Deposition Of Adatoms Research Articles

Monodispersed mesoscopic star-shaped gold particles via silver-ion-assisted multi-directional growth for highly sensitive SERS-active substrates

Surface-enhanced Raman scattering (SERS) exploits localized surface plasmon resonances in metallic nanostructures to significantly amplify Raman signals and perform ultrasensitive analyses. A critical factor for SERS-based analysis systems is the formation of numerous electromagnetic hot spots within the nanostructures, which represent regions with highly concentrated fields emerging from excited localized surface plasmons. These intense hotspot fields can amplify the Raman signal by several orders of magnitude, facilitating analyte detection at extremely low concentrations and highly sensitive molecular identification at the single-nanoparticle level. In this study, mesoscopic star-shaped gold particles (gold mesostars) were synthesized using a three-step seed-mediated growth approach coupled with the addition of silver ions. Our study confirms the successful synthesis of gold mesostars with numerous sharp tips via the multi-directional growth effect induced by the underpotential deposition of silver adatoms (AgUPD) onto the gold surfaces. The AgUPD process affects the nanocrystal growth kinetics of the noble metal and its morphological evolution, thereby leading to intricate nanostructures with high-index facets and protruding tips or branches. Mesoscopic gold particles with a distinctive star-like morphology featuring multiple sharp projections from the central core were synthesized by exploiting this phenomenon. Sharp tips of the gold mesostars facilitate intense localized electromagnetic fields, which result in strong SERS enhancements at the single-particle level. Electromagnetic fields can be further enhanced by interparticle hot spots in addition to the intraparticle local field enhancements when arranged in multilayered arrays on substrates, rendering these arrays as highly efficient SERS-active substrates with improved sensitivity. Evaluation using Raman-tagged analytes revealed a higher SERS signal intensity compared to that of individual mesostars because of interparticle hot spots enhancements. These substrates enabled analyte detection at a concentration of 10− 9 M, demonstrating their remarkable sensitivity for trace analysis applications.

Cooperative Effect of Cations and Catalyst Structure in Tuning Alkaline Hydrogen Evolution on Pt Electrodes.

The kinetics of hydrogen evolution reaction (HER) in alkaline media, a reaction central to alkaline water electrolyzers, is not accurately captured by traditional adsorption-based activity descriptors. As a result, the exact mechanism and the main driving force for the water reduction or HER rate remain hotly debated. Here, we perform extensive kinetic measurements on the pH- and cation-dependent HER rate on Pt single-crystal electrodes in alkaline conditions. We find that cations interacting with Pt step sites control the HER activity, while they interact only weakly with Pt(111) and Pt(100) terraces and, therefore, cations do not affect HER kinetics on terrace sites. This is reflected by divergent activity trends as a function of pH as well as cation concentration on stepped Pt surfaces vs Pt surfaces that do not feature steps, such as Pt(111). We show that HER activity can be optimized by rationally tuning these step-cation interactions via selective adatom deposition at the steps and by choosing an optimal electrolyte composition. Our work shows that the catalyst and the electrolyte must be tailored in conjunction to achieve the highest possible HER activity.

Roles of Re and Cs Promoters and Organochlorine Moderators in the Synthesis of Ethylene Oxide on Ag‐based Catalysts

AbstractC2H4−O2 reactions form ethylene oxide (EO) on Ag nanoparticles dispersed on α‐Al2O3 and promoted with alkali and other elements, with Re and Cs most frequently used in practice. Traces of alkyl chlorides (e. g., C2H5Cl) and alkanes in much larger amounts are added to reactants to balance the rate of deposition and removal (and the coverage) of Cl adatoms (Cl*) on Ag surfaces. Such Cl adlayers retain Ag surface ensembles that form O2‐derived intermediates that favor EO synthesis, but typically decrease O2 activation rates. A series of Ag/α‐Al2O3 catalysts (with and without Re or Cs) are used here to examine the role of promoters and Cl moderators through an analysis of the effects of reaction conditions and C2H5Cl levels using convection‐reaction constructs and a mechanistic formalism that considers O2 (as chemisorbed O2*) as the reactant in EO synthesis through one electrophilic O‐atom, with the second O‐atom (O*) acting as a unselective nucleophile that must be scavenged by a sacrificial reductant (C2H4 or EO); such channels are precluded by any intervening O2 dissociation events (that form two O*). O2 consumption rates in C2H4−O2 reactions decrease 10‐fold upon exposing Ag/α‐Al2O3 to C2H5Cl, evincing persistent Cl* species that block active sites and require >104 C2H4 oxidation turnovers to be removed. Activation barriers do not change but relative rates of epoxidation versus combustion increase in the presence of this refractory Cl* adlayer, which reduces the number and shrinks the size of available site ensembles without altering their intrinsic reactivity for O2 activation to form O2* but attenuating rates of its subsequent dissociation. Refractory O* adlayers also form on Ag surfaces, as shown by the accumulation of persistent O* species upon exposing reduced Ag particles to N2O. Inter‐atom repulsive forces weaken O* binding and destabilize N2O decomposition transition states to eventually allow stable N2 and O2 evolution for catalytic N2O decomposition, which occurs at landing ensembles formed at interstices of refractory adlayers. Cl* forms denser adlayers than O*, as evidenced by a 10‐fold decrease not only to C2H4−O2 rates but also to N2O stoichiometric and catalytic rates and O* uptakes. The occasional evolution of O2, which forms larger landing ensembles that more readily form 2O* from O2, occurs with higher frequency from O* than mixed O*/Cl* adlayers, and this effect of Cl* to inhibit (O−O)* dissociation is demonstrated in CO probe reaction studies, which show that highly reactive bound dioxygen species are retained to a greater extent when adlayers comprise both Cl* and O*. Re and Cs do not influence the nature of such adlayers but increase and decrease, respectively, the number of acid sites and selectivity losses via EO combustion. Their respective domains may also block a modest fraction of Ag surfaces without consequences on intrinsic O2 activation rates or EO selectivities. The effects of Re beyond those reported here may emerge upon synthetic protocols that alter Re location and Ag−Re intimacy to enable channels which utilize both O‐atoms in epoxidation.

Roughness Factors of Electrodeposited Nanostructured Copper Foams

Copper-based electrocatalytic materials play a critical role in various electrocatalytic processes, including the electroreduction of carbon dioxide and nitrate. Three-dimensional nanostructured electrodes are particularly advantageous for electrocatalytic applications due to their large surface area, which facilitates charge transfer and mass transport. However, the real surface area (RSA) of electrocatalysts is a crucial parameter that is often overlooked in experimental studies of high-surface-area copper electrodes. In this study, we investigate the roughness factors of electrodeposited copper foams with varying thicknesses and morphologies, obtained using the hydrogen bubble dynamic template technique. Underpotential deposition (UPD) of metal adatoms is one of the most reliable methods for estimating the RSA of highly dispersed catalysts. We aim to illustrate the applicability of UPD of lead for the determination of the RSA of copper deposits with hierarchical porosity. To find the appropriate experimental conditions that allow for efficient minimization of the limitations related to the slow diffusion of lead ions in the pores of the material and background currents of the reduction of traces of oxygen, we explore the effect of lead ion concentration, stirring rate, scan rate, monolayer deposition time and solution pH on the accuracy of RSA estimates. Under the optimized measurement conditions, Pb UPD allowed to estimate roughness factors as high as 400 for 100 µm thick foams, which translates into a specific surface area of ~6 m2·g−1. The proposed measurement protocol may be further applied to estimate the RSA of copper deposits with similar or higher roughness.

Harmonic generation in bent graphene with artificially enhanced spin-orbit coupling

We theoretically investigate the nonlinear response of bent graphene, in the presence of artificially-enhanced spin-orbit coupling, which can occur either via adatom deposition, or by placing the sheet of bent graphene in contact with a spin-orbit active substrate. We discuss the interplay between the spin-orbit coupling and the artificial magnetic field generated by the bending, for both the cases of Rashba and intrinsic spin-orbit coupling. For the latter, we introduce a spin-field interaction Hamiltonian addressing directly the electron spin as a degree of freedom. Our findings reveal that in this case, by controlling the amount of spin-orbit coupling, it is possible to significantly tune the spectrum of the nonlinear signal, achieving, in principle, efficient conversion of light from THz to UV region.

Theoretical Analysis of the Flower‐Shaped Pattern Distribution in Self‐Catalyzed GaN Nanorod

The strain‐induced growth of self‐induced GaN nanorods (NRs) on the sapphire substrate is investigated experimentally. From cathodoluminescence (CL) results, it is noticed that the distributions of the flower‐shaped pattern are varied with the increment in NR height. Based on the experimental observation, a simulation model for NR formation is established, which is in good agreement with the experimental data. Then, the preferred nucleation position for adatom deposition in the NR growth process is theoretically analyzed. Finally, an equilibrium growth condition for the vapor–solid (VS) and vapor–liquid–solid (VLS) mechanism of GaN NR growth is proposed.

Enhancement of the magnetic anisotropy in single semiconductor nanowires via surface doping and adatom deposition

The magnetic anisotropy of single semiconductor (ZnO and GaN) nanowires incorporating both a transition metal (Co and Mn, respectively) as a substitutional surface dopant and a heavy metal (Au, Bi, or Pt) adatom is studied by performing density-functional supercell calculations with the Hubbard U correction. It is found that a substantial enhancement in the magnetic anisotropy energy is obtained through the deposition of Bi; the deposition of Au and Pt leads to significant variation in other magnetic properties, but not in the magnetic anisotropy energy. An analysis within a band description shows that the coexistence of Bi adatom and a surface dopant with large spin moment activates a mechanism involving reorientation and readjustment of the spin moments of electrons in occupied bands in response to the change of magnetization direction, which promotes giant magnetic anisotropy. Our results for adsorption energetics indicate that the accommodation of Bi in the neighborhood of the surface dopant is more likely in GaN nanowires, because the Bi adatom does (not) tend to be closer to the Mn (Co) dopant on the surface of GaN (ZnO) nanowire. The stability of GaN nanowire with giant magnetic anisotropy owing to the incorporation of both Mn and Bi is demonstrated by performing ab initio molecular dynamics simulations at temperatures considerably higher than room temperature. These results suggest that adatom deposition and surface doping can be used complementarily to develop single nanowire-based spintronic devices.

UV-assisted anchoring of gold nanoparticles into TiO2 nanotubes for oxygen electroreduction

• Au nanoparticles are deposited on TiO 2 nanotubular layers via photocatalytic reduction. • ORR overvoltage of photodeposited AuNPs is lower than AuNPs loaded from colloids. • ORR overvoltage of AuNPs-TNT depends on size, concentration and structure of AuNPs. Gold nanoparticles (AuNPs) have been deposited on titania nanotubular layers (TNT) via photocatalytic deposition, and the activity of the obtained AuNPs-TNT systems toward oxygen electroreduction reaction (ORR) in an alkaline medium has been studied and compared with the activity of AuNPs-TNT composites prepared from Au colloidal solutions. Two photodeposition methods were utilized for anchoring of AuNPs: direct UV-irradiation of a TNT electrode immersed into a HAuCl 4 containing solution (TNT-Au1 composites) and initial adsorption of AuCl 4 − ions on TNT followed by UV-irradiation (TNT-Au2 composites). The size, spatial distribution, structure and surface of AuNPs deposited on TNT layers were studied via scanning and transmission electron microscopy, optical spectroscopy and underpotential deposition of lead ad-atoms on gold. It was found that these parameters depend on the photodeposition method. The TNT-Au2 composites have smaller size, higher surface concentration and more uniform distribution of AuNPs in the TNT layers as compared with the TNT-Au1 systems. The electrocatalytic efficiency of Au-TNT electrodes in ORR was found to depend on various factors such as doping level of TNT support (governed by annealing temperature), AuNPs size and their loading amount. The electroreduction of oxygen was observed at less negative potentials when Au nanoparticles were grown on the TNT surface by photoreduction in comparison with the TNT electrodes modified with AuNPs from sols. The enhanced activity of the photocatalytically prepared AuNPs-TNT composites can be explained by the consolidation of the interface between gold nanoparticles and TiO 2 support and the absence of ligands on the AuNPs surface.

Electrochemistry of bismuth interlayers in (Bi2)m(Bi2Te3)n superlattice

Selective electrochemical transformations of bismuth interlayers in (Bi2)m(Bi2Te3)n superlattices can be of interest as a means of thermoelectric materials design based on bismuth telluride. In this work, the interlayers in the electrodeposited (Bi2)m(Bi2Te3)n superlattice structures formed by pulse potential controlled electrodeposition were characterized with electrochemical microgravimetry on quartz crystal electrodes, cyclic voltammetry, potentiodynamic electrochemical impedance spectroscopy (PDEIS), and in situ Raman spectroscopy. The oxidation potential of bismuth in the interlayers is in between the potentials of metallic bismuth and bismuth telluride anodic oxidation, which allows electrochemical detection and selective anodic dissolution of the interlayer bismuth. Microgravimetry and cyclic voltammetry have provided monitoring of bismuth interlayer dissolution and the subsequent underpotential deposition (upd) of bismuth adatoms onto Bi2Te3 layers in the electrochemically created slits. PDEIS provided separate monitoring of the interfacial charge transfer, spatially restricted diffusion, capacitance of faradaic origin, and double-layer capacitance, which disclosed different variations of the electrochemical interface area in the superlattices with initial bismuth content below and above that of Bi4Te3. In situ Raman spectroscopy has monitored the removal of bismuth interlayers and distinguished different locations of Bi adatoms in two stages of Bi upd. The electrochemically created slits of molecular dimension have a potential of being used as sieves, e.g., to provide selective accessibility of the electrochemically created centers inside them to molecules and ions in multi-component solutions.

Fluence-dependent microstructure and nanomechanical property in Co-Ni-V medium entropy alloy thin films

Via tuning deposition power, a series of Co-Ni-V medium entropy alloy thin films, growing in a nanocolumn manner, with different microstructures and morphologies were synthesized. With increasing fluence, both the crystallinity and nanocolumn size experienced a process of first increasing and then decreasing, controlled by the adatom surface diffusion vs. deposition rate competition. Meanwhile, continuous strengthening with fluence was ascribed to improved bonding and reduced fraction of boundary at low fluence and amorphization reinforcement effect in high fluence range.

Charge Transport Study of in-Situ Cesium Doped Monolayer Graphene

Modifying graphene with surface adsorbates is a widely studied way of modifying graphene’s electronic properties. Different graphene/adatom systems have shown that it is possible to open a band gap in graphene1, engineer topological insulators2 and create magnetic moments3. The atomic thickness of graphene maximizes the effect of adsorbates, enabling chemical sensors that achieve single molecule sensitivity4. Alkali metal adatoms are a particularly efficient dopant for graphene due to their high electronegativity. Lithium/graphene systems have been studied for in the context of low-dimensional superconductivity5 and achieving ultrafast diffusion of lithium6 for battery applications.However, doping graphene with alkali metal adatoms bears challenges. Experiments with alkali metals must be conducted in an ultra-high vacuum or inert gas environment due to the high reactivity of the alkali. Alkali metal adsorbed graphene is not air stable, which imposes limits on the available characterization methods. An impurity free graphene surface must be achieved prior to adsorption to achieve efficient adsorption and avoid unwanted parasitic reactions. This problem is particularly acute for graphene samples prepared by the use of polymer handles. Alkali metal atoms can also intercalate under the graphene layer depending on substrate and sample preparation conditions. Moreover, it is possible for adatoms to form clusters on graphene surface7which negatively impacts both doping uniformity and efficiency.In this work, we report a new method of alkali doping of graphene to reach ultra-high doping (~1014cm-2) for charge transport studies beyond the limit of ionic liquid gating. We work with chemical vapor deposition grown graphene transferred onto quartz substrates. Quartz is the substrate of choice due to its chemical inertness and optical transparency, with the latter enabling non-invasive Raman spectroscopy through the substrate. Micron scale graphene devices were prepared using lithography-based methods and the samples were thermally annealed in a nitrogen glove box environment to desorb water prior to alkali doping. The graphene was subsequently exposed to cesium vapor at different temperatures using a flip-chip method that allows hermetic sealing of the air sensitive samples in an inert gas environment with a liquid cesium source of cesium vapour. We measured the in-situ variation of graphene resistivity as cesium atoms are adsorbed onto the graphene surface, and resistivity is modulated by charge transfer doping. Evidence of ultra-high doping is shown via Raman spectroscopy performed through the quartz substrate window, with G-peak shifts from 1589 cm-1 up to 1608 cm-1. Hall measurements in-situ further confirm the strong doping. We measured the electronic transport properties of cesium doped graphene at temperatures as low as 1.2 K and under magnetic fields up to 7 T. Weak-localization, magnetoresistance and Hall resistance are measured and analyzed. 1. Elias, D. C.; Nair, R. R.; Mohiuddin, T. M.; Morozov, S. V.; Blake, P.; Halsall, M. P.; Ferrari, A. C.; Boukhvalov, D. W.; Katsnelson, M. I.; Geim, A. K.; Novoselov, K. S., Control of graphene's properties by reversible hydrogenation: evidence for graphane. Science 2009, 323 (5914), 610-3.2. Weeks, C.; Hu, J.; Alicea, J.; Franz, M.; Wu, R., Engineering a Robust Quantum Spin Hall State in Graphene via Adatom Deposition. Physical Review X 2011, 1 (2).3. Hong, X.; Zou, K.; Wang, B.; Cheng, S. H.; Zhu, J., Evidence for spin-flip scattering and local moments in dilute fluorinated graphene. Phys Rev Lett 2012, 108 (22), 226602.4. Schedin, F.; Geim, A. K.; Morozov, S. V.; Hill, E. W.; Blake, P.; Katsnelson, M. I.; Novoselov, K. S., Detection of individual gas molecules adsorbed on graphene. Nat Mater 2007, 6 (9), 652-5.5. Profeta, G.; Calandra, M.; Mauri, F., Phonon-mediated superconductivity in graphene by lithium deposition. Nat Phys 2012, 8 (2), 131-134.6. Kühne, M.; Paolucci, F.; Popovic, J.; Ostrovsky, P. M.; Maier, J.; Smet, J. H., Ultrafast lithium diffusion in bilayer graphene. Nat Nanotechnol 2017, 12, 895.7. Fan, X.; Zheng, W. T.; Kuo, J. L.; Singh, D. J., Adsorption of single Li and the formation of small Li clusters on graphene for the anode of lithium-ion batteries. ACS Appl Mater Interfaces 2013, 5 (16), 7793-7.

Electronic transport properties of a lithium-decorated ZrTe5 thin film

Through a combination of single crystal growth, experiments involving in situ deposition of surface adatoms, and complimentary modeling, we examine the electronic transport properties of lithium-decorated ZrTe5 thin films. We observe that the surface states in ZrTe5 are robust against Li adsorption. Both the surface electron density and the associated Berry phase are remarkably robust to adsorption of Li atoms. Fitting to the Hall conductivity data reveals that there exist two types of bulk carriers: those for which the carrier density is insensitive to Li adsorption, and those whose density decreases during initial Li depositions and then saturates with further Li adsorption. We propose this dependence is due to the gating effect of a Li-adsorption-generated dipole layer at the ZrTe5 surface.

Interfacial Study of Nickel-Modified Pt(111) Surfaces in Phosphate-Containing Solutions: Effect on the Hydrogen Evolution Reaction.

The surface modification of electrodes attracts great interest in electrocatalysis. It has often been observed that deposition of foreign adatoms on the surface of an electrode can originate a significant enhancement in the catalytic activity. For example, it has been reported that nickel deposits on Pt surfaces improve the rate of the hydrogen evolution reaction (HER, Nature Energy 2017, 2, 17031). During the deposition process of such metal adlayers, the pH and the nature of the ions in the electrolyte play an important role. Phosphate species are typically used to prepare buffer solutions in a wide range of pH. Therefore, electrolytes containing phosphate species are used in a large number of applications. However, the effect of phosphate on platinum surface modification with nickel deposits has not been studied yet. In this work, new data about the interaction of phosphate with nickel adatoms deposited on Pt(111) at pH 5 is investigated using cyclic voltammetry and infrared spectroscopy. The results show that, when nickel is in solution, the phosphate ions are adsorbed at lower potentials than in the absence of nickel. In addition, Laser-Induced Temperature Jump Technique demonstrates that nickel facilitates the adsorption of phosphate because of a shift of the potential of zero charge (pzc) toward negative potentials. This increases the magnitude of the positive electric field on the electrode surface, at a given potential E>pzc, facilitating the adsorption of anions. CO displacement technique has been also employed to obtain additional information about co-adsorbed phosphate on nickel adlayers. Finally, the HER has been studied at pH 5 in the presence of nickel, with and without phosphate in the bulk solution.

Gold Nanotetrapods with Unique Topological Structure and Ultranarrow Plasmonic Band as Multifunctional Therapeutic Agents.

Owing to their excellent surface plasmonic properties, Au nanobranches have drawn increasing attention in various bioapplications, such as contrast agents for photoacoustic imaging, nanomedicines for photothermal therapy, and carriers for drug delivery. The monodispersity and plasmonic bandwidth of Au nanobranches are of great importance for the efficacy of those bioapplications. However, it is still a challenge to accurately synthesize size- and shape-controlled Au nanobranches. Here we report a facile seed-mediated growth method to synthesize monodisperse Au nanotetrapods (NTPs) with tunable and ultranarrow plasmonic bands. The NTPs have a novel D2d symmetry with four arms elongated in four ⟨110⟩ directions. The growth mechanism of NTPs relies on the delicate kinetic control of deposition and diffusion rates of adatoms. Upon laser irradiation, the PEGylated NTPs possess remarkable photothermal conversion efficiencies and photoacoustic imaging properties. The NTPs can be applied as a multifunctional theranostic agent for both photoacoustic imaging and image-guided photothermal therapy.

Transport properties of bilayer graphene decorated by K adatoms in the framework of Thomas-Fermi screening

We report the transport properties of bilayer graphene (BLG) due to the increase of Coulomb potential fluctuations and the decrease of K adatom concentration $({\mathrm{n}}_{\mathrm{K}})$ induced by diffusion and cluster formation of the K adatom as a function of temperature (20--300 K) and time at room temperature (RT). Upon K adatom deposition on BLG at $T=20$ K, conductivity decreased due to the emergence of Coulomb scatterers, and the dependence of conductivity transformed from linear $(\ensuremath{\sigma}\ensuremath{\sim}{n}^{\ensuremath{\alpha}},\phantom{\rule{0.16em}{0ex}}\ensuremath{\alpha}\ensuremath{\sim}1)$ to superlinear $(\ensuremath{\alpha}\ensuremath{\sim}1.5)$. As the inhomogeneity of the Coulomb potential on BLG increased by cluster formation of K adatoms, the magnitude of the conductivity increased, and the dependence of conductivity on charge carrier density (curvature) shifted towards linear behavior. We fit the experimental data with Boltzmann transport theory to show that the changes in the transport properties of BLG in the presence of charged impurities originate from two factors, ${\mathrm{n}}_{\mathrm{K}}$ and the Thomas-Fermi screening vector $({\mathrm{q}}_{\mathrm{TF}})$, which are both affected by cluster formation of K adatoms on BLG and the subsequent increase of Coulomb potential inhomogeneity.

Transoid-to-Cisoid Conformation Changes of Single Molecules on Surfaces Triggered by Metal Coordination.

Conformational isomers are stereoisomers that can interconvert over low potential barriers by rotation around a single bond. However, such bond rotation is hampered by geometrical constraints when molecules are adsorbed on surfaces. Here, we show that the adsorption of 4,4′-bis(4-carboxyphenyl)-6,6′-dimethyl-2,2′-bipyridine molecules on surfaces leads to the appearance of prochiral single molecules on NiO(001) and to enantiopure supramolecular domains on Au(111) surfaces containing the transoid-molecule conformation. Upon additional Fe adatom deposition, molecules undergo a controlled interconversion from a transoid-to-cisoid conformation as a result of coordination of the Fe atoms to the 2,2′-bipyridine moieties. As confirmed by atomic force microscopy images and X-ray photoelectron spectroscopy measurements, the resulting molecular structures become irreversibly achiral.

Mechanism of glycerol oxidation reaction on silver-modified palladium electrode in alkaline medium

The silver-modified Pd (Ag/Pd) electrode was prepared by underpotential deposition of Cu adatoms, followed by galvanic displacement with Ag atoms to investigate the effect of silver modification on the catalysis and mechanism for glycerol oxidation reaction (GOR) of Pd. Cyclic voltammograms in alkaline glycerol solution exhibited that the Ag/Pd electrode had ca. 100 mV less positive onset potential of the GOR current density and higher peak current density than the Pd electrode, indicating that the GOR activity of Pd was enhanced by surface modification with Ag atoms. In potentiostatic electrolysis at −0.1 V vs. Hg/HgO, GOR mainly began with the oxidation of a terminal OH group for both electrodes, and glycerate and glycolate were major products. The glycolate production was more active for the Ag/Pd electrode. The in situ infrared reflectance-absorption spectra (IRAS) exhibited that GOR products with one or two carbons were detected at lower potentials for the Ag/Pd electrode, indicating that the CC bond cleavage was facilitated by the Ag modification.

Morphology and optical properties of Ge nanocrystalline films grown by nonequilibrium epitaxy on Si (001) surface

Optical properties and morphology of thin films with Ge and SiGe nanocrystallites are studied by using the methods of Raman scattering, multi-angle ellipsometry, and X-ray measurements. Our observations showed that low-temperature Ge epitaxy on Si(001) surface at 350 °C and at high growth rate leads to the formation of thin films consisting of Ge nanocrystallites with the porosity of about 50%. Deposition of Si adatoms on the film surface stimulates the reconstruction of the surface with nanocrystallites and results in the increase of the degree of Ge crystallinity, coalescence of adjacent nanocrystallites, and in a slight Si-Ge mixing. The change in the values of the optical constants due to silicon deposition is described by means of Bruggeman approximation. The main reasons for these changes are the film crystallization and the appearance of Si crystalline phase in the structures with Si capping layer. The prepared Ge nanocrystalline solids, as well as the films covered with Si, may be used in quantum dot solar cells due to the high absorption capacity of the films and devices working in the hopping regime.

The Different Faces of 4'-Pyrimidinyl-Functionalized 4,2':6',4''-Terpyridines: Metal-Organic Assemblies from Solution and on Au(111) and Cu(111) Surface Platforms.

A comparative investigation of crystal growth from solution and on-surface assembly in vacuo between copper and three 4'-(2-R-pyrimidin-5-yl)-4,2':6',4''-terpyridines, with R = H (1), Me (2), or Et (3), is presented. In solution, ligand 3 combines with copper(II) acetate or copper(I) triflate in MeOH solution to give [Cu2(OAc)4(3)]n or {[Cu(3)(OMe)(MeOH)][CF3SO3]·MeOH}n. In [Cu2(OAc)4(3)]n, paddle-wheel {Cu2(μ-OAc)4} nodes direct the assembly of one-dimensional (1D) zigzag chains which pack into two-dimensional (2D) sheets. In {[Cu(3)(OMe)(MeOH)][CF3SO3]·MeOH}n, the solvent is a ligand and also generates {Cu2(μ-OMe)2} units which function as planar 4-connecting nodes to generate a 2D (4,4) net with ligand 3. On Au(111) or Cu(111) surfaces in vacuo, no additional solvent or anions are involved in the assembly. The different substituents in 1, 2, or 3 allow precise molecular resolution imaging in scanning tunneling microscopy. On Au(111), 1 and 2 assemble into close-packed assemblies, while 3 forms a regular porous network. The deposition of Cu adatoms results in reorganization leading to ladder-shaped surface metal-organic motifs. These on-surface coordination assemblies are independent of the 4'-substituent in the 4,2':6',4''-tpy and are reproduced on Cu(111) where Cu adatoms are available during the deposition and relaxation process at room temperature. Upon annealing at elevated temperatures, the original surface assemblies of 1 and 3 are modified and a transition from ladders into rhomboid structures is observed; for 2, a further quasi-hexagonal nanoporous network is observed.

Tuning the Surface Morphologies and Properties of ZnO Films by the Design of Interfacial Layer

Wurtzite ZnO films were grown on MgO(111) substrates by plasma-assisted molecular beam epitaxy (MBE). Different initial growth conditions were designed to monitor the film quality. All the grown ZnO films show highly (0001)-oriented textures without in-plane rotation, as illustrated by in situ reflection high-energy electron diffraction (RHEED) and ex situ X-ray diffraction (XRD). As demonstrated by atomic force microscopy (AFM) images, “ridge-like” and “particle-like” surface morphologies are observed for the ZnO films grown in a molecular O2 atmosphere with and without an initial deposition of Zn adatoms, respectively, before ZnO growth with oxygen plasma. This artificially designed interfacial layer deeply influences the final surface morphology and optical properties of the ZnO film. From room-temperature photoluminescence (PL) measurements, a strong defect-related green luminescence band appears for the ZnO film with a “particle-like” morphology but was hardly observed in the films with flat “ridge-like” surface morphologies. Our work suggests that the ZnO crystallinity can be improved and defect luminescence can be reduced by designing interfacial layers between substrates and epilayers.