous Gold-PANI Micro-Electrodes for High-Performance On-Chip Micro-Supercapacitors.

The downsizing of microscale energy storage devices is crucial for powering modern on-chip technologies by miniaturizing electronic components. Developing high-performance microscale energy devices, such as micro-supercapacitors, is essential through processing smart electrodes for on-chip structures. In this context, we introduce porous gold (Au) interdigitated electrodes (IDEs) as current collectors for micro-supercapacitors, using polyaniline as the active material. These porous Au IDE-based symmetric micro-supercapacitors (P-SMSCs) show a remarkable enhancement in charge storage performance, with a 187% increase in areal capacitance at 2.5 mA compared to conventional flat Au IDE-based devices, despite identical active material loading times. Our P-SMSCs achieve an areal capacitance of 60 mF/cm2, a peak areal energy density of 5.44 μWh/cm2, and an areal power of 2778 μW/cm2, surpassing most reported SMSCs. This study advances high-performance SMSCs by developing highly porous microscale planar current collectors, optimizing microelectrode use, and maximizing capacity within a compact footprint.

Infrared routing and switching with tunable spectral bandwidth using arrays of metallic nanoantennas.

We study infrared routing and switching with tunable spectral bandwidth using in-plane scattering of light by flat Au nanoantenna arrays. The base dimensions of these nanoantennas are approximately 250 by 850 nm, while their heights vary from 20 to 150 nm. Our results show that, with the increase in height, the arrays become more efficient scatterers while their spectra broaden within the 1-1.6 $\mu$m range. Our findings demonstrate that such processes strongly depend on the incident light polarization. For a given polarization, the incident light is efficiently scattered in only two opposite directions along the plane of the arrays, with insignificant transmission. Switching such a polarization by 90$^\circ$, however, suppresses this process, allowing the light to mostly pass through the arrays with minimal scattering. These unique characteristics suggest a tunable beam splitter application in the 1-1.6 $\mu$m range and even longer wavelengths.

Partial Oxidation of Methanol on Gold: How Selectivity Is Steered by Low-Coordinated Sites.

Partial methanol oxidation proceeds with high selectivity to methyl formate (MeFo) on nanoporous gold (npAu) catalysts. As low-coordinated sites on npAu were suggested to affect the selectivity, we experimentally investigated their role in the isothermal selectivity for flat Au(111) and stepped Au(332) model surfaces using a molecular beam approach under well-defined conditions. Direct comparison shows that steps enhance desired MeFo formation and lower undesired overoxidation. DFT calculations reveal differences in oxygen distribution that enhance the barriers to overoxidation at steps. Thus, these results provide an atomic-level understanding of factors controlling the complex reaction network on gold catalysts, such as npAu.

Polar Self-Organization of Ferroelectric Nematic-Liquid-Crystal Molecules on Atomically Flat Au(111) Surface.

Understanding nanoscale mechanisms responsible for the recently discovered ferroelectric nematics can be helped by direct visualization of self-assembly of strongly polar molecules. Here, we report on scanning tunneling microscopy studies of monomolecular layers of a ferroelectric nematic liquid crystal on a reconstructed Au(111) surface. The monolayers are obtained by deposition from a solution at ambient conditions. The adsorbed ferroelectric nematic molecules self-assemble into regular rows with tilted orientation, resembling a layered structure of a smectic C. Remarkably, each molecular dipole in this architecture is oriented along the same direction giving rise to polar ferroelectric ordering.

Simultaneous Surface-Enhanced Raman Scattering with a Kerr Gate for Fluorescence Suppression.

The combination of surface-enhanced and Kerr-gated Raman spectroscopy for the enhancement of the Raman signal and suppression of fluorescence is reported. Surface-enhanced Raman scattering (SERS)-active gold substrates were demonstrated for the expansion of the surface generality of optical Kerr-gated Raman spectroscopy, broadening its applicability to the study of analytes that show a weak Raman signal in highly fluorescent media under (pre)resonant conditions. This approach is highlighted by the well-defined spectra of rhodamine 6G, Nile red, and Nile blue. The Raman spectra of fluorescent dyes were obtained only when SERS-active substrates were used in combination with the Kerr gate. To achieve enhancement of the weaker Raman scattering, Au films with different roughnesses or Au-core-shell-isolated nanoparticles (SHINs) were used. The use of SHINs enabled measurement of fluorescent dyes on non-SERS-active, optically flat Au, Cu, and Al substrates.

Dramatic Electrochemical Tuning of the Plasmonic Spectrum of a Metal Nanoparticle on a Mirror

Enhancement of electric fields in the nanometric gap between plasmonic nanostructures is widely exploited for sensing, enhanced spectroscopies and photochemistry. Plasmonic properties of nanostructures with ultrathin gaps, such as nanoparticles (NPs) positioned on a flat metal surface (a mirror), have attracted much attention in recent years [1]. We studied the effect of electrochemical control on the plasmonic properties of single Au and Ag NPs on a mirror. We found that the coupled plasmonic resonance could be reversibly tuned over a range of tenths of nanometers, more than an order of magnitude higher than expected based just on capacitive charging of the NPs.Our experimental system consisted of single Au or Ag NPs (50 nm – 100 nm) adsorbed on a self-assembled monolayer (SAM) of either polyelectrolytes, cysteamine (CEA) or ethanedithiol (EDT) deposited on an atomically flat 100nm thick Au electrode prepared by template stripping. The NPs were either bare (prepared by H2 reduction) or citrate-stabilized and the system was immersed in a basic solution.Coupling to the mirror electrode resulted in the appearance of several bands in the plasmonic spectrum of individual NPs, as measured by dark-field microspectroscopy (Fig. 1a), and the lowest-energy band could be attributed to the coupled plasmon. Variation of the electrode potential generated a giant, though reversi shift of the spectrum. A plot of the peak position of the coupled plasmon band displayed an S-shaped, phase-transition like behavior (Fig. 1b).This remarkable result could not be observed with individual NPs deposited on non-metallic surfaces, and can therefore be attributed to a dramatic modulation of the coupling between the particles and the mirror with electrode potential.Figure 1. Scattering spectra (a) and variation of the spectral position of the coupled plasmon peak (b) of bare AuNP (ca. 60 nm) on CEA/Au electrode. Inset in (a): Scheme of NP on the mirror.

Modeling Field Electron Emission from a Flat Au (100) Surface with Density-Functional Theory

Field electron emission, or electron tunneling through a potential energy (PE) barrier under the influence of a strong electrostatic (ES) or radio frequency (RF) field, is of broad interest to the accelerator physics community. For example, it is the source of undesirable dark currents in resonant cavities, providing a limit to high-field operation. Field electron emission can also be applied to quasi-statically model electron emission induced by the electric field in a laser pulse. The classical approach to field electron emission is the Fowler–Nordheim (FN) framework, which incorporates a simplified PE profile and various assumptions. Here, we build a more realistic model using the PE and charge densities derived from a density-functional theory (DFT) calculation. We examine the correction factors associated with each model assumption. Compared to the FN framework, our results can be extended up to 80 GV/m, a limit that has been reached in laser-induced strong field emission scenarios.

Investigating the effects of solution viscosity on the stability and success rate of SECCM imaging

Due to the capability of simultaneously detecting the morphology and electrochemical information of samples and limiting the electrochemical reaction to a range approximately the size of the inner diameter of the pipette tip opening, scanning electrochemical cell microscopy (SECCM) enables higher precision local electrochemical measurement and surface material delivery and has been demonstrating unique advantages and broad application prospects. However, the meniscus droplet at the pipette tip of SECCM is equivalent to the opening radius of the pipette tip, which is usually tens of nanometers to hundreds of nanometers. The tiny meniscus droplet makes it susceptible to evaporation and crystallization, which increases the likelihood of the pipette colliding with the sample during the scanning process, resulting in the failure of scanning. In this paper, the influence of solution viscosity on the shape variation of the droplet at the tip during the movement of the pipette of SECCM was studied by finite element analysis. It is proved that the increase of solution viscosity is helpful in reducing the shape variation of the droplet at the tip during the movement of the pipette. Then scanning experiments were carried out using a flat Au substrate and Au substrates with rounded triangle and rounded rectangular convex structures as the samples. According to the experimental results, increasing solution viscosity improves scanning success rates and scanning quality and effectively lowers the MSE of the scanning results. The experimental results also show that SECCM can image at a higher speed when the solution's viscosity increases since the deformation of the droplet at the tip is less than with a typical solution.

Direct nano-imaging of light-matter interactions in nanoscale excitonic emitters

Strong light-matter interactions in localized nano-emitters placed near metallic mirrors have been widely reported via spectroscopic studies in the optical far-field. Here, we report a near-field nano-spectroscopic study of localized nanoscale emitters on a flat Au substrate. Using quasi 2-dimensional CdSe/CdxZn1-xS nanoplatelets, we observe directional propagation on the Au substrate of surface plasmon polaritons launched from the excitons of the nanoplatelets as wave-like fringe patterns in the near-field photoluminescence maps. These fringe patterns were confirmed via extensive electromagnetic wave simulations to be standing-waves formed between the tip and the edge-up assembled nano-emitters on the substrate plane. We further report that both light confinement and in-plane emission can be engineered by tuning the surrounding dielectric environment of the nanoplatelets. Our results lead to renewed understanding of in-plane, near-field electromagnetic signal transduction from the localized nano-emitters with profound implications in nano and quantum photonics as well as resonant optoelectronics.

Wafer‐scale single‐crystalline MoSe2 and WSe2 monolayers grown by molecular‐beam epitaxy at low‐temperature — the role of island‐substrate interaction and surface steps

AbstractUltrathin two‐dimensional transition‐metal dichalcogenides (TMDs) have been pursued extensively in recent years for interesting physics and application potentials. For the latter, it is essential to synthesize crystalline TMD monolayers at wafer‐scale. Here, we report growth of single‐crystalline MSe2 (M = Mo, W) monolayers at wafer‐scale by molecular‐beam epitaxy at low temperatures (200–400°C) on nominally flat Au(1 1 1) substrates. The epifilms have low intrinsic defect densities of low 1012 cm−2. The grown films have then been exfoliated and transferred onto SiO2/Si by a wet chemical process, on which some optical measurements are performed, revealing high spatial uniformity of the samples. We also establish that MSe2 grows on Au via the van der Waals epitaxy mechanism, where a continuous film extends across the whole surface, overhangs atomic‐layer steps on substrate. We identify that the growth of highly crystalline MSe2 is promoted by an enhanced interaction between Au substrate and MSe2 islands rather than by the guidance of surface steps on substrate. The latter only arrests MSe2 lateral growth if they are multilayer high.Key points MBE growth of wafer‐scale highly crystalline TMD monolayers at low‐temperature is achieved. Island‐substrate interaction is found to play a critical role in vdW epitaxy of single‐crystalline TMDs on on‐axis substates. The TMD monolayers are of high uniformity and low intrinsic defect density.

Binding structure, breaking forces and conductance of Au-Octanedithiol-Au molecular junction under stretching processes: a DFT-NEGF study

Au-n-octanedithiol-Au molecular junction (Au-SC8S-Au) has been investigated using density functional theory combined with the nonequilibrium Green’s function approach. Theoretically calculated results are used to build the relationship between the interface binding structures and single-molecule quantum conductance of n-octanedithiol (SC8S) embodied in a gold nanogap with or without stretching forces. To understand the electron transport mechanism in the single molecular nanojunction, we designed three types of Au-SC8S-Au nanogaps, including flat electrode through an Au atom connecting (Model I), top-pyramidal or flat electrodes with the molecule adsorbing directly (Model II), and top-pyramidal Au electrodes with Au atomic chains (Model III). We first determined the optimized structures of different Au-SC8S-Au nanogaps, and then predicted the distance-dependent stretching force and conductance in each case. Our calculated results show that in the Model I with an Au atom bridging the flat Au (111) gold electrodes and the SC8S molecule, the conductance decreases exponentially before the fracture of Au–Au bond, in a good agreement with the experimental conductance in the literature. For the top-pyramidal electrode Models II and III, the magnitudes of molecular conductance are larger than that in Model I. Our theoretical calculations also show that the Au–Au bond fracture takes place in Models I and III, while the Au–S bond fracture appears in Model II. This is explained due to the total strength of three synergetic Au–Au bonds stronger than an Au–S bond in Model II. This is supported from the broken force about 2 nN for the Au–Au bond and 3 nN for the Au–S bond.

Biomimetic platinum forest enables 3D micro-supercapacitors with enhanced areal performance

Nowadays, the rapid development of portable micro-electronics has stimulated a significantly increasing demand in micro-supercapacitors (MSCs) for efficient micropower sources. However, the performance of MSCs is hindered by the dense electrode design with sluggish ion diffusion or reaction kinetics and tortuous charge transfer pathways, especially at high mass loading. Inspired by the structure of natural forest with efficient solar energy utilization, we fabricate an innovative biomimetic Pt forest (named forest-like Pt) as a robust three-dimensional (3D) conductive current collector by a simple one-step electrodeposition process. This hierarchical nanoarchitecture significantly improves the exposed surface areas of active electrode materials. As a proof-of-concept, 3D MSCs based on poly(3,4-ethylenedioxythiophene) (PEDOT) conducting polymer grown on such forest-like Pt exhibit an enhanced areal capacitance of 69.3 mF cm−2 at 0.1 mA cm−2, which is more than 5-fold larger than that of pristine PEDOT-based MSCs using conventional flat Au current collectors. Furthermore, the assembled 3D MSCs show a high areal energy density (6.16 μW h cm−2) and outstanding rate capability (63.2 mF cm−2 even at 5 mA cm−2). Thus, this novel design concept provides a new approach to build advanced electrode nanoarchitectures for the next-generation MSCs.

Controlling Surface Wettability and Plasmonic Resonance of Au/ZnO Heterostructured Films

This work investigated the (0002) textured ZnO films without and with the addition of an Au continuous top layer and its effects on their surface wettability and plasmonic resonance characteristics. The ZnO films were directly fabricated onto glass substrates at the synthesized temperature of 300 °C via a plasma-enhanced chemical vapor deposition (PECVD) system, and the as-synthesized ZnO film exhibited an average optical transmittance value of 85%. The ultraviolet (UV) light irradiation can be applied to enhance the hydrophilicity, changing it from a hydrophobic status to hydrophilic status due to the existing and adjustable characteristics of the photocatalytic activity. On the other hand, the surface wetting/contact angle (CA) value of the ZnO film with a controllable surface wettability switched from 94° (hydrophobicity) to 44° (hydrophilicity), after it was exposed to UV light irradiation for 5 min, and stably reversed back to hydrophobicity (92°) via a post-annealed treatment using rapid thermal annealing (RTA) at 350 °C for 5 min in air. A fast, simple, and reversible method for switching between hydrophilic and hydrophobic status is claimed in this present work. The improved surface plasmonic resonance is owning to the coupled electron and photon oscillations that can be obtained and produced at the interface between the flat Au layer and ZnO (metal/metallic oxide) heterostructured films for future applications of various wide-bandgap compound semiconductors.

Electrodeposition of Three-Dimensional Au Nanowire Networks and Their Application As Catalysts for Methanol Electro-Oxidation

In this talk we will first present the synthesis of free-standing, stable gold nanowire network with controlled morphology and geometry by ion-track technology and electrodeposition. Etched ion-track membranes with interconnected nanochannels are produced by sequential GeV heavy ion irradiation of polymer foils from four directions, and subsequent etching and enlargment of the created ion-tracks. Au nanowire networks with three different nanowire diameters are synthesized by potentiostatic electrodeposition in the templates. Nanowire growth rate and homogeneity are tuned by varying the deposition potential. The electrochemical surface area was determined for each sample by CV analysis of surface oxide reduction reaction charge transfer. We will also discuss the catalytic performance of these Au nanowire networks towards methanol electro-oxidation, acting as an electrode in a half-cell setup. High current density and high catalytic activity were recorded. The Au nanowire networks provided up to 200 times higher peak current density than a flat Au electrode, along with excellent long term cyclability, which the current density drops only 5% over 200 CV cycles. SEM studies of the morphology and crystallinity of the nanowires before and after the methanol oxidation reaction will also be presented in the talk.Figure 1. (a) SEM image of Au nanowire network, (b) Cyclic Voltammograms recorded for a of Au nanowire network in 0.1 M KOH with (solid line) and without (dash line) 1 M MeOH. Figure 1

Quantitative determination of the electric field strength in a plasmon focus from ponderomotive energy shifts

Abstract Spectroscopic photoemission microscopy is used to detect and quantify a ponderomotive shift in the energy of electrons that are emitted from a surface plasmon polariton focus. The focus is formed on an atomically flat Au(111) surface by an Archimedean spiral and is spatiotemporally separated from the circularly polarized light pulse used to excite the spiral. A spectroscopic analysis of electrons emitted from the focus exhibits a peaked above-threshold electron emission spectrum. From the shift of the peaks as function of laser power the field strength of the surface plasmon polariton was quantitatively determined without free parameters. Estimations of the Keldysh parameter γ = 4.4 and the adiabaticity parameter δ = 4700 indicate that electron emission occurs in a regime of multiplasmon absorption and nonlocalized surface plasmon fields.

(Invited, Digital Presentation) Influence of Hemisphere-Shaped Nanodimples of Gold Electrode on Capacitance in Ionic Liquid

Ionic liquids (ILs) have attracted much attention as promising electrolytes for electrochemical devices due to their wide electrochemical window (stability) and negligible vaporization. For such applications, nanostructured electrodes have advantage on their large surface area leading to accumulation of large density energy at the interface. However, recent reports on IL/electrode interfaces revealed that quite unique structures can be formed, and it is not clear how the interface forms and how it changes by forming an electric double layer (EDL). In this study, we investigated the interfacial capacitance of nanostructured Au electrodes using electrochemical impedance spectroscopy (EIS) and IR measurements.Polystyrene beads were self-assembled in a close packed form on a gold substrate by dipping in polystyrene beads solution and rapid drying. Au electrodeposition on thus prepared surface followed by removal of the beads resulted in the fabrication of a nanostructured Au electrode with periodic dimples. Electrochemical behavior of a ferrocene dissolved ionic liquid (1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) amide (BMI-TFSA)) at the nanostructured and flat Au electrodes were investigated by EIS. We found that the capacitance of the nanostructured electrode was smaller than that of the flat electrode in the whole potential range. This result suggests that the thickness of the electric double layer formed in the nano-sized dimple is thicker than that formed on the flat surface. In the case of nanostructured Au electrode having 160 nm diameter dimples, the large capacitance was observed comparing with other electrodes having the dimples of different sizes. In addition, on the negative-going scan, the capacitance takes maximum at 0.1 V vs. Fc/Fc+, whereas no peak was found on the reverse positive-going scan. This result indicates that the exchange of cation/anion layers smoothly proceeded on the negative-going scan, whereas such a smooth exchange was prevented due to strongly surface-adsorbed BMIM+ on the positive-going scan. We also found that the hysteresis behavior was relatively suppressed in the case of the electrodes having 70 nm and 120 nm diameter dimples. We carried out the In-situ ATR-IR measurement to investigate the structure of ionic liquid molecules at the ionic liquid/electrode interface. The details of the relationships between the arrangement of ionic liquid at the interface and the capacitance of the electrode will be discussed.

Visualizing On-Surface Decomposition Chemistry at the Nanoscale Using Tip-Enhanced Raman Spectroscopy.

Chemical imaging of molecular decomposition processes at solid-liquid interfaces is a long-standing problem in achieving mechanistic understanding. Conventional analytical tools fail to meet this challenge due to the lack of required chemical sensitivity and specificity at the nanometer scale. In this work, we demonstrate that high-resolution hyperspectral tip-enhanced Raman spectroscopy (TERS) imaging can be a powerful analytical tool for studying on-surface decomposition chemistry at the nanoscale. Specifically, we present a TERS-based hyperspectral approach to visualize the on-surface decomposition process of a pyridine-4-thiol self-assembled monolayer on atomically flat Au(111) surfaces under ambient conditions. Reactive intermediates involved in the degradation process are spectroscopically detected with 5 nm spatial resolution. With supporting density functional theory simulations, a key species could be assigned to the disulfide reaction intermediate. This work opens a new application area for studying on-surface decomposition chemistry and related dynamics quantitatively at solid-liquid interfaces with nanometer spatial resolution.

Enhanced Light Absorption and Efficient Carrier Collection in MoS2 Monolayers on Au Nanopillars.

We fabricated hybrid nanostructures consisting of MoS2 monolayers and Au nanopillar (Au-NP) arrays. The surface morphology and Raman spectra showed that the MoS2 flakes transferred onto the Au-NPs were very flat and nonstrained. The Raman and photoluminescence intensities of MoS2/Au-NP were 3- and 20-fold larger than those of MoS2 flakes on a flat Au thin film, respectively. The finite-difference time-domain calculations showed that the Au-NPs significantly concentrated the incident light near their surfaces, leading to broadband absorption enhancement in the MoS2 flakes. Compared with a flat Au thin film, the Au-NPs enabled a 6-fold increase in the absorption in the MoS2 monolayer at a wavelength of 615 nm. The contact potential difference mapping showed that the electric potential at the MoS2/Au contact region was higher than that of the suspended MoS2 region by 85 mV. Such potential modulation enabled the Au-NPs to efficiently collect photogenerated electrons from the MoS2 flakes, as revealed by the uniform positive surface photovoltage signals throughout the MoS2 surface.