Charged Adatoms Research Articles

Topological boundary states in engineered quantum-dot molecules on the InAs(111)A surface: Odd numbers of quantum dots

Atom manipulation by scanning tunneling microscopy was used to construct quantum dots on the InAs(111)A surface. Each dot comprised six ionized indium adatoms. The positively charged adatoms create a confining potential acting on surface-state electrons, leading to the emergence of a bound state associated with the dot. By lining up the dots into N-dot chains with alternating tunnel coupling between them, quantum-dot molecules were constructed that revealed electronic boundary states as predicted by the Su-Schrieffer-Heeger (SSH) model of one-dimensional topological phases. Dot chains with odd N were constructed such that they host a single end or domain-wall state, allowing one to probe the localization of the boundary state on a given sublattice by scanning tunneling spectroscopy. We found probability density also on the forbidden sublattice together with an asymmetric energy spectrum of the chain-confined states. This deviation from the SSH model arises because the dots are charged and create a variation in on-site potential along the chain—which does not remove the boundary states but shifts their energy away from the midgap position. Our results demonstrate that topological boundary states can be created in quantum-dot arrays engineered with atomic-scale precision. Published by the American Physical Society 2024

Quantum dots on the InAs(110) cleavage surface created by atom manipulation

Cryogenic scanning tunneling microscopy was employed in combination with density-functional theory calculations to explore quantum dots made of In adatoms on the InAs(110) surface. Each adatom adsorbs at a surface site coordinated by one cation and two anions, and transfers one electron to the substrate, creating an attractive quantum well for electrons at the surface. We used the scanning-probe tip to assemble the positively charged adatoms into precisely defined quantum dots exhibiting a bound state roughly 0.1 eV below the Fermi level at an intrinsic linewidth of only ∼4 meV, as revealed by scanning tunneling spectroscopy. For quantum-dot dimers, we observed the emergence of a bonding and an antibonding state with even and odd wave-function character, respectively, demonstrating the capability to engineer quasimolecular electronic states. InAs(110) constitutes a promising platform in this respect because highly perfect surfaces can be readily prepared by cleavage and charged adatoms can be generated by the scanning-probe tip. Published by the American Physical Society 2024

Enhanced High Power Impulse Magnetron Sputter Processes

SummaryHigh power impulse magnetron sputtering (HIPMS) has emerged as a useful approach for depositing highly dense and smooth coatings of electrically conductive materials. Recent advances in power supply technology have further enabled HIPMS through the addition of a positive kick in the pulse cycle which supplies a bias at the surface of the sputter target which expels sputter target ions and sends more charged adatoms toward the substrate. This has been demonstrated with critical materials like diamond‐like carbon and plasmonic materials. Material specific pulse magnitudes and durations can be developed to achieve new novel thin film morphologies.

Topological states in dimerized quantum-dot chains created by atom manipulation

Topological electronic phases exist in a variety of naturally occurring materials but can also be created artificially. We used a cryogenic scanning tunneling microscope to create dimerized chains of identical quantum dots on a semiconductor surface and to demonstrate that these chains give rise to one-dimensional topological phases. The dots were assembled from charged adatoms, creating a confining potential with single-atom precision acting on electrons in surface states of the semiconductor. Coupling between the dots leads to electronic states localized at the ends of the chains, as well as at deliberately created internal domain walls, in agreement with the predictions of the Su-Schrieffer-Heeger model. Scanning tunneling spectroscopy also reveals deviations from this well-established model manifested in an asymmetric level spectrum and energy shifts of the boundary states. The deviations arise because the dots are charged and hence lead to an onsite potential that varies along the chain. We show that this variation can be mitigated by electrostatic gating using auxiliary charged adatoms, enabling fine-tuning of the boundary states and control of their superposition. The experimental data, which are complemented by theoretical modeling of the potential and the resulting eigenstates, reveal the important role of electrostatics in these engineered quantum structures.

Tunable high workfunction contacts: Doped graphene

Contact electrodes with high work functions can enable significant enhancement in optoelectronic device performance due to their important role in efficient extracting/injecting carriers especially from optically active materials with high electron affinity or deep valence band edge, such as CdTe and some perovskites. With such materials becoming increasingly important in emerging solar cell technologies, the need for high work function electrodes has become of timely importance. In this work, p-doped graphene is investigated using first principle calculations, as a potential high work function contact electrode material for optoelectronic device applications. We found that chemical doping based on the adsorption of different non-metallic adatoms on graphene allows tuning the work function which can reach as high as 5.76 eV. A range of p-dopant adatoms, with varying doping concentrations, was investigated and we showed that the largest change of the work function is caused by chlorine and bromine dopants: a 4% concentration of Cl and Br dopants results in an increase of the work function of graphene from 4.38 eV to 5.76 eV and 5.71 eV, respectively. Furthermore, the calculations show that this significant increase in graphene’s work function is mainly due to the charge transfer from graphene to p-dopant adatoms, which increases the concentration of holes at the graphene surface, and hence, increases its work function. We also analyzed the stability conditions for absorbed halogen adatoms on graphite. In particular, we found that halogen molecules formation process should be significantly inhibited by electrostatic repulsion between charged adatoms which provides additional barrier for them to get closer to react. These findings provide valuable guidance to experimental efforts towards the realization of tunable high work function graphene-based electrodes.

The effect of oxygen vacancy at CO oxidation on anatase (001)-supported single-Au catalyst

The catalytic performance of CO oxidation on the TiO2-supported gold catalysts would be affected by the O vacancies on a TiO2 surface. First-principle studies here are focused on how the O vacancy addresses the performance of single atom catalysts on CO oxidation. Three possible configurations of gold adatoms and O vacancies on anatase TiO2(001) support are considered as follows: A gold adatom above an O vacancy, a gold adatom or two gold adatoms above an O vacancy dimer. The O vacancy dimer favors the binding of negatively charged gold adatoms on anatase TiO2(001) support. However, the dual gold adatoms slightly increase the barrier energy in CO oxidation through the Au-assisted Mars-van Krevelen mechanism. The formation of a stable carbonate on the initial-existing O vacancy reveals that the extra O vacancy deteriorates the catalytical performance of CO oxidation. In final, the high catalytic performances of TiO2/Au catalyst are attributed to the synergistic effects between a negatively charged Au adatom and a lower-coordinated Ti3+ ion.

Enhanced High Power Impulse Magnetron Sputter Processes

SummaryHigh power impulse magnetron sputtering (HIPMS) has emerged as a useful approach for depositing highly dense and smooth coatings of electrically conductive materials. Recent advances in power supply technology have further enabled HIPMS through the addition of a positive kick in the pulse cycle which supplies a bias at the surface of the sputter target which expels sputter target ions and sends more charged adatoms toward the substrate. This has been demonstrated with critical materials like diamond‐like carbon and plasmonic materials. Material specific pulse magnitudes and durations can be developed to achieve new novel thin film morphologies.

Cs adsorption on Bi2Se3

Bi2Se3 is a topological insulator whose unique properties result from topological surface states (TSS) in the band gap. The adsorption of Cs onto a Bi2Se3 surface is investigated by low energy ion scattering and work function measurements. Much of the deposited Cs quickly diffuses to the step edges forming one-dimensional chains of positively charged adatoms, along with some deposition on the terraces. The work function decreases until a coverage of 0.1 ML is reached, beyond which it increases slightly. The minimum in the work function is due to depolarization of the dipoles induced when the concentration of adatoms in the chains reaches a critical value. A slow diffusion of adsorbed Cs from the terraces to the step edges is also marked by changes in the neutralization of scattered Na+ and work function over time. The spatial distribution of the conductive charges in the TSS, which are primarily positioned between the first and second atomic layers, is confirmed by comparison of the neutralization of Na+ scattered from Bi and Se.

SERS active Ag-SiO2 nanoparticles obtained by laser ablation of silver in colloidal silica.

Highly stable Ag–SiO2 nanoparticle composites were first obtained by laser ablation of a silver target in an aqueous colloidal dispersion of silica and examined by UV–vis absorption spectroscopy, transmission electron microscopy and Raman spectroscopy. The surface enhanced Raman scattering (SERS) activity of these nanocomposites was tested using 2,2’-bipyridine as a molecular reporter and excitation in the visible and near-IR spectral regions. The computational DFT approach provided evidence of ligand adsorption on positively charged adatoms of the silver nanostructured surface, in a very similar way to the metal/molecule interaction occurring in the corresponding Ag(I) coordination compound.

Effect of uniaxial stress on the electrochemical properties of graphene with point defects

We report a calculational study of electron states and the resulting electrochemical properties of uniaxially strained graphene with point defects. For this study the reduction of ferricyanide to ferrocyanide serves as a benchmark electrochemical reaction. We find that the heterogeneous electron transfer activity of the perfect graphene electrode rises under uniaxial strain. However, evolution of the cathodic reaction rate depends on the direction of strain. For moderate lattice deformations, the zigzag strain improves electrochemical performance better than the armchair strain. Standard rate constant increases by 50% at the zigzag strain of 10%. Vacancies, covalently bonded moieties, charged adatoms and substitutional impurities in the zigzag strained graphene induce changes in the shape of the curve of the cathodic reaction rate. However, this changes do not translate into the electrocatalytic activity. Vacancies and covalently bonded moieties at concentration of 0.1% do not affect the electrochemical performance. Charged adatoms and substitutional impurities give a slight increase in the standard rate constant by, respectively, 2.2% and 3.4%.

Halogen-Adatom Mediated Phase Transition of Two-Dimensional Molecular Self-Assembly on a Metal Surface.

Construction of tunable and robust two-dimensional (2D) molecular arrays with desirable lattices and functionalities over a macroscopic scale relies on spontaneous and reversible noncovalent interactions between suitable molecules as building blocks. Halogen bonding, with active tunability of direction, strength, and length, is ideal for tailoring supramolecular structures. Herein, by combining low-temperature scanning tunneling microscopy and systematic first-principles calculations, we demonstrate novel halogen bonding involving single halogen atoms and phase engineering in 2D molecular self-assembly. On the Au(111) surface, we observed catalyzed dehalogenation of hexabromobenzene (HBB) molecules, during which negatively charged bromine adatoms (Brδ-) were generated and participated in assembly via unique C-Brδ+···Brδ- interaction, drastically different from HBB assembly on a chemically inert graphene substrate. We successfully mapped out different phases of the assembled superstructure, including densely packed hexagonal, tetragonal, dimer chain, and expanded hexagonal lattices at room temperature, 60 °C, 90 °C, and 110 °C, respectively, and the critical role of Brδ- in regulating lattice characteristics was highlighted. Our results show promise for manipulating the interplay between noncovalent interactions and catalytic reactions for future development of molecular nanoelectronics and 2D crystal engineering.

Functionalization of γ-graphyne by transition metal adatoms

Transition Metal (TM) atoms adsorption on γ-graphyne is here studied to unravel the electronic and magnetic properties tuning of this 2D carbon allotrope, with possible repercussions on molecular storage, sensing, and catalytic properties. A thorough density functional theory study, including dispersion, of the structural, energetic, diffusivity, magnetic, and doping properties for all 3d, 4d, and 5d TM adatoms adsorbed on γ-graphyne is provided. Overall, TMs strongly chemisorb on γ-graphyne acetylenic rings, except d10 group XII TMs which physisorb. Diffusion energy barriers span the 0.5–3.5 eV and adatom height with respect the γ-graphyne sheet seems to be governed by the TM atomic radius. All TMs are found to give n-doped γ-graphyne, where charge transfer decays along d series due to the increasing electronegativity of TMs. Middle TMs infer noticeable magnetism to γ-graphyne, yet magnetism is heavily quenched for early and late TMs. The large adsorption energies close to parent TM bulk cohesive energies, the high diffusion energy barriers, and the coulombic repulsion between positively charged TM adatoms provide a good environment for TMs to disperse over the γ-graphyne.

Role of Acoustoelectric Interaction in the Formation of Nanoscale Periodic Structures of Adsorbed Atoms

The role of acoustoelectric effects in the formation of nanoscale structures of adatoms, resulting from the self-consistent interaction of adatoms with a surface acoustic wave and the electronic subsystem, is studied for the case of charged and uncharged adatoms. It is shown that an increase in the doping level of a semiconductor with donor impurities at a fixed average adatom concentration results in an increase in the critical temperature below which self-organization processes occur.

Tracking the Effect of Adatom Electronegativity on Systematically Modified AlGaN/GaN Schottky Interfaces.

The influence of surface modifications on the Schottky barrier height for gallium nitride semiconductor devices is frequently underestimated or neglected in investigations thereof. We show that a strong dependency of Schottky barrier heights for nickel/aluminum-gallium nitride (0001) contacts on the surface terminations exists: a linear correlation of increasing barrier height with increasing electronegativity of superficial adatoms is observed. The negatively charged adatoms compete with the present nitrogen over the available gallium (or aluminum) orbital to form an electrically improved surface termination. The resulting modification of the surface dipoles and hence polarization of the surface termination causes observed band bending. Our findings suggest that the greatest Schottky barrier heights are achieved by increasing the concentration of the most polarized fluorine-gallium (-aluminum) bonds at the surface. An increase in barrier height from 0.7 to 1.1 eV after a 15% fluorine termination is obtained with ideality factors of 1.10 ± 0.05. The presence of surface dipoles that are changing the surface energy is proven by the sessile drop method as the electronegativity difference and polarization influences the contact angle. The extracted decrease in the Lifshitz-van-der-Waals component from 48.8 to 40.4 mJ/m(2) with increasing electronegativity and concentration of surface adatoms confirms the presence of increasing surface dipoles: as the polarizability of equally charged anions decreases with increasing electronegativity, the diiodomethane contact angles increase significantly from 14° up to 39° after the 15% fluorine termination. Therefore, a linear correlation between increasing anion electronegativity of the (Al)GaN termination and total surface energy within a 95% confidence interval is obtained. Furthermore, our results reveal a generally strong Lewis basicity of (Al)GaN surfaces explaining the high chemical inertness of the surfaces.

Reconfigurable Quantum-Dot Molecules Created by Atom Manipulation.

Quantum-dot molecules were constructed on a semiconductor surface using atom manipulation by scanning tunneling microscopy (STM) at 5 K. The molecules consist of several coupled quantum dots, each of which comprises a chain of charged adatoms that electrostatically confines intrinsic surface-state electrons. The coupling takes place across tunnel barriers created reversibly using the STM tip. These barriers have an invariant, reproducible atomic structure and can be positioned-and repeatedly repositioned-to create a series of reconfigurable quantum-dot molecules with atomic precision.

Trapping of Charged Gold Adatoms by Dimethyl Sulfoxide on a Gold Surface.

We report the formation of dimethyl sulfoxide (DMSO) molecular complexes on Au(111) enabled by native gold adatoms unusually linking the molecules via a bonding of ionic nature, yielding a mutual stabilization between molecules and adatom(s). DMSO is a widely used polar, aprotic solvent whose interaction with metal surfaces is not fully understood. By combining X-ray photoelectron spectroscopy, low temperature scanning tunneling microscopy, and density functional theory (DFT) calculations, we show that DMSO molecules form complexes made by up to four molecules arranged with adjacent oxygen terminations. DFT calculations reveal that most of the observed structures are accurately reproduced if, and only if, the negatively charged oxygen terminations are linked by one or two positively charged Au adatoms. A similar behavior was previously observed only in nonstoichiometric organic salt layers, fabricated using linkage alkali atoms and strongly electronegative molecules. These findings suggest a motif for anchoring organic adlayers of polar molecules on metal substrates and also provide nanoscale insight into the interaction of DMSO with gold.

Static and dynamic buckling of reconstructions at triple steps on Si(111) surfaces

Triple steps on Si(111) surfaces are popular building blocks for bottom-up nanostructure assembly, conferring size uniformity and precise positioning of growing nanostructures. In this work, we employ the Si(7 7 10) regular stepped surface as model system to study the triple steps by scanning tunneling microscopy (STM) and large-scale first-principles calculations. We find a surprising cohabitation of reconstruction elements at the step edge that either buckles statically or dynamically at room temperature. The driving force for the observed sequence of buckling patterns is traced back to Coulomb interactions involving charged adatoms and rest-atoms lying on a mini-terrace. These results reconcile the Si(111) triple step model with the experimental STM data.

On the charge transfer in the “single-sheet graphene-intercalated metal layer-SiC substrate” system

The proposed scheme for the consideration of charge transfer in the three-layer Gr/Me/SiC system (where Gr is a single-sheet graphene, Me is an intercalated metal layer, and SiC is a substrate) contains three stages. At the first stage, a metal monolayer adsorbed on silicon carbide is considered and the charge of adatoms in this monolayer is calculated. At the second stage, the shift of the Dirac point of free-standing single-layer graphene in an electrostatic field induced by charged adatoms of the monolayer is estimated. At the third stage, a weak interaction between Me/SiC and free-standing graphene is included, which allows electrons to tunnel but does not significantly distort the density of states of free-standing graphene. Estimations are performed for n- and p-type 6H-SiC(0001) substrates and Cu, Ag, and Au layers. The charge state of the graphene sheet and the shift of the Dirac point with respect to the Fermi level of the system are calculated. A comparison with the available experimental and theoretical results shows that the proposed scheme works quite satisfactorily.

Atomic-Scale Engineering of the Electrostatic Landscape of Semiconductor Surfaces

A low-temperature scanning tunneling microscope was used in conjunction with density functional theory calculations to determine the binding sites and charge states of adsorbed Ga and Mn atoms on GaAs(110). To quantify the adatom charge states (both +1e), the Coulomb interaction with an individual Mn acceptor is measured via tunneling spectroscopy and compared with theoretical predictions. Several methods for positioning these charged adatoms are demonstrated, allowing us to engineer the electrostatic landscape of the surface with atomic precision.

Electron spin relaxation in graphene with random Rashba field: comparison of the D'yakonov–Perel' and Elliott–Yafet-like mechanisms

To understand the main spin relaxation mechanism in graphene, we investigate the spin relaxation with random Rashba field (RRF) induced by both adatoms and a substrate using the kinetic spin Bloch equation approach. The charged adatoms, on the one hand, enhance the Rashba spin–orbit coupling locally and, on the other hand, serve as Coulomb potential scatterers. Both effects contribute to spin relaxation limited by the D'yakonov–Perel' (DP) mechanism. In addition, the RRF also causes spin relaxation by spin-flip scattering, manifesting itself as an Elliott–Yafet (EY)-like mechanism. Both mechanisms are sensitive to the correlation length of the RRF, which may be affected by environmental parameters such as electron density and temperature. Fitting and comparing the experiments of the Groningen group (Józsa et al 2009 Phys. Rev. B 80 241403(R)) and the Riverside group (Pi et al 2010 Phys. Rev. Lett.104 187201; Han and Kawakami 2011 Phys. Rev. Lett.107 047207), which show either DP (with the spin relaxation rate being inversely proportional to the momentum scattering rate) or EY-like (with the spin relaxation rate being proportional to the momentum scattering rate) properties, we suggest that the DP mechanism dominates the spin relaxation in graphene. The latest experimental finding of a nonmonotonic dependence of spin relaxation time on diffusion coefficient by Jo et al 2011 (Phys. Rev. B 84 075453) is also well reproduced by our model.