Thickness-Dependent Band Gap Modification in BaBiO3_{3}

The material BaBiO$_{3}$ is known for its insulating character. However, for thin films, in the ultra-thin limit, metallicity is expected because BaBiO$_{3}$ is suggested to return to its undistorted cubic phase where the oxygen octahedra breathing mode will be suppresse as reported recently. Here, we confirm the influence of the oxygen breathing mode on the size of the band gap. The electronic properties of a BaBiO$_{3}$ thickness series are studied using \textit{in-situ} scanning tunneling microscopy. We observe a wide-gap ($E_\textrm{G}$~$>$ 1.2 V) to small-gap~($E_\textrm{G}$~$\approx$ 0.07 eV) semiconductor transition as a function of a decreasing BaBiO$_{3}$ film thickness. However, even for an ultra-thin BaBiO$_{3}$ film, no metallic state is present. The dependence of the band gap size is found to be coinciding with the intensity of the Raman response of the breathing phonon mode as a function of thickness

Toward the Assembly of 2D Tunable Crystal Patterns of Spherical Colloids on a Wafer-Scale

Entering an era of miniaturization prompted scientists to explore strategies to assemble colloidal crystals for numerous applications, including photonics. However, wet methods are intrinsically less versatile than dry methods, whereas the manual rubbing method of dry powders has been demonstrated only on sticky elastomeric layers, hindering particle transfer in printing applications and applicability in analytical screening. To address this clear impetus of broad applicability, we explore here the assembly on nonelastomeric, rigid substrates by utilizing the manual rubbing method to rapidly (≈20 s) attain monolayers comprising hexagonal closely packed (HCP) crystals of monodisperse dry powder spherical particles with a diameter ranging from 500 nm to 10 μm using a PDMS stamp. Our findings elucidate that the tribocharging-induced electrostatic attraction, particularly on relatively stiff substrates, and contact mechanics force between particles and substrates are critical contributors to attain large-scale HCP structures on conductive and insulating substrates. The best performance was obtained with polystyrene and PMMA powder, while silica was assembled only in HCP structures on fluorocarbon-coated substrates under zero-humidity conditions. Finally, we successfully demonstrated the assembly of tunable crystal patterns on a wafer-scale with great control on fluorocarbon-coated wafers, which is promising in microelectronics, bead-based assays, sensing, and anticounterfeiting applications

Molecular dynamics and energy landscape of decanethiolates in self-assembled monolayers on Au(111) studied by scanning tunneling microscopy

The energetics and dynamics of the various phases of decanethiolate self-assembled monolayers on Au(111) surfaces were studied with scanning tunneling microscopy. We have observed five different phases of the decanethiolate monolayer on Au(111): four ordered phases (β, δ, χ*, and φ) and one disordered phase (ε). We have determined the boundary free energies between the disordered and order phases by analyzing the thermally induced meandering of the domain boundaries. On the basis of these results, we are able to accurately predict the two-dimensional phase diagram of the decanethiolate/Au(111) system. The order-disorder phase transition of the χ* phase occurs at 295 K, followed by the order-disorder phase transition of the β phase at 325 K. Above temperatures of 325 K, only the densely packed φ and disordered ε phases remain. Our findings are in good agreement with the phase diagram of the decanethiolate/Au(111) system that was put forward by Poirier et al. [ Langmuir 2001, 17 (4), 1176-1183 ]

Spatially resolved electronic structure of twisted graphene

We have used scanning tunneling microscopy and spectroscopy to resolve the spatial variation of the density of states of twisted graphene layers on top of a highly oriented pyrolytic graphite substrate. Owing to the twist a moire pattern develops with a periodicity that is substantially larger than the periodicity of a single layer graphene. The twisted graphene layer has electronic properties that are distinctly different from that of a single layer graphene due to the nonzero interlayer coupling. For small twist angles (about 1-3.5 degree) the integrated differential conductivity spectrum exhibits two well-defined Van Hove singularities. Spatial maps of the differential conductivity that are recorded at energies near the Fermi level exhibit a honeycomb structure that is comprised of two inequivalent hexagonal sub-lattices. For energies |E-E_F|>0.3 eV the hexagonal structure in the differential conductivity maps vanishes. We have performed tight-binding calculations of the twisted graphene system using the propagation method, in which a third graphene layer is added to mimic the substrate. This third layer lowers the symmetry and explains the development of the two hexagonal sub-lattices in the moire pattern. Our experimental results are in excellent agreement with the tight-binding calculations.Comment: To appear in Phys. Rev.

Nanoscale work function contrast induced by decanethiol self-assembled monolayers on Au(111)

In this paper, we obtain maps of the spatial tunnel barrier variations in self-assembled monolayers of organosulfurs on Au(111). Maps down to the sub-nanometer scale are obtained by combining topographic scanning tunneling microscopy images with dI/dz spectroscopy. The square root of the tunnel barrier height is directly proportional to the local work function and the dI/dz signal. We use ratios of the tunnel barriers to study the work function contrast in various decanethiol phases: the lying-down striped β phase, the dense standing-up φ phase, and the oxidized decanesulfonate λ phase. We compare the induced work function variations too: the work function contrast induced by a lying-down striped phase in comparison to the modulation induced by the standing-up φ phase, as well as the oxidized λ phase. By performing these comparisons, we can account for the similarities and differences in the effects of the mechanisms acting on the surface and extract valuable insights into molecular binding to the substrate. The pillow effect, governing the lowering of the work function due to lying-down molecular tails in the striped low density phases, seems to have quite a similar contribution as the surface dipole effect emerging in the dense standing-up decanethiol phases. The dI/dz spectroscopy map of the nonoxidized β phase compared to the map of the oxidized λ phase indicates that the strong binding of molecules to the substrate is no longer present in the latter.Fil: Tsvetanova, Martina. University of Twente; Países BajosFil: Oldenkotte, Valent J. S.. University of Twente; Países BajosFil: Bertolino, María Candelaria. University of Twente; Países Bajos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Gao, Yuqiang. University of Twente; Países BajosFil: Siekman, Martin H.. University of Twente; Países BajosFil: Huskens, Jurriaan. University of Twente; Países BajosFil: Zandvliet, Harold J. W.. University of Twente; Países BajosFil: Sotthewes, Kai. University of Twente; Países Bajo

Structural and electronic properties of single molecules and organic layers on surfaces

Single molecules and organic layers on well-defined solid surfaces have attracted tremendous attention owing to their interesting physical and chemical properties. The ultimate utility of single molecules or self-assembled monolayers (SAMs) for potential applications is critically dependent on the structural, electronic and dynamic properties. Therefore is it important to study the structural and electronic properties as well as the dynamic processes of single molecules and organic layers on surfaces. Using scanning tunneling microscopy (STM) single molecules or organic layers on surfaces are studied while their electronic and dynamic properties are probed using scanning tunneling spectroscopy (STS). In order to design and realize single-molecule devices it is essential to obtain a good understanding of the properties of an individual molecule. The transport through a single octanethiol molecule trapped between an STM tip and a Pt/Ge(001) substrate is systematically studied. Spatially resolved current-time (I(t)) spectroscopy combined with current-distance (I(z)) spectroscopy has been used to characterize the dynamic behavior of copper-phthalocyanine (CuPc) molecules adsorbed on a Au-modified Ge(001) surface. Also a new approach to measure the spatially resolved thermovoltage in an STM is described. The bulk part of this thesis describes the dynamics of SAMs or single molecules that interact with a surface using different scanning tunneling spectroscopic tools. Deep insights discovered in the dynamics of the SAMs down to the single molecular level were obtained. In addition, the conductance of an octanethiol and the switching frequency of a CuPc molecule can be accurately adjusted by precisely adjusting the tip-molecule distance. The work in this thesis further enhances the knowledge of dynamic processes in SAMs and other molecular systems induced by the interaction with the surface

Free energy of domain walls and order-disorder transition in a triangular lattice with anisotropic nearest-neighbor interactions

We have derived exact expressions for the domain wall free energy along the three high-symmetry directions of a triangular lattice with anisotropic nearest-neighbor interactions. The triangular lattice undergoes an order-disorder phase transition at a temperature Tc given by e-(ϵ1+ϵ2)/2kTc+e-(ϵ2+ϵ3)/2kTc+e-(ϵ3+ϵ1)/2kTc=1, where ϵ1, ϵ2, ϵ3 are the nearest-neighbor interaction energies, and ϵ1+ϵ2>0, ϵ2+ϵ3>0, ϵ3+ϵ1>0. Finally, we have derived expressions for the thermally induced meandering of the domain walls at temperatures below the phase transition temperature. We show how these expressions can be used to extract the interaction energies of two-dimensional systems with a triangular lattice

Water confined in two-dimensions: Fundamentals and applications

The behavior of water in close proximity to other materials under ambient conditions is of great significance due to its importance in a broad range of daily applications and scientific research. The structure and dynamics of water at an interface or in a nanopore are often significantly different from those of its bulk counterpart. Until recently, experimental access to these interfacial water structures was difficult to realize. The advent of two-dimensional materials, especially graphene, and the availability of various scanning probe microscopies were instrumental to visualize, characterize and provide fundamental knowledge of confined water. This review article summarizes the recent experimental and theoretical progress in a better understanding of water confined between layered Van der Waals materials. These results reveal that the structure and stability of the hydrogen bonded networks are determined by the elegant balance between water-surface and water-water interactions. The water-surface interactions often lead to structures that differ significantly from the conventional bilayer model of natural ice. Here, we review the current knowledge of water adsorption in different environments and intercalation within various confinements. In addition, we extend this review to cover the influence of interfacial water on the two-dimensional material cover and summarize the use of these systems in potential novel applications. Finally, we discuss emerged issues and identify some flaws in the present understanding