III-V antimonide nanowires are among the most interesting semiconductors for transport physics, nanoelectronics and long-wavelength optoelectronic devices due to their optimal material properties. In order to investigate their complex crystal structure evolution, faceting and composition, we report a combined scanning electron microscopy (SEM), transmission electron microscopy (TEM), and scanning tunneling microscopy (STM) study of gold-nucleated ternary InAs/InAs(1-x)Sb(x) nanowire heterostructures grown by molecular beam epitaxy. SEM showed the general morphology and faceting, TEM revealed the internal crystal structure and ternary compositions, while STM was successfully applied to characterize the oxide-free nanowire sidewalls, in terms of nanofaceting morphology, atomic structure and surface composition. The complementary use of these techniques allows for correlation of the morphological and structural properties of the nanowires with the amount of Sb incorporated during growth. The addition of even a minute amount of Sb to InAs changes the crystal structure from perfect wurtzite to perfect zinc blende, via intermediate stacking fault and pseudo-periodic twinning regimes. Moreover, the addition of Sb during the axial growth of InAs/InAs(1-x)Sb(x) heterostructure nanowires causes a significant conformal lateral overgrowth on both segments, leading to the spontaneous formation of a core-shell structure, with an Sb-rich shell.
High-density packing in organic crystals is usually associated with an increase of the coordination between molecules. Such a concept is not necessarily extended to two-dimensional molecular networks self-assembled on a solid surface, for which we demonstrate the key role of the surface in inducing the optimal packing. By a combination of scanning tunneling microscopy experiments and multiscale computer simulations, we study the phase transition between two polymorphs. We find that, contrary to intuition, the structure with the lowest packing fraction corresponds to the highest molecular coordination number, due to the competition between surface and intermolecular forces. Having the lowest free energy, this structure spreads out as the most stable polymorph over a wide range of molecular concentrations.
An open‐and‐shut case: By using tailored molecules, the formation of open or close‐packed supramolecular network can be achieved on a silicon‐based surface. The role of molecule–molecule interactions and molecule–substrate interactions to control the geometry of organic network on semi‐conductor surface is investigated.
The engineering of a complete adlayer of organic nanolines by supramolecular self-assembly has been achieved for the first time on a silicon-based surface at room temperature and has been studied by scanning tunneling microscopy. This complete adlayer has been successfully obtained thanks to the combination of a specific Si(111)-B square root 3x square root 3R30 degrees semiconductive surface and of strong hydrogen bonds between a pair of dipolar molecules.
The self-assembly of two-dimensional (2D) molecular structures on a solid surface relies on the subtle balance between non covalent intermolecular and molecule-surface forces. The energetics of 2D molecular lattices forming different patterns on a passivated semiconductor surface are here investigated by a combination of atomistic simulation methods. Densityfunctional theory provides structure and charges of the molecules, while metadynamics with empirical forces provides a best guess for the lowest-energy adsorption sites of single molecules and dimers. Subsequently, molecular dynamics simulations of extended molecular assemblies with empirical forces yield the most favorable lattice structures at finite temperature and pressure.
Chiral assemblies of achiral molecules: High‐resolution STM images of zwitterionic organic dipoles deposited on Si(111)‐7×7 show a chiral molecular assembly on this surface (see picture). Density functional calculations demonstrate that a sulfonato group can act as an electrostatic shield that protects the π skeleton of organic molecules from the dangling bonds of semiconductor surfaces, which is a major advance in the deposition of π‐conjugated molecules.
We report a significant and persistent enhancement of the conductivity in free-standing non-intentionally doped InAs nanowires upon irradiation in ultra-high vacuum. Combining four-point probe transport measurements performed on nanowires with different surface chemistries, field effect based measurements and numerical simulations of the electron density, the change in the conductivity is found to be caused by an increase in the surface free carrier concentration. Although an electron beam of a few keV, typically used for the inspection and the processing of materials, propagates through the entire nanowire cross-section, we demonstrate that the electrical properties of the nanowire are predominantly affected by radiation-induced defects occurring at the nanowire surface and not in the bulk.
International audienceIndividual adsorbed Cu-5,10,15,20-tetrakis(3,5-di-tert-butylphenyl) porphyrin is observed by STM on a Si(111)-B surface with an atomic resolution at room temperature. The conformational modifications after the adsorption on the surface is successfully interpreted thanks to DFT calculations performed on the entire system (molecule and substrate)
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