Correlation between Electronic Configuration and Magnetic Stability in Dysprosium Single Atom Magnets.

Single atom magnets offer the possibility of magnetic information storage in the most fundamental unit of matter. Identifying the parameters that control the stability of their magnetic states is crucial to design novel quantum magnets with tailored properties. Here, we use X-ray absorption spectroscopy to show that the electronic configuration of dysprosium atoms on MgO(100) thin films can be tuned by the proximity of the metal Ag(100) substrate onto which the MgO films are grown. Increasing the MgO thickness from 2.5 to 9 monolayers induces a change in the dysprosium electronic configuration from 4f9 to 4f10. Hysteresis loops indicate long magnetic lifetimes for both configurations, however, with a different field-dependent magnetic stability. Combining these measurements with scanning tunneling microscopy, density functional theory, and multiplet calculations unveils the role of the adsorption site and charge transfer to the substrate in determining the stability of quantum states in dysprosium single atom magnets.

Growth Phase- and Desiccation-Dependent Acinetobacter baumannii Morphology: An Atomic Force Microscopy Investigation.

Acinetobacter baumannii has emerged as a major bacterial pathogen during the past three decades. The majority of the A. baumannii infections occur in hospitals and are caused by strains endowed with high desiccation tolerance, which represents an essential feature for the adaptation to the nosocomial environment. This work aims at investigating the desiccation response of the multidrug-resistant A. baumannii strain ACICU as a function of the bacterial growth phase and oxygen availability, by correlating bacterial survival with shape alterations. The three-dimensional morphological analysis of bacteria was carried out by atomic force microscopy (AFM), following the evolution of bacterial shape descriptors, such as the area, volume, roughness of individual cell membranes, and the cell cluster roughness, which exhibited peculiar and distinctive behavior as a function of the growth conditions. AFM images of A. baumannii ACICU cells revealed the prevalence of the coccoid morphology at all growth stages, with a tendency to reduce their size in the stationary phase, accompanied by a higher survival rate to air-drying. Moreover, cells harvested from the logarithmic phase featured a larger volume and resulted to be more sensitive to desiccation compared to the cells harvested at later growth stages. In addition, oxygen deprivation caused a significant decrease in cellular size and was associated with the formation of pores in the cell membrane, accompanied by a relative reduction in culturability after desiccation. Morphological plasticity and multidrug resistance may contribute to desiccation tolerance and therefore to persistence in the hospital setting.

Terahertz absorption-saturation and emission from electron-doped germanium quantum wells.

We study radiative relaxation at terahertz frequencies in n-type Ge/SiGe quantum wells, optically pumped with a terahertz free electron laser. Two wells coupled through a tunneling barrier are designed to operate as a three-level laser system with non-equilibrium population generated by optical pumping around the 1→3 intersubband transition at 10 THz. The non-equilibrium subband population dynamics are studied by absorption-saturation measurements and compared to a numerical model. In the emission spectroscopy experiment, we observed a photoluminescence peak at 4 THz, which can be attributed to the 3→2 intersubband transition with possible contribution from the 2→1 intersubband transition. These results represent a step towards silicon-based integrated terahertz emitters.

Surface-enhanced Raman scattering (SERS)-based immunosystem for ultrasensitive detection of the 90K biomarker.

The research and the individuation of tumour markers in biological fluids are currently one of the main tools to support diagnosis, prognosis, and monitoring of the therapeutic response in oncology. Although the identification of tumour markers in asymptomatic patients is crucial for early diagnosis, its application is still limited by the relatively low sensitivity and the complexity of existing methods (i.e. ELISA, mass spectrometry). We developed an easy, fast, and ultrasensitive surface-enhanced Raman scattering (SERS)-based system, for the detection and quantitation of the LGALS3BP (90K) biomarker that was used as a model, based on the development of antibody-functionalized nanostructured gold surfaces. The detection system was effective for the ultrasensitive detection and characterization of samples of different biochemical compositions. In conclusion, this work could provide the foundation for the development of a medical diagnostic device with the highest predictive power when compared with the methods currently used in cancer diagnostics.

Corroles at the Real Solid-Liquid Interface: In Situ STM Investigation of a Water-Soluble Corrole Layer Deposited onto Au(111).

Corrole derivatives have been recently employed in many applications at the solid-liquid interface. Therefore, the structural arrangement of the molecular layers in direct contact with the liquid is of fundamental interest. We investigated in solution the deposition of molecular layers of the previously prepared water-soluble phosphorus complex of a 2-sulfonato-10-(4-sulfonatophenyl)-5,15-dimesitylcorrole [see synthesis in our previous paper, M. Naitana et al., Chem. Eur. J. 2017, 23, 905-916]. The layer formation of P corroles onto the Au(111) surface was monitored by STM in situ, that is, with the substrate immersed in the solution. Marked differences in the morphology between the organic layer formed on the substrate and that deposited after solvent evaporation (drop casting) are reported. In particular, the coating of gold was more effective and stable in the presence of liquid. Preservation of functionality of the corrole molecules after adsorption was verified. This result validates the relevance of corrole layers at the solid-liquid interface to exploit the peculiar properties of these molecules in real-world applications.

Magnetic Properties of Metal⁻Organic Coordination Networks Based on 3d Transition Metal Atoms.

The magnetic anisotropy and exchange coupling between spins localized at the positions of 3d transition metal atoms forming two-dimensional metal⁻organic coordination networks (MOCNs) grown on a Au(111) metal surface are studied. In particular, we consider MOCNs made of Ni or Mn metal centers linked by 7,7,8,8-tetracyanoquinodimethane (TCNQ) organic ligands, which form rectangular networks with 1:1 stoichiometry. Based on the analysis of X-ray magnetic circular dichroism (XMCD) data taken at T = 2.5 K, we find that Ni atoms in the Ni⁻TCNQ MOCNs are coupled ferromagnetically and do not show any significant magnetic anisotropy, while Mn atoms in the Mn⁻TCNQ MOCNs are coupled antiferromagnetically and do show a weak magnetic anisotropy with in-plane magnetization. We explain these observations using both a model Hamiltonian based on mean-field Weiss theory and density functional theory calculations that include spin⁻orbit coupling. Our main conclusion is that the antiferromagnetic coupling between Mn spins and the in-plane magnetization of the Mn spins can be explained by neglecting effects due to the presence of the Au(111) surface, while for Ni⁻TCNQ the metal surface plays a role in determining the absence of magnetic anisotropy in the system.

A Highly Emissive Water-Soluble Phosphorus Corrole.

The synthesis, spectroscopic, and optical properties of the water-soluble phosphorus complex of a 2-sulfonato-10-(4-sulfonatophenyl)-5,15-dimesitylcorrole have been investigated. The compound was prepared by adopting a novel strategy for the corrole sulfonation, leading to the regioselective isomer in an almost quantitative yield. The phosphorus coordination has a key role in determining the corrole substitution pattern, limiting the formation of poly-substituted species, which affected the reaction of the corrole free base. The resulting complex shows excellent optical properties in terms of emission quantum yield, also in polar protic solvents, including water. 31 P NMR spectroscopy in CD3 OD indicates that the P sulfonate complex has been isolated in a hexacoordinated geometry with two different ligands (L1=-OH, L2=-OCH3 ), and it is prone to axial ligand exchange with methanol, with no evidence of intermediate pentacoordinated species. The morphological characterization of thin layers of the P corrole deposited onto an Au(111) surface showed that the addition of an intermediate layer of reduced graphene oxide allows for a better control of corrole aggregation, inducing also transformation of the Au(111) reconstructed surface.

On-Surface Molecular Recognition Driven by Chalcogen Bonding.

Chalcogen bonding interactions (ChBIs) have been widely employed to create ordered noncovalent assemblies in solids and liquids. Yet, their ability to engineer molecular self-assembly on surfaces has not been demonstrated. Here, we report the first demonstration of on-surface molecular recognition solely governed by ChBIs. Scanning tunneling microscopy and ab initio calculations reveal that a pyrenyl derivative can undergo noncovalent chiral dimerization on the Au(111) surface through double Ch···N interactions involving Te- or Se-containing chalcogenazolo pyridine motifs. In contrast, reference chalcogenazole counterparts lacking the pyridyl moiety fail to form regular self-assemblies on Au, resulting in disordered assemblies.

Selective Growth of GaP Crystals on CMOS-Compatible Si Nanotip Wafers by Gas Source Molecular Beam Epitaxy.

Gallium phosphide (GaP) is a III-V semiconductor with remarkable optoelectronic properties, and it has almost the same lattice constant as silicon (Si). However, to date, the monolithic and large-scale integration of GaP devices with silicon remains challenging. In this study, we present a nanoheteroepitaxy approach using gas-source molecular-beam epitaxy for selective growth of GaP islands on Si nanotips, which were fabricated using complementary metal-oxide semiconductor (CMOS) technology on a 200 mm n-type Si(001) wafer. Our results show that GaP islands with sizes on the order of hundreds of nanometers can be successfully grown on CMOS-compatible wafers. These islands exhibit a zinc-blende phase and possess optoelectronic properties similar to those of a high-quality epitaxial GaP layer. This result marks a notable advancement in the seamless integration of GaP-based devices with high scalability into Si nanotechnology and integrated optoelectronics.

Bio-physical mechanisms of dehydrating membranes of Acinetobacter baumannii linked to drought-resistance.

Acinetobacter baumanni, is an opportunistic nosocomial multi-drug resistant bacterium, which represents a threat for human health. This pathogen is able to persist in intensive care units thanks to its extraordinary resistance towards dehydration, whose mechanisms are unknown and enable it to easily spread through surfaces, contaminating also medical devices. In this article we reveal, with a multimodal approach, based on µ-R Spectroscopy, Gas Chromatography coupled to Mass Spectroscopy, Atomic Force Microscopy and Fluorescence Recovery After Photobleaching, the bio-physical mechanisms that the membrane of two A. baumannii strains undergoes during dehydration. Showing a substantial decoupling of the phase transition from liquid crystalline to gel phase from evidence of cell lysis. Such decoupling may be the core of the resistance of A. baumannii against dehydration and highlights the different ability to resist to drought between strains.

Slow Magnetic Relaxation of Dy Adatoms with In-Plane Magnetic Anisotropy on a Two-Dimensional Electron Gas.

We report on the magnetic properties of Dy atoms adsorbed on the (001) surface of SrTiO3. X-ray magnetic circular dichroism reveals slow relaxation of the Dy magnetization on a time scale of about 800 s at 2.5 K, unusually associated with an easy-plane magnetic anisotropy. We attribute these properties to Dy atoms occupying hollow adsorption sites on the TiO2-terminated surface. Conversely, Ho atoms adsorbed on the same surface show paramagnetic behavior down to 2.5 K. With the help of atomic multiplet simulations and first-principles calculations, we establish that Dy populates also the top-O and bridge sites on the coexisting SrO-terminated surface. A simple magnetization relaxation model predicts these two sites to have an even longer magnetization lifetime than the hollow site. Moreover, the adsorption of Dy on the insulating SrTiO3 crystal leads, regardless of the surface termination, to the formation of a spin-polarized two-dimensional electron gas of Ti 3dxy character, together with an antiferromagnetic Dy-Ti coupling. Our findings support the feasibility of tuning the magnetic properties of the rare-earth atoms by acting on the substrate electronic gas with electric fields.

Tuning the Doping of Epitaxial Graphene on a Conventional Semiconductor via Substrate Surface Reconstruction.

Combining scanning tunneling microscopy and angle-resolved photoemission spectroscopy, we demonstrate how to tune the doping of epitaxial graphene from p to n by exploiting the structural changes that occur spontaneously on the Ge surface upon thermal annealing. Furthermore, using first-principle calculations, we build a model that successfully reproduces the experimental observations. Since the ability to modify graphene electronic properties is of fundamental importance when it comes to applications, our results provide an important contribution toward the integration of graphene with conventional semiconductors.

Submicron Size Schottky Junctions on As-Grown Monolayer Epitaxial Graphene on Ge(100): A Low-Invasive Scanned-Probe-Based Study.

We report on the investigation of the Schottky barrier (SB) formed at the junction between a metal-free graphene monolayer and Ge semiconductor substrate in the as-grown epitaxial graphene/Ge(100) system. In order to preserve the heterojunction properties, we defined submicron size graphene/Ge junctions using the scanning probe microscopy lithography in the local oxidation configuration, a low-invasive processing approach capable of inducing spatially controlled electrical separations among tiny graphene regions. Characteristic junction parameters were estimated from I-V curves obtained using conductive-atomic force microscopy. The current-voltage characteristics showed a p-type Schottky contact behavior, ascribed to the n-type to p-type conversion of the entire Ge substrate due to the formation of a large density of acceptor defects during the graphene growth process. We estimated, for the first time, the energy barrier height in the as-grown graphene/Ge Schottky junction (φB ≈ 0.45 eV) indicating an n-type doping of the graphene layer with a Fermi level ≈ 0.15 eV above the Dirac point. The SB devices showed ideality factor values around 1.5 pointing to the high quality of the heterojunctions.

van der Waals Heteroepitaxy of Germanene Islands on Graphite.

We fabricated flat, two-dimensional germanium sheets showing a honeycomb lattice that matches that of germanene by depositing submonolayers of Ge on graphite at room temperature and subsequent annealing to 350 °C. Scanning tunneling microscopy shows that the germanene islands have a small buckling with no atomic reconstruction and does not give any hints for alloy formation and hybridization with the substrate. Our density functional theory calculations of the structural properties agree well with our experimental findings and indicate that the germanene sheet interacts only weakly with the substrate underneath. Our band structure calculations confirm that the Dirac cone of free-standing germanene is preserved for layers supported on graphite. The germanene islands show a small but characteristic charge transfer with the graphite substrate which is predicted by our ab initio simulations in excellent agreement with scanning tunneling spectroscopy measurements.

Complex Magnetic Exchange Coupling between Co Nanostructures and Ni(111) across Epitaxial Graphene.

We report on the magnetic coupling between isolated Co atoms as well as small Co islands and Ni(111) mediated by an epitaxial graphene layer. X-ray magnetic circular dichroism and scanning tunneling microscopy combined with density functional theory calculations reveal that Co atoms occupy two distinct adsorption sites, with different magnetic coupling to the underlying Ni(111) surface. We further report a transition from an antiferromagnetic to a ferromagnetic coupling with increasing Co cluster size. Our results highlight the extreme sensitivity of the exchange interaction mediated by graphene to the adsorption site and to the in-plane coordination of the magnetic atoms.

Beneficial defects: exploiting the intrinsic polishing-induced wafer roughness for the catalyst-free growth of Ge in-plane nanowires.

We outline a metal-free fabrication route of in-plane Ge nanowires on Ge(001) substrates. By positively exploiting the polishing-induced defects of standard-quality commercial Ge(001) wafers, micrometer-length wires are grown by physical vapor deposition in ultra-high-vacuum environment. The shape of the wires can be tailored by the epitaxial strain induced by subsequent Si deposition, determining a progressive transformation of the wires in SiGe faceted quantum dots. This shape transition is described by finite element simulations of continuous elasticity and gives hints on the equilibrium shape of nanocrystals in the presence of tensile epitaxial strain. PACS: 81.07.Gf; 68.35.bg; 68.35.bj; 62.23.Eg.