Single Au Adatoms Research Articles

Blue phosphorene on Au(111): theoretical, spectroscopic and diffraction analysis reveal the role of single Au adatoms.

In investigating the monoatomic layers of P, several stable two-dimensional (2D) allotropes have been theoretically predicted. Among them, single-layer blue phosphorus (BlueP) appears to deliver promising properties. After initial success, where the structure of BlueP triangular patches on Au(111) was conceived on the basis of scanning tunneling microscopy (STM) and density functional theory (DFT), the surface structure model was revisited multiple times with increasing accuracy and insight of theoretical calculations and experimental datasets. Interestingly, the quest for a reliable atomic structure model of BlueP on Au(111) turned out to be very contentious and challenging, particularly considering the possible incorporation of Au atoms in the 2D sheet of P. This article proposes an extended report on theoretical findings that can be extracted from DFT calculations of the orbital projected band structure and employed for an efficient comparison protocol between the calculations and experimental datasets obtained from angle-resolved photoemission spectroscopy (ARPES). The findings, together with experimental and simulated data from STM imaging and surface X-ray diffraction (SXRD), show a clear way to verify the presence and characterize the stabilizing effect of foreign atoms in 2D materials.

On-surface synthesis of ballbot-type N-heterocyclic carbene polymers.

N-Heterocyclic carbenes (NHCs) are established ligands for metal complexes and surfaces. Here we go beyond monomeric NHCs and report on the synthesis of NHC polymers on gold surfaces, consisting of ballbot-type repeating units bound to single Au adatoms. We designed, synthesized and deposited precursors containing different halogens on gold surfaces under ultrahigh vacuum. Conformational, electronic and charge transport properties were assessed by combining low-temperature scanning tunneling microscopy, non-contact atomic force microscopy, X-ray photoelectron spectroscopy, first-principles calculations and reactive force field simulations. The confirmed ballbot-type nature of the NHCs explains the high surface mobility of the incommensurate NHC polymers, which is prerequisite for their desired spatial alignment. The delicate balance between mobility and polymerization rate allows essential parameters for controlling polymer directionality to be derived. These polymers open up new opportunities in the fields of nanoelectronics, surface functionalization and catalysis.

Reduction and oxidation of Au adatoms on the CeO2(111) surface - DFT+U versus hybrid functionals.

Recently we showed that Au atoms may titrate Ce3+ ions in near-surface layers of reduced CeO2(111). This surface contained oxygen vacancies in subsurface position within the topmost O-Ce-O trilayer [Pan et al., Phys. Rev. Lett., 2013, 111, 206101.]. The present work builds upon these findings and discusses additional results obtained using PBE+U and hybrid functionals. These approaches do not predict the same relative stabilities for the various adsorption sites of a single Au adatom at an O-defect concentration of a ¼ ML or 1.984 nm-2. We attribute this discrepancy to a different alignment within the O 2p-Ce 4f gap, i.e. a different order by energy of partially occupied Ce 4f and Au 6s orbitals. The energy offset of these orbitals matters, because the adsorption of Au0(6s1) atop Ce3+(4f1) or atop a subsurface oxygen atom in the first coordination shell of a Ce3+(4f1) involves creation of Au-(6s2) and Ce4+(4f0) ions. The electron transfer to Au is coupled to stabilizing ionic relaxation in the lattice, commonly known as polaronic distortion, reinforcing the Au-Ce bond. The order of 4f and 6s orbitals depends on the density functional approximation and is also strongly influenced by the oxygen defect concentration.

Density Functional Investigation of the Inclusion of Gold Clusters on a CH3S Self-Assembled Lattice on Au(111)

We employ first-principles density functional theoretical calculations to address the inclusion of gold (Au) clusters in a well-packed CH3S self-assembled lattice. We compute CH3S adsorption energies to quantify the energetic stability of the self-assembly and gold adsorption and dissolution energies to characterize the structural stability of a series of Au clusters adsorbed at the SAM-Au interface. Our results indicate that the inclusion of Au clusters with less than four Au atoms in the SAM-Au interface enhances the binding of CH3S species. In contrast, larger Au clusters destabilize the self-assembly. We attribute this effect to the low-coordinated gold atoms in the cluster. For small clusters, these low-coordinated sites have significantly different electronic properties compared to larger islands, which makes the binding with the self-assembly energetically more favorable. Our results further indicate that Au clusters in the SAM-Au interface are thermodynamically unstable and they will tend to dissolve, producing Au adatoms incorporated in the self-assembly in the form of CH3S-Au-SCH3 species. This is due to the strong S-Au bond which stabilizes single Au adatoms in the self-assembly. Our results provide solid insight into the impact of adatom islands at the CH3S-Au interface.

Imaging, single atom contact and single atom manipulations at low temperature using the new ScientaOmicron LT-UHV-4 STM

The performances of the new ScientaOmicron LT-UHV 4-STM microscope have been certified by a series of state-of-art STM experiments on an Au(1 1 1) surface at 4.3 K. During the STM operation of the 4 STM scanners (independently or in parallel with an inter tip apex front to front distance down to a few tens of nanometers), a ΔZ stability of about 2 pm per STM was demonstrated. With this LT-UHV 4-STM stability, single Au atom manipulation experiments were performed on Au(1 1 1) by recording the pulling, sliding and pushing manipulation signals per scanner. Jump to contact experiments lead to perfectly linear low voltage I-V characteristics on a contacted single Au ad-atom with no need of averaging successive I-V’s. Our results show how this new instrument is exactly 4 times a very precise single tip LT-UHV-STM. Two tips surface conductance measurements were performed on Au(1 1 1) using a lock-in technique in a floating sample mode of operation to capture the Au(1 1 1) surface states via two STM tips dI/dV characteristics.

Supramolecular Rotor and Translator at Work: On-Surface Movement of Single Atoms.

A supramolecular nanostructure composed of four 4-acetylbiphenyl molecules and self-assembled on Au (111) was loaded with single Au adatoms and studied by scanning tunneling microscopy at low temperature. By applying voltage pulses to the supramolecular structure, the loaded Au atoms can be rotated and translated in a controlled manner. The manipulation of the gold adatoms is driven neither by mechanical interaction nor by direct electronic excitation. At the electronic resonance and driven by the tunneling current intensity, the supramolecular nanostructure performs a small amount of work of about 8 × 10(-21) J, while transporting the single Au atom from one adsorption site to the next. Using the measured average excitation time necessary to induce the movement, we determine the mechanical motive power of the device, yielding about 3 × 10(-21) W.

Dissociative adsorption of water on Au/MgO/Ag(001) from first principles calculations

The molecular and dissociative adsorption of water on a Ag-supported 1 ML, 2 ML and 3 ML-a six atomic layer-thick MgO films with a single Au adatom is investigated using density functional theory calculations. The obtained results are compared to a bulk MgO(001) surface with an Au atom. On thin films the negatively charged Au strengthens the binding of the polar water molecule due to the attractive Au–H interaction. The adsorption energy trends of OH and H with respect to the film thickness depend on an adsorption site. In the case OH or H binds atop Au on MgO/Ag(001), the adsorption becomes more exothermic with the increasing film thickness, while the reverse trend is seen when the adsorption takes place on bare MgO/Ag(001). This behavior can be explained by different bonding mechanisms identified with the Bader analysis. Interestingly, we find that the rumpling of the MgO film and the MgO–Ag interface distance correlate with the charge transfer over the thin film and the interface charge, respectively. Moreover, we employ a modified Born–Haber-cycle to analyze the effect of film thickness to the adsorption energy of isolated Au and OH species on MgO/Ag(001). The analysis shows that the attractive Coulomb interaction between the negatively charged adsorbate and the positive MgO–Ag-interface does not completely account for the weaker binding with increasing film thickness. The redox energy associated with the charge transfer from the interface to the adsorbate is more exothermic with the increasing film thickness and partly compensates the decrease in the attractive Coulomb interaction.

Manipulation of the charge state of single Au atoms on insulating multilayer films.

We show charge-state manipulation of single Au adatoms on 2-11 monolayer (ML) thick NaCl films on Cu surfaces by attaching or detaching single electrons via the tip of an atomic force microscope (AFM). Tristate charge control (neutral, negatively charged, and positively charged) is achieved. On Cu(100) and Cu(111) supports, charge tristability is achieved independently of the NaCl layer thickness. In contrast, on Cu(311), only Au anions are stable on the thinnest NaCl films, but neutral and positive charge states become sufficiently long lived on films thicker than 4 ML to allow AFM-based charge-state-manipulation experiments.

Direct observation of hopping and merging of single Au adatoms to form dimers on Si(111)-(7 × 7)

Au single adatoms and dimers were imaged on Si(111)-(7 × 7) at different temperatures and bias voltages using a variable-temperature scanning tunneling microscope. At room temperature (RT), a single Au adatom induces sharp highlighted triangular features in the half unit cells (HUCs) of Si(111)-(7 × 7). These triangular features become fuzzy at temperatures lower than 225 K, as a result of the reduced moving speed of the single Au adatoms inside the HUCs. The formation of an Au adatom dimer was directly observed at RT when a single Au adatom in a HUC jumped into a neighboring HUC that already contained a single Au adatom. The Au adatom dimer appears either as a noisy feature in the central area of the HUC defined by three Si center adatoms or as a bright protrusion located close to a corner Si adatom site at RT. It was observed that a noisy feature also can change into a bright protrusion, inducing charge redistribution in the nearby Si adatoms in both the occupied and neighboring HUCs.

Ordered Array of Single Adatoms with Remarkable Thermal Stability:Au/Fe3O4(001)

Gold deposited on the Fe3O4(001) surface at room temperature was studied using scanning tunneling microscopy (STM) and x-ray photoelectron spectroscopy (XPS). This surface forms a (√2 × √2)R45° reconstruction, where pairs of Fe and neighboring O ions are slightly displaced laterally producing undulating rows with "narrow" and "wide" hollow sites. At low coverages, single Au adatoms adsorb exclusively at the narrow sites, with no significant sintering up to annealing temperatures of 400 °C. We propose the strong site preference to be related to charge and orbital ordering within the first subsurface layer of Fe3O4(001)-(√2 × √2)R45°. Because of its high thermal stability, this could prove an ideal model system for probing the chemical reactivity of single atomic species.

Stabilizing Gold Adatoms by Thiophenyl Derivatives: A Possible Route toward Metal Redispersion

Tris(phenylthio)benzene molecules have been synthesized in order to explore their ability to trap single Au adatoms on an Au(111) surface. The resulting metal-organic complexes have been characterized with low-temperature scanning tunneling microscopy and infrared reflection absorption spectroscopy; possible structure models have been derived from density functional calculations. Upon room temperature deposition, the thiophenyl derivatives form dimer structures, comprising two molecules and six Au adatoms. Below 100 K, isolated molecules are found as well that have trapped up to six Au atoms. On the basis of the experimental results and calculated formation energies of the complexes, we discuss potential applications of the thioethers for the redispersion of metals on a catalyst surface. First experiments performed on Au particle ensembles prepared on alumina thin films suggest that the molecular ligands are indeed able to change the distribution of gold on the oxide surface.

Mass Spectrometry and Dynamics of Gold Adatoms Observed on the Surface of Size-Selected Au Nanoclusters

We report the imaging, mass spectrum, and dynamical behavior of adatoms and small clusters observed on the surface facets of size-selected, truncated octahedral gold clusters, Au(N) (N = 923 ± 23), via aberration-corrected scanning transmission electron microscopy. Our quantitative atom counting measurements show that most (~70%) of the species on the surface are single Au adatoms. Such species are now proposed as key elements of the atomic structure of both monolayer-protected nanoclusters (nanoparticles) and self-assembled monolayers and may also play a role in gold nanocatalysis. The adatoms are found on both {100} and {111} facets with similar probabilities.

Molecular hydrogen adsorption at surface adatoms

Using electron-energy-loss spectroscopy, we have measured preferential adsorption of molecular hydrogen at Cu and Au adatoms deposited on a cold Cu(100) surface. We show, with particular attention to the D(2)-Au system, that the molecules adsorb at the adatoms, with an enhanced binding energy. The adsorption state is not of chemisorption character, the D(2) rotational and internal vibrational transition energies are close to the corresponding gas phase values, a characteristic property of a physisorbed state. A revealing signature of the D(2)-Au interaction is an induced dipole activity of the rotational transition, which discriminates molecules adsorbed at the adatoms from those adsorbed on the bare substrate surface. The average number of molecules per Au atom depends on the Au coverage and increases at lower coverages, for example, at 4% of an adatom monolayer, there are approximately six D(2) molecules per Au adatom. In this limit, Au monomers prevail, and a cluster of six D(2) around a single Au adatom appears to be an optimal dense two-dimensional configuration.

Molecular dynamics study of gold adatom diffusion on low-index copper surfaces

The transport properties of single Au adatoms on low-index Cu surfaces have been studied using molecular dynamics. We found that on the Cu(001) face, the adatom substitutes a surface Cu atom via the exchange diffusion mechanism, while this process is absent on the Cu(111) surface. On the Cu(110) face, hopping and exchange diffusion processes coexist with almost equal probability. The migration energies associated with the various diffusion processes have been deduced. It turns out that the diffusion of Au adatoms differs significantly from Cu self-diffusion on the low-index Cu surfaces. In addition, the calculated adatom binding energies, as well as the temperature dependence of the mean-square-displacements and the relaxed positions in the normal to the surfaces direction are compatible with the diffusion results.