Polygonal tessellations as predictive models of molecular monolayers.

Molecular self-assembly plays a very important role in various aspects of technology as well as in biological systems. Governed by covalent, hydrogen or van der Waals interactions-self-assembly of alike molecules results in a large variety of complex patterns even in two dimensions (2D). Prediction of pattern formation for 2D molecular networks is extremely important, though very challenging, and so far, relied on computationally involved approaches such as density functional theory, classical molecular dynamics, Monte Carlo, or machine learning. Such methods, however, do not guarantee that all possible patterns will be considered and often rely on intuition. Here, we introduce a much simpler, though rigorous, hierarchical geometric model founded on the mean-field theory of 2D polygonal tessellations to predict extended network patterns based on molecular-level information. Based on graph theory, this approach yields pattern classification and pattern prediction within well-defined ranges. When applied to existing experimental data, our model provides a different view of self-assembled molecular patterns, leading to interesting predictions on admissible patterns and potential additional phases. While developed for hydrogen-bonded systems, an extension to covalently bonded graphene-derived materials or 3D structures such as fullerenes is possible, significantly opening the range of potential future applications.

Reexamination of Damping in Sliding Friction.

Friction is responsible for about one-third of the primary energy consumption in the world. So far, a thorough atomistic understanding of the frictional energy dissipation mechanisms is still lacking. The Amontons' law states that kinetic friction is independent of the sliding velocity while the Prandtl-Tomlinson model suggests that damping is proportional to the relative sliding velocity between two contacting objects. Through careful analysis of the energy dissipation process in atomic force microscopy measurements, here we propose that damping force is proportional to the tip oscillation speed induced by friction. It is shown that a physically well-founded damping term can better reproduce the multiple peaks in the velocity-dependent friction force observed in both experiments and molecular dynamics simulations. Importantly, the analysis gives a clear physical picture of the dynamics of energy dissipation in different friction phases, which provides insight into long-standing puzzles in sliding friction, such as velocity weakening and spring-stiffness-dependent friction.

Structural superlubricity and ultralow friction across the length scales.

Structural superlubricity, a state of ultralow friction and wear between crystalline surfaces, is a fundamental phenomenon in modern tribology that defines a new approach to lubrication. Early measurements involved nanometre-scale contacts between layered materials, but recent experimental advances have extended its applicability to the micrometre scale. This is an important step towards practical utilization of structural superlubricity in future technological applications, such as durable nano- and micro-electromechanical devices, hard drives, mobile frictionless connectors, and mechanical bearings operating under extreme conditions. Here we provide an overview of the field, including its birth and main achievements, the current state of the art and the challenges to fulfilling its potential.

Moiré-Tile Manipulation-Induced Friction Switch of Graphene on a Platinum Surface.

Friction control and technological advancement are intimately intertwined. Concomitantly, two-dimensional materials occupy a unique position for realizing quasi-frictionless contacts. However, the question arises of how to tune superlubric sliding. Drawing inspiration from twistronics, we propose to control superlubricity via moiré patterning. Friction force microscopy and molecular dynamics simulations unequivocally demonstrate a transition from a superlubric to dissipative sliding regime for different twist angles of graphene moirés on a Pt(111) surface triggered by the normal force. This follows from a novel mechanism at superlattice level where, beyond a critical load, moiré tiles are manipulated in a highly dissipative shear process connected to the twist angle. Importantly, the atomic detail of the dissipation associated with the moiré tile manipulation─i.e., enduring forced registry beyond a critical normal load─allows the bridging of disparate sliding regimes in a reversible manner, thus paving the road for a subtly intrinsic control of superlubricity.

Atomic Friction Processes of Two-Dimensional Materials.

In this Perspective, we present the recent advances in atomic friction measured of two-dimensional materials obtained by friction force microscopy. Starting with the atomic-scale stick-slip behavior, a beautiful highly nonequilibrium process, we discuss the main factors that contribute to determine sliding friction between single asperity and a two-dimensional sheet including chemical identity of material, thickness, external load, sliding direction, velocity/temperature, and contact size. In particular, we focus on the latest progress of the more complex friction behavior of moiré systems involving 2D layered materials. The underlying mechanisms of these frictional characteristics observed during the sliding process by theoretical and computational studies are also discussed. Finally, a discussion and outlook on the perspective of this field are provided.

Quantitative determination of atomic buckling of silicene by atomic force microscopy.

The atomic buckling in 2D "Xenes" (such as silicene) fosters a plethora of exotic electronic properties such as a quantum spin Hall effect and could be engineered by external strain. Quantifying the buckling magnitude with subangstrom precision is, however, challenging, since epitaxially grown 2D layers exhibit complex restructurings coexisting on the surface. Here, we characterize using low-temperature (5 K) atomic force microscopy (AFM) with CO-terminated tips assisted by density functional theory (DFT) the structure and local symmetry of each prototypical silicene phase on Ag(111) as well as extended defects. Using force spectroscopy, we directly quantify the atomic buckling of these phases within 0.1-Å precision, obtaining corrugations in the 0.8- to 1.1-Å range. The derived band structures further confirm the absence of Dirac cones in any of the silicene phases due to the strong Ag-Si hybridization. Our method paves the way for future atomic-scale analysis of the interplay between structural and electronic properties in other emerging 2D Xenes.

Piranha-etched titanium nanostructure reduces biofilm formation in vitro.

OBJECTIVES: Nano-modified surfaces for dental implants may improve gingival fibroblast adhesion and antibacterial characteristics through cell-surface interactions. The present study investigated how a nanocavity titanium surface impacts the viability and adhesion of human gingival fibroblasts (HGF-1) and compared its response to Porphyromonas gingivalis with those of marketed implant surfaces. MATERIAL AND METHODS: Commercial titanium and zirconia disks, namely, sandblasted and acid-etched titanium (SLA), sandblasted and acid-etched zirconia (ZLA), polished titanium (PT) and polished zirconia (ZrP), and nanostructured disks (NTDs) were tested. Polished titanium disks were etched with a 1:1 combination of 98% H2SO4 and 30% H2O2 (piranha etching) for 5 h at room temperature to produce the NTDs. Atomic force microscopy was used to measure the surface topography, roughness, adhesion force, and work of adhesion. MTT assays and immunofluorescence staining were used to examine cell viability and adhesion after incubation of HGF-1 cells on the disk surfaces. After incubation with P. gingivalis, conventional culture, live/dead staining, and SEM were used to determine the antibacterial properties of NTD, SLA, ZLA, PT, and ZrP. RESULTS: Etching created nanocavities with 10-20-nm edge-to-edge diameters. Chemical etching increased the average surface roughness and decreased the surface adherence, while polishing and flattening of ZrP increased adhesion. However, only the NTDs inhibited biofilm formation and bacterial adherence. The NTDs showed antibacterial effects and P. gingivalis vitality reductions. The HGF-1 cells demonstrated greater viability on the NTDs compared to the controls. CONCLUSION: Nanocavities with 10-20-nm edge-to-edge diameters on titanium disks hindered P. gingivalis adhesion and supported the adhesion of gingival fibroblasts when compared to the surfaces of currently marketed titanium or zirconia dental implants. CLINICAL RELEVANCE: This study prepared an effective antibacterial nanoporous surface, assessed its effects against oral pathogens, and demonstrated that surface characteristics on a nanoscale level influenced oral pathogens and gingival fibroblasts. CLINICAL TRIAL REGISTRATION: not applicable.

Velocity Dependence of Moiré Friction.

Friction force microscopy experiments on moiré superstructures of graphene-coated platinum surfaces demonstrate that in addition to atomic stick-slip dynamics, a new dominant energy dissipation route emerges. The underlying mechanism, revealed by atomistic molecular dynamics simulations, is related to moiré ridge elastic deformations and subsequent relaxation due to the action of the pushing tip. The measured frictional velocity dependence displays two distinct regimes: (i) at low velocities, the friction force is small and nearly constant; and (ii) above some threshold, friction increases logarithmically with velocity. The threshold velocity, separating the two frictional regimes, decreases with increasing normal load and moiré superstructure period. Based on the measurements and simulation results, a phenomenological model is derived, allowing us to calculate friction under a wide range of room temperature experimental conditions (sliding velocities of 1-104 nm/s and a broad range of normal loads) and providing excellent agreement with experimental observations.

N=8 Armchair Graphene Nanoribbons: Solution Synthesis and High Charge Carrier Mobility.

Structurally defined graphene nanoribbons (GNRs) have emerged as promising candidates for nanoelectronic devices. Low band gap (<1 eV) GNRs are particularly important when considering the Schottky barrier in device performance. Here, we demonstrate the first solution synthesis of 8-AGNRs through a carefully designed arylated polynaphthalene precursor. The efficiency of the oxidative cyclodehydrogenation of the tailor-made polymer precursor into 8-AGNRs was validated by FT-IR, Raman, and UV/Vis-near-infrared (NIR) absorption spectroscopy, and further supported by the synthesis of naphtho[1,2,3,4-ghi]perylene derivatives (1 and 2) as subunits of 8-AGNR, with a width of 0.86 nm as suggested by the X-ray single crystal analysis. Low-temperature scanning tunneling microscopy (STM) and solid-state NMR analyses provided further structural support for 8-AGNR. The resulting 8-AGNR exhibited a remarkable NIR absorption extending up to ∼2400 nm, corresponding to an optical band gap as low as ∼0.52 eV. Moreover, optical-pump TeraHertz-probe spectroscopy revealed charge-carrier mobility in the dc limit of ∼270 cm2  V-1 s-1 for the 8-AGNR.

Flexible Superlubricity Unveiled in Sidewinding Motion of Individual Polymeric Chains.

A combination of low temperature atomic force microcopy and molecular dynamic simulations is used to demonstrate that soft designer molecules realize a sidewinding motion when dragged over a gold surface. Exploiting their longitudinal flexibility, pyrenylene chains are indeed able to lower diffusion energy barriers via on-surface directional locking and molecular strain. The resulting ultralow friction reaches values on the order of tens of pN reported so far only for rigid chains sliding on an incommensurate surface. Therefore, we demonstrate how molecular flexibility can be harnessed to realize complex nanomotion while retaining a superlubric character. This is in contrast with the paradigm guiding the design of most superlubric nanocontacts (mismatched rigid contacting surfaces).

On-Surface Synthesis of Unsaturated Hydrocarbon Chains through C-S Activation.

We use an on-surface synthesis approach to drive the homocoupling reaction of a simple dithiophenyl-functionalized precursor on Cu(111). The C-S activation reaction is initiated at low annealing temperature and yields unsaturated hydrocarbon chains interconnected in a fully conjugated reticulated network. High-resolution atomic force microscopy imaging reveals the opening of the thiophenyl rings and the presence of trans- and cis-oligoacetylene chains as well as pentalene units. The chemical transformations were studied by C 1s and S 2p core level photoemission spectroscopy and supported by theoretical calculations. At higher annealing temperature, additional cyclization reactions take place, leading to the formation of small graphene flakes.

On-Surface Synthesis of Porphyrin-Complex Multi-Block Co-Oligomers by Defluorinative Coupling.

On-surface chemical reaction has become a very powerful technique to synthesize nanostructures by linking small molecules in the bottom-up approach. Given the fact that most reactants are simultaneously activated at certain temperatures, a sequential reaction in a controlled way has remained challenging. Here, we present an on-surface synthesis of multi-block co-oligomers from trifluoromethyl (CF3 ) substituted porphyrin metal complexes. The oligomerization on Au(111) is demonstrated with a combination of bond-resolved scanning probe microscopy and density functional theory (DFT) calculations. Even after the first oligomerization of single monomer unit, the termini of the oligomer keep the CF3 group, which can be used as a reactant for further coupling in a sequential order. Consequently, copper, cobalt, and palladium complexes of bisanthracene-fused porphyrin oligomers were linked with each other in a designed order.

Sequential Bending and Twisting around C-C Single Bonds by Mechanical Lifting of a Pre-Adsorbed Polymer.

Bending and twisting around carbon-carbon single bonds are ubiquitous in natural and synthetic polymers. Force-induced changes were so far not measured at the single-monomer level, owing to limited ways to apply local forces. We quantified down to the submolecular level the mechanical response within individual poly-pyrenylene chains upon their detachment from a gold surface with an atomic force microscope at 5 K. Computer simulations based on a dedicated force field reproduce the experimental traces and reveal symmetry-broken bent and rotated conformations of the sliding physisorbed segment besides steric hindrance of the just lifted monomer. Our study also shows that the tip-molecule bond remains intact but remarkably soft and links force variations to complex but well-defined conformational changes.

Head-to-Tail Oligomerization by Silylene-Tethered Sonogashira Coupling on Ag(111).

On-surface synthesis is a powerful method for the fabrication of π-conjugated nanomaterials. Herein, we demonstrate chemoselective Sonogashira coupling between (trimethylsilyl)ethynyl and chlorophenyl groups in silylethynyl- and chloro-substituted partially fluorinated phenylene ethynylenes (SiCPFPEs) on Ag(111). The desilylative Sonogashira coupling occurred with high chemoselectivity up to 75 %, while the competing Ullmann and desilylative Glaser homocoupling reactions were suppressed. A combination of bond-resolved scanning tunneling microscopy/atomic force microscopy (STM/AFM) and DFT calculations revealed that the oligomers were obtained by the formation of intermolecular silylene tethers (-Me2 Si-) through CH3 -Si bond activation at 130 °C and subsequent elimination of the tethers at an elevated temperature of 200 °C.

On-Surface Synthesis of Nitrogen-Doped Kagome Graphene.

Nitrogen-doped Kagome graphene (N-KG) has been theoretically predicted as a candidate for the emergence of a topological band gap as well as unconventional superconductivity. However, its physical realization still remains very elusive. Here, we report on a substrate-assisted reaction on Ag(111) for the synthesis of two-dimensional graphene sheets possessing a long-range honeycomb Kagome lattice. Low-temperature scanning tunneling microscopy (STM) and atomic force microscopy (AFM) with a CO-terminated tip supported by density functional theory (DFT) are employed to scrutinize the structural and electronic properties of the N-KG down to the atomic scale. We demonstrate its semiconducting character due to the nitrogen doping as well as the emergence of Kagome flat bands near the Fermi level which would open new routes towards the design of graphene-based topological materials.

Bottom-up Synthesis of Nitrogen-Doped Porous Graphene Nanoribbons.

Although methods for a periodic perforation and heteroatom doping of graphene sheets have been developed, patterning closely spaced holes on the nanoscale in graphene nanoribbons is still a challenging task. In this work, nitrogen-doped porous graphene nanoribbons (N-GNRs) were synthesized on Ag(111) using a silver-assisted Ullmann polymerization of brominated tetrabenzophenazine. Insights into the hierarchical reaction pathways from single molecules toward the formation of one-dimensional organometallic complexes and N-GNRs are gained by a combination of scanning tunneling microscopy (STM), atomic force microscopy (AFM) with CO-tip, scanning tunneling spectroscopy (STS), and density functional theory (DFT).

Band Gap of Atomically Precise Graphene Nanoribbons as a Function of Ribbon Length and Termination.

We study the band gap of finite N A = 7 armchair graphene nanoribbons (7-AGNRs) on Au(111) through scanning tunneling microscopy/spectroscopy combined with density functional theory calculations. The band gap of 7-AGNRs with lengths of 8 nm and more is converged to within 50 meV of its bulk value of ≈ 2 . 3 eV , while the band gap opens by several hundred meV in very short 7-AGNRs. We demonstrate that even an atomic defect, such as the addition of one hydrogen atom at the termini, has a significant effect - in this case, lowering the band gap. The effect can be captured in terms of a simple analytical model by introducing an effective "electronic length".

Plasma-assisted catalytic formation of ammonia in N2-H2 plasma on a tungsten surface.

Plasma catalysis has drawn attention in the past few decades as a possible alternative to the Haber-Bosch process for ammonia production. In particular, radio frequency plasma assisted catalysis has the advantage of its adaptability to the industrial scale. However, in the past years, very few experimental studies have focused on the synthesis of ammonia from nitrogen/hydrogen radio frequency plasma. As a consequence, to date, there has been little agreement about the complex mechanisms underlying the radio frequency plasma-catalyst interactions. Gaining such an understanding is therefore essential for exploiting the potential of radio frequency plasma catalysis for ammonia production. In this study, we present results of ammonia formation from a nitrogen/hydrogen radio frequency plasma both without and with a tungsten catalyst for different initial nitrogen ratios. High yields of ammonia up to 32% at 25/75% of nitrogen/hydrogen were obtained using a combination of radio frequency low pressure plasma and a W surface as a catalyst. Furthermore, based on chemical analysis of the catalytic surface composition, a formation pathway of ammonia via the Eley-Rideal mechanism between adsorbed nitrogen and hydrogen from the gas phase is presented.

Quantum Dots Embedded in Graphene Nanoribbons by Chemical Substitution.

Bottom-up chemical reactions of selected molecular precursors on a gold surface can produce high quality graphene nanoribbons (GNRs). Here, we report on the formation of quantum dots embedded in an armchair GNR by substitutional inclusion of pairs of boron atoms into the GNR backbone. The boron inclusion is achieved through the addition of a small amount of boron substituted precursors during the formation of pristine GNRs. In the pristine region between two boron pairs, the nanoribbons show a discretization of their valence band into confined modes compatible with a Fabry-Perot resonator. Transport simulations of the scattering properties of the boron pairs reveal that they selectively confine the first valence band of the pristine ribbon while allowing an efficient electron transmission of the second one. Such band-dependent electron scattering stems from the symmetry matching between the electronic wave functions of the states from the pristine nanoribbons and those localized at the boron pairs.

A Two-Dimensional Polymer Synthesized at the Air/Water Interface.

A trifunctional, partially fluorinated anthracene-substituted triptycene monomer was spread at an air/water interface into a monolayer, which was transformed into a long-range-ordered 2D polymer by irradiation with a standard UV lamp. The polymer was analyzed by Brewster angle microscopy, scanning tunneling microscopy measurements, and non-contact atomic force microscopy, which confirmed the generation of a network structure with lattice parameters that are virtually identical to a structural model network based on X-ray diffractometry of a closely related 2D polymer. The nc-AFM images highlight the long-range order over areas of at least 300×300 nm2 . As required for a 2D polymer, the pore sizes are monodisperse, except for the regions where the network is somewhat stretched because it spans over protrusions. Together with a previous report on the nature of the cross-links in this network, the structural information provided herein leaves no doubt that a 2D polymer has been synthesized under ambient conditions at an air/water interface.