Au Surface Research Articles

Noncontact Layer Stabilization of Azafullerene Radicals: Route toward High-Spin-Density Surfaces.

We deposit azafullerene C59N• radicals in a vacuum on the Au(111) surface for layer thicknesses between 0.35 and 2.1 monolayers (ML). The layers are characterized using X-ray photoemission (XPS) and X-ray absorption fine structure (NEXAFS) spectroscopy, low-temperature scanning tunneling microscopy (STM), and by density functional calculations (DFT). The singly unoccupied C59N orbital (SUMO) has been identified in the N 1s NEXAFS/XPS spectra of C59N layers as a spectroscopic fingerprint of the molecular radical state. At low molecular coverages (up to 1 ML), films of monomeric C59N are stabilized with the nonbonded carbon orbital neighboring the nitrogen oriented toward the Au substrate, whereas in-plane intermolecular coupling into diamagnetic (C59N)2 dimers takes over toward the completion of the second layer. By following the C59N• SUMO peak intensity with increasing molecular coverage, we identify an intermediate high-spin-density phase between 1 and 2 ML, where uncoupled C59N• monomers in the second layer with pronounced radical character are formed. We argue that the C59N• radical stabilization of this supramonolayer phase of monomers is achieved by suppressed coupling to the substrate. This results from molecular isolation on top of the passivating azafullerene contact layer, which can be explored for molecular radical state stabilization and positioning on solid substrates.

In situ surface evolution dynamics of external-electric-field-triggered structural oscillation on Au(111)

Surface nanostructures serve as an essential role in determining intrinsic physical features and device performance in solid materials. Here, this work systematically investigates the surface dynamical evolution at the nanoscale on Au(111) induced by a “tip-to-surface” external electric field through a scanning tunneling microscope (STM). The Au(111) steps exhibit a “compact to fractal” reconstruction under a relatively high electric field, in which the transition is strengthened with increasing the applied electric field. Inversely, a “fractal to compact” morphological transition enables to be self-triggered at Au(111) surface steps upon a normal STM imaging electric field (very low). These two reversible structural changes are attributed to the diffusion-limited aggregation mechanism where the diffusion barriers were quantified as 0.64–0.75 eV varied with the regularity in step edges. In addition, we further simulate a “terrace-edge-kink” model to trace the effect of atomic coordination on structural transition, determining the surface step edge stability. This study presents insight into morphological and structural transformation at surface steps induced by variant external electric fields, establishing a deep understanding in the nature of surface evolution dynamics.

Long and isolated graphene nanoribbons by on-surface polymerization on Au(111)

Low electronic gap graphene nanoribbons (GNRs) are used for the fabrication of nanomaterial-based devices and, when isolated, for mono-molecular electronics experiences, for which a well-controlled length is crucial. Here, an on-surface chemistry protocol is monitored for producing long and well-isolated GNR molecular wires on an Au(111) surface. The two-step Ullmann coupling reaction is sequenced in temperature from 100 °C to 350 °C by steps of 50 °C, returning at room temperature between each step and remaining in ultrahigh vacuum conditions. After the first annealing step at 100 °C, the monomers self-organize into 2-monolayered nano-islands. Next, the Ullmann coupling reaction takes place in both 1st and 2nd layers of those nano-islands. The nano-island lateral size and shape are controlling the final GNR lengths. Respecting the above on-surface chemistry protocol, an optimal initial monomer coverage of ~1.5 monolayer produces isolated GNRs with a final length distribution reaching up to 50 nm and a low surface coverage of ~0.4 monolayer suitable for single molecule experiments.

Impact of grain-dependent boron uptake on the nano-electrical and local optical properties of polycrystalline boron doped CVD diamond

Boron-doped diamond (BDD) films grown by chemical vapor deposition (CVD) exhibit unique electrical and optical properties owing to the non-uniform uptake of boron dopants across grains. This study utilizes scanning probe microscopy and confocal micro- spectroscopy techniques to elucidate the influence of grain-dependent boron incorporation on the nano-electrical and local optical characteristics of polycrystalline BDD. The CVD- grown BDD film contained crystallites up to tens of microns, while the surface comprised 200…800 nm grains. Scanning spreading resistance microscopy (SSRM) revealed significant nanoscale resistance variations among individual grains, attributable to differential boron distributions. No distinct grain boundary features were discernible in SSRM data, likely due to the high boron doping of ~ 3·10 19 cm –3 . SSRM of the Au surface of a BDD/Ti/Pd/Au contact indicated a comparable granular morphology but three orders lower resistance. A network of more resistive grain boundaries was evident, modulated by underlying BDD grain clusters. Photoluminescence spectroscopy showed characteristic bands of nitrogen-vacancy centers and donor-acceptor pairs. Confocal Raman and photoluminescence mapping elucidated substantial spatial heterogeneity in micrometer- scale grains regarding crystal quality, boron and nitrogen concentrations, related to preferential incorporation. The observed peculiarities in BDD’s structural and nano- electrical characteristics stem from inherent growth inhomogeneities and grain-dependent boron uptake influenced by defects and strain fields modifying local chemical potentials. This multifaceted nanoscale examination provides critical insights into optimizing electrical and optical properties of BDD films by controlling synthesis conditions and minimizing defects for tailored performance in electronic, electrochemical, and quantum applications.

Effect of Surface Pt Doping on the Reactivity of Au(111) Surfaces towards Methanol Dehydrogenation: A First-Principles Density Functional Theory Investigation

The surprisingly high catalytic activity of gold has been known to the heterogeneous catalysis community since the mid-1980s. Significant efforts have been directed towards improving the reactivity of these surfaces towards important industrial reactions. One such strategy is the introduction of small amounts of other metals to create Au-based surface alloys. In this work, we investigated the synergistic effect of the Pt doping of a Au(111) surface on decreasing the activation barrier of the methanol dehydrogenation elementary step within first-principles density functional theory. To this end, we constructed several models of Pt-doped Au(111) surfaces, including a full Pt overlayer and monolayer. The effect of Pt surface doping was then investigated via the computation of the adsorption energies of the various chemical species involved in the catalytic step and the estimation of the activation barriers of methanol dehydrogenation. Both the electronic and strain effects induced by Pt surface doping substantially lowered the activation energy barrier of this important elementary reaction step. Moreover, in the presence of preadsorbed atomic oxygen, Pt surface doping could be used to reduce the activation energy for methanol dehydrogenation to as low as 0.1 eV.

Deformation twin traces on gold surfaces: A pathway to tailored epitaxial growth of 1D semiconductors.

The field of one-dimensional semiconducting materials holds a wide variety of captivating applications, such as photovoltaic cells, electronic devices, catalysis cells, lasers, and more. The tunability of electrical, mechanical, or optical attributes of a semiconductor crystal relies on the ability to control and pattern the crystal's growth direction, orientation, and dimensions. In this study, we harvest the unique properties of crystallographic defects in Au substrates, specifically twin boundaries, to fabricate selective epitaxial growth of semiconducting nanocrystals. Different crystallographic defects were previously shown to enhance materials properties, such as, screw dislocations providing spiral crystal growth, dislocation outcrops, and vacancies increasing their catalytic activity, dislocation strengthening, and atomic doping changing the crystal's electrical properties. Here, we present a unique phenomenon of directed growth of semiconductor crystals of gold(I)-cyanide (AuCN) on the surface of thin Au layers, using traces of deformation twins on the surface. We show that emergence of deformation twins to the {111} Au surface leads to the formation of ledges, exposing new {001} and {111} facets on the surface. We propose that this phenomenon leads to epitaxial growth of AuCN on the freshly exposed {111} facets of the twin boundary trace ledges. Specific orientations of the twin boundaries with respect to the Au surface allow for patterned growth of AuCN in the <110> orientations. Nano-scale patterning of AuCN semiconductors may provide an avenue for property tuning, particularly the band gap acquired.

Ultrafast dynamics and ablation mechanism in femtosecond laser irradiated Au/Ti bilayer systems

Abstract The significance of ultrafast laser-induced energy and mass transfer at interfaces has been growing in the field of nanoscience and technology. Nevertheless, the complexity arising from non-linear and non-equilibrium optical-thermal-mechanical interactions results in intricate transitional behaviors. This complexity presents challenges when attempting to analyze these phenomena exclusively through modeling or experimentation. In this study, we conduct time-resolved reflective pump-probe imaging and molecular-dynamics coupled two-temperature model (MD-TTM) simulations to investigate the ultrafast dynamics and ablation mechanism of Au/Ti bilayer systems. The calculated energy absorption curves indicate that Au film reduces the energy deposition in the underlying Ti layer, resulting in reduced melting and evaporation rate of Ti. The phase transition process induces different mechanical responses. The potential energy patterns indicate that the expansion of vapor Ti extrudes the surface Au layer outward. In simulated stress distribution images, the Au layer can hamper the expansion of the vapor-phase Ti and brings dynamic compressive stress to the residual Ti layer. When the compressive stress transforms into tensile stress, the material is removed through mechanical damage. Therefore, both Au and Ti in the 20 nm Au-covered Ti are completely removed. Our approach elucidates the ablation mechanism within the Au/Ti bilayer system and offers fresh insights into managing thermo-mechanical responses within analogous systems.

In Situ Probing of CO2 Reduction on Cu-Phthalocyanine-Derived Cux O Complex.

An in situ measurement of a CO2 reduction reaction (CO2 RR) in Cu-phthalocyanine (CuPC) molecules adsorbed on an Au(111) surface is performed using electrochemical scanning tunneling microscopy. One intriguing phenomenon monitored in situ during CO2 RR is that a well-ordered CuPC adlayer is formed into an unsuspected nanocluster via molecular restructuring. At an electrode potential of -0.7V versus Ag/AgCl, the Au surface is covered mainly with the clusters, showing restructuring-induced CO2 RR catalytic activity. Using a measurement of X-ray photoelectron spectroscopy, it is revealed that the nanocluster represents a Cu complex with its formation mechanism. This work provides an in situ observation of the restructuring of the electrocatalyst to understand the surface-reactive correlations and suggests the CO2 RR catalyst works at a relatively low potential using the CuPC-derived Cu nanoclusters as active species.

Design of a Facile Antifouling Sensor Based on the Synergy between an Antibody and Phase-Transited BSA.

Nonspecific adsorption has always been a critical challenge for sensor detection; thus, an efficient and facile approach for fabricating antifouling sensors is highly desirable. Here, we developed an antifouling coating on sensor surfaces, conveniently made with a simple drip of phase-transited BSA (PTB) followed by a modification with a peanut allergen antibody, which unexpectedly provides synergistic antifouling properties in sensors. Atomic force microscopy and scanning electron microscopy were used to evaluate the surface evenness. Optimizations in terms of PTB modification time and concentrations were performed using surface plasmon resonance by measuring protein resistance capabilities. Compared to bare Au surfaces, the PTB-modified surfaces exhibited low adsorption against BSA (<10 ng/cm2) and good resistance against lysozyme (Lyz). After immobilizing antibodies, the antifouling performance of the sensor coatings had an obvious enhancement, with almost no BSA adsorption and low lysozyme adsorption. The target recognition was also analyzed to verify the good sensing performance of the antifouling sensor. This understanding of antibody synergy provides suggestions for the development of antifouling sensors.

&lt;i&gt;In Situ&lt;/i&gt; TEM Observation of the Ultrasonic Bonding Process

In the ultrasonic bonding process, oxides existing on the metal surfaces are removed, and bonding is achieved by bringing clean surfaces to be in contact with each other. However, the bonding process with microstructure variation is not well understood due to experimental difficulties. In this study, using a newly developed sample holder, which enables ultrasonic bonding in a TEM, we directly observed the bonding process at the nanoscale. The bonding process of Au foils with a clean surface was investigated and compared to that of Al foils with a stable oxide film, a bonding inhibitor, on the surface. During the Al ultrasonic bonding process, the nanoparticles generated dispersed over the entire bonding interface and finally formed a fine grain region at the interface. In contrast, in Au bonding, the nanoparticles generated tended to accumulate at the local area of the Au surface and form bridge-like connections between Au foils. It was considered that these differences in bonding behavior were caused by the surface conditions of the materials to be bonded.

Observing π-Au Interaction between Aromatic Molecules and Single Au Nanodimers with a Subnanometer Gap by SERS.

Interface interaction between aromatic molecules and noble metals plays a prominent role in fundamental science and technological applications. However, probing π-metal interactions under ambient conditions remains challenging, as it requires characterization techniques to have high sensitivity and molecular specificity without any restrictions on the sample. Herein, the interactions between polycyclic aromatic hydrocarbon (PAH) molecules and Au nanodimers with a subnanometer gap are investigated by surface-enhanced Raman spectroscopy (SERS). A cleaner and stronger plasmonic field of subnanometer gap Au nanodimer structures was constructed through solvent extraction. High sensitivity and strong π-Au interaction between PAHs and Au nanodimers are observed. Additionally, the density functional theory calculation confirmed the interactions of PAHs physically absorbed on the Au surface; the binding energy and differential charge further theoretically indicated the correlation between the sensitivity and the number of PAH rings, which is consistent with SERS experimental results. This work provides a new method to understand the interactions between aromatic molecules and noble metal surfaces in an ambient environment, also paving the way for designing the interfaces in the fields of catalysis, sensors, and molecular electronics.

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.

Influence of van der Waals Interactions between the Alkyl Chains of Surface Ligands on the Size and Size Distribution of Nanocrystals Prepared by the Digestive Ripening Process.

Thermal heating of polydispersed nanocrystals (NCs) with surface-active organic ligands in a solvent leads to the formation of monodispersed NCs, and this process is known as digestive ripening (DR). Here, by performing DR on Au NCs using different-chain-length amine and thiol ligands, we evidently show that ligands with C12 chain length result in the formation of NCs with narrow size distributions when compared to C8, C16, and C20 chain length ligands. Furthermore, our findings also show that in the case of alkyl thiol, the NC size remains more or less the same, while the size distribution gets altered significantly with the chain length. On the other hand, both size and size distribution are affected significantly when the alkyl amine chain length is varied. Fourier transform infrared (FTIR) studies indicate that the van der Waals (vdW) interactions are weakest when the amine with C12 carbon chain is used as the DR agent, while in the case of thiols, molecules with C8 and C12 chain lengths have nearly the same vdW interactions (with C12 slightly weaker than C8), which are weaker than those of C16 and C20. Molecular dynamics (MD) simulation results corroborate the experimental observations and suggest that due to more defects in the alkyl chain, the C8 and C12 (amine as well as thiol) ligands are disordered and less stable on Au(111) and Au(100) surfaces. This could result in efficient etching and redeposition, making the ligands with C8 and C12 chain lengths the better DR agents.

Length-Dependent Magnetic Evolution of Anthenes on Au(111).

Nanographenes with zigzag edges, for example, anthenes, exhibit a unique nonbonding π-electron state, which can be described as a spin-polarized edge state that yields specific magnetic ground state. However, prior researches on the magnetism of anthenes with varying lengths on a surface is lacking. This study systematically fabricated anthenes with inherent zigzag carbon atoms of different lengths ranging from bisanthene to hexanthene. Their magnetic evolution on the Au(111) surface was analyzed through bond-resolved scanning probe techniques and density functional theory calculations. The analyses revealed a transition in magnetic properties associated with the length of the anthenes, arising from the imbalance between hybridization energy and the Coulomb repulsion between valence electrons. With the increasing length of the anthenes, the ground state transforms gradually from a closed-shell to an antiferromagnetic open-shell singlet, exhibiting a weak exchange coupling of 4 meV and a charge transfer-induced doublet. Therefore, this study formulated a chemically tunable platform to explore size-dependent π magnetism at the atomic scale, providing a framework for research in organic spintronics.

Length‐Dependent Magnetic Evolution of Anthenes on Au(111)

AbstractNanographenes with zigzag edges, for example, anthenes, exhibit a unique nonbonding π‐electron state, which can be described as a spin‐polarized edge state that yields specific magnetic ground state. However, prior researches on the magnetism of anthenes with varying lengths on a surface is lacking. This study systematically fabricated anthenes with inherent zigzag carbon atoms of different lengths ranging from bisanthene to hexanthene. Their magnetic evolution on the Au(111) surface was analyzed through bond‐resolved scanning probe techniques and density functional theory calculations. The analyses revealed a transition in magnetic properties associated with the length of the anthenes, arising from the imbalance between hybridization energy and the Coulomb repulsion between valence electrons. With the increasing length of the anthenes, the ground state transforms gradually from a closed‐shell to an antiferromagnetic open‐shell singlet, exhibiting a weak exchange coupling of 4 meV and a charge transfer‐induced doublet. Therefore, this study formulated a chemically tunable platform to explore size‐dependent π magnetism at the atomic scale, providing a framework for research in organic spintronics.

Mixed Nanosphere Assemblies at a Liquid-Liquid Interface.

The in-plane packing of gold (Au), polystyrene (PS), and silica (SiO2) spherical nanoparticle (NP) mixtures at a water-oil interface is investigated in situ by UV-vis reflection spectroscopy. All NPs are functionalized with carboxylic acid such that they strongly interact with amine-functionalized ligands dissolved in an immiscible oil phase at the fluid interface. This interaction markedly increases the binding energy of these nanoparticle surfactants (NPSs). The separation distance between the Au NPSs and Au surface coverage are measured by the maximum plasmonic wavelength (λmax) and integrated intensities as the assemblies saturate for different concentrations of non-plasmonic (PS/SiO2) NPs. As the PS/SiO2 content increases, the time to reach intimate Au NP contact also increases, resulting from their hindered mobility. λmax changes within the first few minutes of adsorption due to weak attractive inter-NP forces. Additionally, a sharper peak in the reflection spectrum at NP saturation reveals tighter Au NP packing for assemblies with intermediate non-plasmonic NP content. Grazing incidence small angle X-ray scattering (GISAXS) and scanning electron microscopy (SEM) measurements confirm a decrease in Au NP domain size for mixtures with larger non-plasmonic NP content. The results demonstrate a simple means to probe interfacial phase separation behavior using in situ spectroscopy as interfacial structures densify into jammed, phase-separated NP films.

Au‐Catalyzed Energy Release in a Molecular Solar Thermal (MOST) System: A Combined Liquid‐Phase and Surface Science Study

AbstractMolecular solar thermal systems (MOSTs) are molecular systems based on couples of photoisomers (photoswitches), which combine solar energy conversion, storage, and release. In this work, we address the catalytically triggered energy release in the promising MOST couple phenylethylesternorbornadiene/quadricyclane (PENBD/PEQC) on a Au(111) surface in a combined liquid‐phase and surface science study. We investigated the system by photoelectrochemical infrared reflection absorption spectroscopy (PEC‐IRRAS) in the liquid phase, conventional IRRAS and synchrotron radiation photoelectron spectroscopy (SRPES) in ultra‐high vacuum (UHV). Au(111) is highly active towards catalytically triggered energy release. In the liquid phase, we did not observe any decomposition of the photoswitch, no deactivation of the catalyst within 100 conversion cycles and we could tune the energy release rate of the heterogeneously catalyzed process by applying an external potential. In UHV, submonolayers of PEQC on Au(111) are back‐converted to PENBD instantaneously, even at 110 K. Multilayers of PEQC are stable up to ~220 K. Above this temperature, the intrinsic mobility of the film is high enough that PEQC molecules come into direct contact with the Au(111) surface, which catalyzes the back‐conversion. We suggest that this process occurs via a singlet–triplet mechanism induced by electronic coupling between the PEQC molecules and the Au(111) surface.

Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis.

Plasmonic catalysts have the potential to accelerate and control chemical reactions with light by exploiting localized surface plasmon resonances. However, the mechanisms governing plasmonic catalysis are not simple to decouple. Several plasmon-derived phenomena, such as electromagnetic field enhancements, temperature, or the generation of charge carriers, can affect the reactivity of the system. These effects are convoluted with the inherent (nonplasmonic) catalytic properties of the metal surface. Disentangling these coexisting effects is challenging but is the key to rationally controlling reaction pathways and enhancing reaction rates. This study utilizes super-resolution fluorescence microscopy to examine the mechanisms of plasmonic catalysis at the single-particle level. The reduction reaction of resazurin to resorufin in the presence of Au nanorods coated with a porous silica shell is investigated in situ. This allows the determination of reaction rates with a single-molecule sensitivity and subparticle resolution. By variation of the irradiation wavelength, it is possible to examine two different regimes: photoexcitation of the reactant molecules and photoexcitation of the nanoparticle's plasmon resonance. In addition, the measured spatial distribution of reactivity allows differentiation between superficial and far-field effects. Our results indicate that the reduction of resazurin can occur through more than one reaction pathway, being most efficient when the reactant is photoexcited and is in contact with the Au surface. In addition, it was found that the spatial distribution of enhancements varies, depending on the underlying mechanism. These findings contribute to the fundamental understanding of plasmonic catalysis and the rational design of future plasmonic nanocatalysts.

On‐Surface Interchain Coupling and Skeletal Rearrangement of Indenofluorene Polymers

AbstractOn‐surface synthesis serves as a powerful approach to construct π‐conjugated carbon nanostructures that are not accessible by conventional wet chemistry. Nevertheless, this method has been limited by the types and numbers of available on‐surface transformations. While the majority of successful cases exploit thermally triggered dehalogenative carbon–carbon coupling and cyclodehydrogenation, rearrangement of appropriate functional moieties has received limited research attention. Here, the unprecedented interchain coupling and thermally induced skeleton rearrangement are described of (dihydro)indeno[2,1‐b]fluorene (IF) polymers on an Au(111) surface under ultrahigh vacuum conditions, leading to different ladder polymers as well as fully fused graphene nanoribbon segments containing pentagonal and heptagonal rings. Au‐coordinated nanoribbons are also observed. All structures are unambiguously characterized by high‐resolution scanning probe microscopy. The current results provide an avenue to fabricating a wider variety of π‐conjugated polymers and carbon nanostructures comprising nonhexagonal rings as well as rarely explored organometallic nanoribbons.

Long Range and Collective Impact of Au Surface Adatoms on Nanofin Growth

Long Range and Collective Impact of Au Surface Adatoms on Nanofin Growth