Search Results (23)

Atomically precise control of metal adatoms on metal surfaces is critical for designing novel low-dimensional materials, and the Sn-Cu(111) system is of particular interest due to the potential of stanene in topological physics. However, conflicting reports on Sn-induced superstructures on Cu(111) highlight the need for clarifying their geometric and electronic properties at low temperatures. We employed scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), angle-resolved photoemission spectroscopy (ARPES), and density functional theory (DFT) to investigate submonolayer (<0.25 ML) Sn adsorption on Cu(111) at 100 K. We confirmed a p(2 × 2) Sn/Cu(111) superstructure with one Sn atom per unit cell and found that Sn preferentially occupies three-fold hcp sites. ARPES measurements of the band structure—including a ~0.3 eV local gap between two specific bands at the ${\overline{\Gamma }}_2$ point in a metallic overall electronic structure—were in good agreement with the DFT results. Notably, the STM-observed p(2 × 2) morphology differs from the honeycomb-like or buckled stanene structures reported on Cu(111), which highlights the intricate interactions between adatoms and the substrate. Full article

The behavior of S and Cs during the alternate adsorption of each adsorbate on the Ni(100) surface is studied at room and elevated temperatures by means of low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), thermal desorption spectroscopy (TDS) and work function (WF) measurements. For Cs deposition on the S-covered Ni(100) surface, the presence of sulfur increases the binding energy and the maximum amount of adsorbed cesium, as happens with other alkalis too. The first Cs overlayer is disordered, while the second strongly interacts with S with a tendency toward a Cs_xS_y surface compound formation. This interaction causes the gradual demetallization of the Cs overlayer with the increasing S coverage in the underlayer. When the Cs_xS_y stoicheometry is complete, however, subsequent Cs deposition forms an independent rather metallic overlayer. When the sulfated covers the surface, S(0.5ML)/Ni(100) is preheated to 1100 K, the S-Ni bond strengthens and S-Cs interaction correspondingly weakens to a degree that the S underlayer retains a periodic structure on the Ni substrate. This behavior indicates that the preheated S/Ni(100) surface is passivated to a degree against Cs with reduced mobility of sulfur adatoms. Differently, when S is adsorbed on the Cs-covered Ni(100) surface at room temperature, sulfur adatoms diffuse underneath the Cs overlayer to interact with the nickel substrate and form the same structural phases as on a clean surface. During that process, the sticking coefficient of sulfur remains constant regardless of the amount of pre-deposited cesium. The presence of Cs, however, increases the amount of S that can be deposited on the Ni substrate, probably in favor of the Cs_xS_y compound formation, which demetallizes the surface independent of the sequence of adsorption. Full article

To probe the properties of single atoms is a challenging task, especially from the experimental standpoint, due to sensitivity limits. Nevertheless, it is sometimes possible to achieve this by making corresponding choices and adjustments to the experimental technique and sample under investigation. In the present case, the absolute value of the electronic charge the Fe atoms acquire when they are adsorbed on the surface of aluminum oxide α-Al₂O₃(0001) was measured by a set of surface-sensitive techniques: low-energy ion scattering (LEIS), Auger electron spectroscopy (AES), low-energy electron diffraction (LEED), and work function (WF) measurements, in combination with density functional theory (DFT) calculations. The main focus was the submonolayer coverage of Fe atoms in situ deposited on the well-ordered stoichiometric α-Al₂O₃(0001) 7 nm thick film formed on a Mo(110) crystal face. An analysis of the evolution of the Fe LVV Auger triplet upon variation of the Fe coverage shows that there is electronic charge transfer from Fe to alumina and that its value gradually decreases as the Fe coverage grows. The same trend is also predicted by the DFT results. Extrapolation of the experimental Fe charge value versus coverage plot yields an estimated value of a single Fe atom adsorbed on α-Al₂O₃(0001) of 0.98e (electron charge units), which is in reasonable agreement with the calculated value (+1.15e). The knowledge of this value and the possibility of its adjustment may be important points for the development and tuning of modern sub-nanometer-scale technologies of diverse applied relevance and can contribute to a more complete justification and selection of the corresponding theoretical models. Full article

Ultrathin NiO films, ranging from 1 to 16 monolayers (ML) in thickness, have been stabilized via reactive molecular beam epitaxy on the (001) surface of a metastable body-centered cubic (BCC) Ni film. Low-energy electron diffraction (LEED) confirms that NiO grows as a crystalline film, exposing the (001) surface. Auger electron spectroscopy (AES) reveals a slight oxygen excess compared to a perfectly stoichiometric NiO film. Scanning tunneling microscopy (STM) shows that at low coverages the film exhibits atomically flat terraces, while at higher coverage a “wedding cake” morphology emerges. Scanning tunneling spectroscopy (STS) reveals a thickness-dependent evolution of the electronic band gap, which increases from 0.8 eV at 3 ML to 3.5 eV at 16 ML. The center of the band gap is approximately 0.2 eV above the Fermi level, indicating that NiO is p-doped. Full article

The surface symmetry of the substrate plays an important role in the epitaxial high-quality growth of 2D materials; however, in-depth and in situ studies on these materials during growth are still limited due to the lack of effective in situ monitoring approaches. In this work, taking the growth of MoSe₂ as an example, the distinct growth processes on Al₂O₃ ($11\overline{2}0$) and Al₂O₃ (0001) are revealed by parallel monitoring using in situ reflectance anisotropy spectroscopy (RAS) and differential reflectance spectroscopy (DRS), respectively, highlighting the dominant role of the surface symmetry. In our previous study, we found that the RAS signal of MoSe₂ grown on Al₂O₃ ($11\overline{2}0$) initially increased and decreased ultimately to the magnitude of bare Al₂O₃ ($11\overline{2}0$) when the first layer of MoSe₂ was fully merged, which is herein verified by the complementary DRS measurement that is directly related to the film coverage. Consequently, the changing rate of reflectance anisotropy (RA) intensity at 2.5 eV is well matched with the dynamic changes in differential reflectance (DR) intensity. Moreover, the surface-dominated uniform orientation of MoSe₂ islands at various stages determined by RAS was further investigated by low-energy electron diffraction (LEED) and atomic force microscopy (AFM). By contrast, the RAS signal of MoSe₂ grown on Al₂O₃ (0001) remains at zero during the whole growth, implying that the discontinuous MoSe₂ islands have no preferential orientations. This work demonstrates that the combination of in situ RAS and DRS can provide valuable insights into the growth of unidirectional aligned islands and help optimize the fabrication process for single-crystal transition metal dichalcogenide (TMDC) monolayers. Full article

The disintegration of a continuous metallic thin film leads to the formation of isolated islands, which can be used for the preparation of plasmonic structures. The transformation mechanism is driven by a thermally accelerated diffusion that leads to the minimalization of surface free energy in the system. In this paper, we report the results of our study on the disintegration of gold thin film and the formation of nanoislands on silicon substrates, both pure and with native silicon dioxide film. To study the processes leading to the formation of gold nanostructures and to investigate the effect of the oxide layer on silicon diffusion, metallic film with a thickness of 3 nm was deposited by molecular beam epitaxy (MBE) technique on both pure and oxidized silicon substrates. Transformation of the thin film was observed by low-energy electron microscopy (LEEM) and a scanning electron microscope (SEM), while the nanostructures formed were observed by atomic force microscope (AFM) method. Structural investigations were performed by low-energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS) methods. Our experiments confirmed a strong correlation between the formation of nanoislands and the presence of native oxide on silicon substrates. Full article

The strict control of the work function of transition metal oxide crystals is of the utmost importance not only to fundamental research but also to applications based on these materials. Transition metal oxides are highly abundant in electronic devices, as their properties can be easily modified using redox processes. However, this ease of tuning is a double-edged sword. With the ease of manipulation comes difficulty in controlling the corresponding process. In this study, we demonstrate how redox processes can be induced in a laboratory setting and how they affect the work function of two model transition metal oxide crystals, namely titanium dioxide TiO₂(110) and strontium titanate SrTiO₃(001). To accomplish this task, we utilized Kelvin Probe Force Microscopy (KPFM) to monitor changes in work function, Scanning Tunneling Microscopy (STM), and Low-Energy Electron Diffraction (LEED) to check the surface morphology and reconstruction, and we also used X-ray Photoelectron Spectroscopy (XPS) to determine how the surface composition evolves. We also show that using redox processes, the work function of titanium dioxide can be modified in the range of 3.4–5.0 eV, and that of strontium titanate can be modified in the range of 2.9–4.5 eV. Moreover, we show that the presence of an oxygen-gaining material in the vicinity of a transition metal oxide during annealing can deepen the changes to its stoichiometry and therefore the work function. Full article

Germanium is an excellent material candidate for various applications, such as field effect transistors and radiation detectors/multijunction solar cells, due to its high carrier mobilities and narrow bandgap, respectively. However, the efficient passivation of germanium surfaces remains challenging. Recently, the most promising results have been achieved with atomic-layer-deposited (ALD) Al₂O₃, but the obtainable surface recombination velocity (SRV) has been very sensitive to the surface state prior to deposition. Based on X-ray photoelectron spectroscopy (XPS) and low-energy electron diffraction (LEED), we show here that the poor SRV obtained with the combination of HF and DIW surface cleaning and ALD Al₂O₃ results from a Ge suboxide interlayer (GeO_x, x < 2) with compromised quality. Nevertheless, our results also demonstrate that both the composition and crystallinity of this oxide layer can be improved with a combination of low-temperature heating and a 300-Langmuir controlled oxidation in an ultrahigh vacuum (LT-UHV treatment). This results in a reduction in the interface defect density (D_it), allowing us to reach SRV values as low as 10 cm/s. Being compatible with most device processes due to the low thermal budget, the LT-UHV treatment could be easily integrated into many future devices and applications. Full article

In this work the n-GaN(1000) surface is used as a source of nitrogen atoms in order to obtain niobium nitride film by a surface-mediated nitridation technique. To this end, the physical vapor deposition of the niobium film on GaN is followed by sample annealing at 1123 K. A thermally induced decomposition of GaN and interfacial mixing phenomena lead to the formation of a niobium nitride compound, which contains Nb from thin film and N atoms from the substrate. The processes allowed the obtaining of ordered NbN_x films on GaN. Structural and chemical properties of both the GaN substrate and NbN_x films were studied in-situ by surface-sensitive techniques, i.e., X-ray and UV photoelectron spectroscopies (XPS/UPS) and a low-energy electron diffraction (LEED). Then, the NbN_x/GaN surface morphology was investigated ex-situ by scanning tunneling microscopy (STM). Full article

Diffraction of photoelectrons emitted from the core 1s and valence band of monolayer and bilayer graphene is studied within the one-step theory of photoemission. The energy-dependent angular distribution of the photoelectrons is compared to the simulated electron reflection pattern of a low-energy electron diffraction experiment in the kinetic energy range up to about 55 eV, and the implications for the structure determination are discussed. Constant energy contours due to scattering resonances are well visible in photoelectron diffraction, and their experimental shape is well reproduced. The example of the bilayer graphene is used to reveal the effect of the scattering by the subsurface layer. The photoemission and LEED patterns are shown to contain essentially the same information about the long-range order. The diffraction patterns of C $1s$ and valence band photoelectrons bear similar anisotropy and are equally suitable for diffraction analysis. Full article

Adsorption and interaction of carbon monoxide (CO) and nitric oxide (NO) molecules on the surface of bare Al-Mo(110) system and on that obtained by its in situ oxidation have been studied in ultra-high vacuum (base pressure: ca. 10⁻⁸ Pa) by means of Auger and X-ray photoelectron spectroscopy (AES, XPS), low energy electron diffraction (LEED), reflection–absorption infrared and thermal desorption spectroscopy (RAIRS, TDS), and by the work function measurements. In order to achieve the Al-Mo(110) alloy the thin aluminum film of a few monolayers thick was in situ deposited onto the Mo(110) crystal and then annealed at 800 K. As a result of Al atoms diffusion into the Mo(110) subsurface region and the chemical reaction, the surface alloy of a hexagonal atomic symmetry corresponding to Al₂Mo alloy is formed. The feature of thus formed surface alloy regarding molecular adsorption is that, unlike the bare Mo(110) and Al(111) substrates, on which both CO and NO dissociate, adsorption on the alloy surface is non-dissociative. Moreover, adsorption of carbon monoxide dramatically changes the state of pre-adsorbed NO molecules, displacing them to higher-coordinated adsorption sites and simultaneously tilting their molecular axis closer to the surface plane. After annealing of this coadsorbed system up to 320 K the (CO + NO → CO₂ + N) reaction takes place resulting in carbon dioxide desorption into the gas phase and nitriding of the substrate. Such an enhancement of catalytic activity of Mo(110) upon alloying with Al is attributed to surface reconstruction resulting in appearance of new adsorption/reaction centers at the Al/Mo interface (steric effect), as well as to the Mo d-band filling upon alloying (electronic effect). Catalytic activity mounts further when the Al-Mo(110) is in situ oxidized. The obtained Al-Mo(110)-O ternary system is a prototype of a metal/oxide model catalysts featuring the metal oxides and the metal/oxide perimeter interfaces as a the most active reaction sites. As such, this type of low-cost metal alloy oxide models precious metal containing catalysts and can be viewed as a potential substitute to them. Full article

One-monolayer (ML) (thin) and 5-ML (thick) Si films were grown on the α-phase Si(111)√3 × √3R30°-Bi at a low substrate temperature of 200 °C. Si films have been studied in situ by reflection electron energy loss spectroscopy (REELS) and Auger electron spectroscopy, as a function of the electron beam incidence angle α and low-energy electron diffraction (LEED), as well as ex situ by grazing incidence X-ray diffraction (GIXRD). Scanning tunneling microscopy (STM), and scanning tunneling spectroscopy (STS) were also reported. The REELS spectra, taken at the Si K absorption edge (~1.840 KeV), reveal the presence of two distinct loss structures attributed to transitions 1s→π* and 1s→σ* according to their intensity dependence on α, attesting to the sp²-like hybridization of the silicon valence orbitals in both thin and thick Si films. The synthesis of a silicon allotrope on the α-phase of Si(111)√3 × √3R30°-Bi substrate was demonstrated by LEED patterns and GIXRD that discloses the presence of a Si stack of 3.099 (3) Å and a √3 × √3 unit cell of 6.474 Å, typically seen for multilayer silicene. STM and STS measurements corroborated the findings. These measurements provided a platform for the new √3 × √3R30° Si allotrope on a Si(111)√3 × √3 R30°-Bi template, paving the way for realizing topological insulator heterostructures from different two-dimensional materials, Bi and Si. Full article

Angle-resolved photoemission from monolayer and bilayer graphene is studied based on an ab initio one-step theory. The outgoing photoelectron is represented by the time-reversed low energy electron diffraction (LEED) state ${\mathsf{\Phi }}_{\mathrm{LEED}}^{*}$, which is calculated using a scattering theory formulated in terms of augmented plane waves. A strong enhancement of the emission intensity is found to occur around the scattering resonances. The effect of the photoelectron scattering by the underlying substrate on the polarization dependence of the photocurrent is discussed. The constant initial state spectra $I({\mathbf{k}}_{\left|\right|},\hslash \omega )$ are compared to electron transmission spectra $T\left(E\right)$ of graphene, and the spatial structure of the outgoing waves is analyzed. It turns out that the emission intensity variations do not correlate with the structure of the $T\left(E\right)$ spectra and are caused by rather subtle interference effects. Earlier experimental observations of the photon energy and polarization dependence of the emission intensity $I({\mathbf{k}}_{\left|\right|},\hslash \omega )$ are well reproduced within the dipole approximation, and the Kohn–Sham eigenstates are found to provide a quite reasonable description of the photoemission final states. Full article

Formation of gold nanosized particles supported by aluminum oxide film grown on Mo(110) substrate and oxidation of carbon monoxide molecules on their surface have been in-situ studied in ultra-high vacuum by means of Auger electron spectroscopy (AES), reflection-absorption infrared spectroscopy (RAIRS), low energy electron diffraction (LEED), atomic force microscopy (AFM), temperature-programmed desorption (TPD), and work function measurements. The main focus was to follow how the thickness of the alumina film influences the efficiency of CO oxidation in an attempt to find out evidence of the possible effect of electron tunneling between the metal substrate and the Au particle through the oxide interlayer. Providing the largest degree of surface identity of the studied metal/oxide system at different thicknesses of the alumina film (two, four, six, and eight monolayers), it was found that the CO oxidation efficiency, defined as CO₂ to CO TPD peaks intensity ratio, exponentially decays with the oxide film thickness growth. Taking into account the known fact that the CO oxidation efficiency depends on the amount of excess charge acquired by Au particle, the latter suggests that electron tunneling adds efficiency to the oxidation process, although not significantly. Full article

Interface properties of iron phthalocyanine (FePc) and perfluorinated iron phthalocyanine (FePcF₁₆) on rutile TiO₂(100) and TiO₂(110) surfaces were studied using X-ray photoemission spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and low-energy electron diffraction (LEED). It is demonstrated that the interaction strength at the interfaces is considerably affected by the detailed preparation procedure. Weak interactions were observed for all studied interfaces between FePc or FePcF₁₆ and rutile, as long as the substrate was exposed to oxygen during the annealing steps of the preparation procedure. The absence of oxygen in the last annealing step only had almost no influence on interface properties. In contrast, repeated substrate cleaning cycles performed in the absence of oxygen resulted in a more reactive, defect-rich substrate surface. On such reactive surfaces, stronger interactions were observed, including the cleavage of some C–F bonds of FePcF₁₆. Full article