Progress in Surface Science最新文献

Spectroscopic measurements with low-temperature scanning tunneling microscopes have been used very successfully for studying not only individual atomic or molecular spins on surfaces but also complexly designed coupled systems. The symmetry breaking of the supporting surface induces magnetic anisotropy which lead to characteristic fingerprints in the spectrum of the differential conductance and can be well understood with simple model Hamiltonians. Furthermore, correlated many-particle states can emerge due to the interaction with itinerant electrons of the electrodes, making these systems ideal prototypical quantum systems. In this manuscript more complex bipartite and spin-chains will be discussed additionally. Their spectra enable to determine precisely the nature of the interactions between the spins which can lead to the formation of new quantum states which emerge by interatomic entanglement.

We review the problem of spin decoherence of magnetic atoms deposited on a surface. Recent breakthroughs in scanning tunnelling microscopy (STM) make it possible to probe the spin dynamics of individual atoms, either isolated or integrated in nanoengineered spin structures. Transport pump and probe techniques with spin polarized tips permit measuring the spin relaxation time $T_1$, while novel demonstration of electrically driven STM single spin resonance has provided a direct measurement of the spin coherence time $T_2$ of an individual magnetic adatom. Here we address the problem of spin decoherence from the theoretical point of view. First we provide a short general overview of decoherence in open quantum systems and we discuss with some detail ambiguities that arise in the case of degenerate spectra, relevant for magnetic atoms. Second, we address the physical mechanisms that allows probing the spin coherence of magnetic atoms on surfaces. Third, we discuss the main spin decoherence mechanisms at work on a surface, most notably, Kondo interaction, but also spin–phonon coupling and dephasing by Johnson noise. Finally, we briefly discuss the implications in the broader context of quantum technologies.

In this review we examine the influence of the line tension τ on droplets and particles at surfaces. The line tension influences the nucleation behavior and contact angle of liquid droplets at both liquid and solid surfaces and alters the attachment energetics of solid particles to liquid surfaces. Many factors, occurring over a wide range of length scales, contribute to the line tension. On atomic scales, atomic rearrangements and reorientations of submolecular components give rise to an atomic line tension contribution τ_atom (∼1 nN), which depends on the similarity/dissimilarity of the droplet/particle surface composition compared with the surface upon which it resides. At nanometer length scales, an integration over the van der Waals interfacial potential gives rise to a mesoscale contribution |τ_vdW| ∼ 1–100 pN while, at millimeter length scales, the gravitational potential provides a gravitational contribution τ_grav ∼ +1–10 μN. τ_grav is always positive, whereas, τ_vdW can have either sign. Near wetting, for very small contact angle droplets, a negative line tension may give rise to a contact line instability. We examine these and other issues in this review.

Sum-frequency generation vibrational spectroscopy (SFG-VS) was first developed in the 1980s and it has been proven a uniquely sensitive and surface/interface selective spectroscopic probe for characterization of the structure, conformation and dynamics of molecular surfaces and interfaces. In recent years, there have been many progresses in the development of methodology and instrumentation in the SFG-VS toolbox that have significantly broadened the application to complex molecular surfaces and interfaces. In this review, after presenting a unified view on the theory and methodology focusing on the SFG-VS spectral lineshape, as well as the new opportunities in SFG-VS applications with such developments, some of the controversial issues that have been puzzling the community are discussed. The aim of this review is to present to the researchers and students interested in molecular surfaces and interfacial sciences up-to-date perspectives complementary to the existing textbooks and reviews on SFG-VS.

Charge separation and transfer at the interface between two materials play a significant role in various atomic-scale processes and energy conversion systems. In this review, we present the mechanism and outcome of charge transfer in TiO₂, which is extensively explored for photocatalytic applications in the field of environmental science. We list several experimental and computational methods to estimate the amount of charge transfer. The effects of the work function, defects and doping, and employment of external electric field on modulating the charge transfer are presented. The interplay between the band bending and carrier transport across the surface and interface consisting of TiO₂ is discussed. We show that the charge transfer can also strongly affect the behavior of deposited nanoparticles on TiO₂ through built-in electric field that it creates. This review encompasses several advances of composite materials where TiO₂ is combined with two-dimensional materials like graphene, MoS₂, phosphorene, etc. The charge transport in the TiO₂-organohalide perovskite with respect to the electron-hole separation at the interface is also discussed.

Designing antibacterial surfaces has become extremely important to minimize Healthcare Associated Infections which are a major cause of mortality worldwide. A previous biocide-releasing approach is based on leaching of encapsulated biocides such as silver and triclosan which exerts negative impacts on the environment and potentially contributes to the development of bacterial resistance. This drawback of leachable compounds led to the shift of interest towards a more sustainable and environmentally friendly approach: contact-killing surfaces. Biocides that can be bound onto surfaces to give the substrates contact-active antibacterial activity include quaternary ammonium compounds (QACs), quaternary phosphoniums (QPs), carbon nanotubes, antibacterial peptides, and N-chloramines. Among the above, QACs and N-chloramines are the most researched contact-active biocides. We review the engineering of contact-active surfaces using QACs or N-chloramines, the modes of actions as well as the test methods. The charge-density threshold of cationic surfaces for desired antibacterial efficacy and attempts to combine various biocides for the generation of new contact-active surfaces are discussed in detail. Surface positive charge density is identified as a key parameter to define antibacterial efficacy. We expect that this research field will continue to attract more research interest in view of the potential impact of self-disinfective surfaces on healthcare-associated infections, food safety and corrosion/fouling resistance required on industrial surfaces such as oil pipes and ship hulls.

Metal–organic coordination structures are materials comprising reticular metal centers and organic linkers in which the two constituents bind with each other via metal–ligand coordination interaction. The underlying chemistry is more than a century old but has attracted tremendous attention in the last two decades owing to the rapidly development of metal–organic (or porous coordination) frameworks. These metal-coordination materials exhibit extraordinarily versatile topologies and many potential applications. Since 2002, this traditionally three-dimensional chemistry has been extended to two-dimensional space, that is, to synthesize metal–organic coordination structures directly on solid surfaces. This endeavor has made possible a wide range of so-called surface-confined metal–organic networks (SMONs) whose topology, composition, property and function can be tailored by applying the principle of rational design. The coordination chemistry manifests unique characteristics at the surfaces, and in turn the surfaces provide additional control for design structures and properties that are inaccessible in three-dimensional space.

In this review, our goal is to comprehensively cover the progress made in the last 15 years in this rapidly developing field. The review summarizes (1) the experimental and theoretical techniques used in this field including scanning tunneling microscopy and spectroscopy, low-energy electron diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, density functional theory, and Monte Carlo and kinetic Monte Carlo simulation; (2) molecular ligands, metal atoms, substrates, and coordination motifs utilized for synthesizing SMON; (3) representative SMON structures with different topologies ranging from finite-size discrete clusters to one-dimensional chains, two-dimensional periodical frameworks and random networks; and (4) the properties and potential applications of SMONs. We conclude the review with some perspectives.

Adsorption geometry and stability of organic molecules on surfaces are key parameters that determine the observable properties and functions of hybrid inorganic/organic systems (HIOSs). Despite many recent advances in precise experimental characterization and improvements in first-principles electronic structure methods, reliable databases of structures and energetics for large adsorbed molecules are largely amiss. In this review, we present such a database for a range of molecules adsorbed on metal single-crystal surfaces. The systems we analyze include noble-gas atoms, conjugated aromatic molecules, carbon nanostructures, and heteroaromatic compounds adsorbed on five different metal surfaces. The overall objective is to establish a diverse benchmark dataset that enables an assessment of current and future electronic structure methods, and motivates further experimental studies that provide ever more reliable data. Specifically, the benchmark structures and energetics from experiment are here compared with the recently developed van der Waals (vdW) inclusive density-functional theory (DFT) method, DFT + vdW^surf. In comparison to 23 adsorption heights and 17 adsorption energies from experiment we find a mean average deviation of 0.06 Å and 0.16 eV, respectively. This confirms the DFT + vdW^surf method as an accurate and efficient approach to treat HIOSs. A detailed discussion identifies remaining challenges to be addressed in future development of electronic structure methods, for which the here presented benchmark database may serve as an important reference.

Superhydrophobic films were prepared using dispersions of fluorinated multi-walled carbon nanotubes (MWCNTs) or nanofibers (CNFs) in toluene. The grafting of polystyrene allowed stable dispersions to be obtained. The grafting of polystyrene (PS), polyacrylic acid (PAA) and polyaniline (PANI) onto nanofibers and MWCNTs was first evidenced by solid state NMR and Infrared Spectroscopy. The graft polymerization of styrene, acrylic acid and aniline monomers was initiated by radicals (dangling bonds) formed due to the initial fluorination. The process appeared as highly versatile and efficient for different polymers. The consumption of those radicals in the course of grafting was evidenced by EPR, through decrease of the spin density. The hydrophobic/hydrophilic character was tuned according to the grafted polymer nature, i.e. hydrophobic with PS or hydrophilic with PAA. Finally, in order to reach superhydrophobicity, films were prepared from CNFs or MWCNTs, irrespective of their average diameter, that allowed adequate structuring of the surface. The presence of fluorine atoms on their surface also favors superhydrophobicity. Water contact angles of 155 ± 2° and 159 ± 2° were measured for the films casted from fluorinated CNFs or MWCNTs with grafted polystyrene, respectively.