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To develop new types of dynamic molecular devices with atomic-scale control over electronic function, new types of molecular switches are needed with time-dependent switching probabilities. We report such a molecular switch based on proton-coupled electron transfer (PCET) reaction with giant hysteric negative differential resistance (NDR) with peak-to-valley ratios of 120 ± 6.6 and memory on/off ratios of (2.4 ± 0.6) × 10 3 . The switching dynamics probabilities are modulated by bias voltage sweep rate and can also be controlled by pH and relative humidity, confirmed by kinetic isotope effect measurements. The demonstrated dynamical and environment-specific modulation of giant NDR and memory effects provide new opportunities for bioelectronics and artificial neural networks., (© 2024. The Author(s).)

Evidence of presolidification, the counterpart to premelting, is reported. Near the eutectic temperature, T_{C}, the propagation direction of thermal gradient driven motion of eutectic Ge-Pt droplets on Ge(110) is determined by presolidification. Well above T_{C}, the micron-sized droplets move towards the hottest location at the substrate, irrespective of crystalline direction. At 90 K above T_{C}, a strong, unanticipated preference for propagation along the substrate [001] azimuth suddenly emerges, which is attributed to presolidification at the liquid-solid interface. The propagation along [001] is accompanied by a distinct change in shape from compact to elongated along [001].

Usually, electronic transport measurements on two-dimensional materials, such as graphene and transition metal dichalcogenides, require deposition of electrodes on top of the material, in, for instance, the form of a Hall bar device. In this work, we show that by making use of a collinear micro-four-point probe, electrical transport measurements on small flakes of graphene can be performed without having to fabricate electrodes on top of the flakes. Using probes with probe pitches down to sub-micrometer scale, we show back-gate tuned transport measurements in graphene on silicon oxide and on hexagonal boron nitride. The charge carrier mobilities and the minimum conductivity of graphene are in good agreement with conventional transport measurements. In addition, we assess the possible damage caused by landing these probes on graphene., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

Two-dimensional transition metal dichalcogenide (TMDC) materials have shown great potential for usage in opto-electronic devices, especially down to the regime of a few layers to a single layer. However, at these limits, the material properties can be strongly influenced by the interfaces. By using photoconductive atomic force microscopy, we show a local enhancement of photoconductivity at the nanoscale in bilayer molybdenum disulfide on mica, where water is confined between the TMDC and the substrate. We have found that the structural phase of the water influences the doping level and thus the tunneling barrier at the nanojunction. This leads to an increase in photocurrent and enhanced photopower generation., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

We present the first experimental evidence of a topological phase transition in a monoelemental quantum spin Hall insulator. Particularly, we show that low-buckled epitaxial germanene is a quantum spin Hall insulator with a large bulk gap and robust metallic edges. Applying a critical perpendicular electric field closes the topological gap and makes germanene a Dirac semimetal. Increasing the electric field further results in the opening of a trivial gap and disappearance of the metallic edge states. This electric field-induced switching of the topological state and the sizable gap make germanene suitable for room-temperature topological field-effect transistors, which could revolutionize low-energy electronics.

The Ge(110) surface reconstructs into ordered and disordered phases, in which the basic unit is a five-membered ring of Ge atoms (pentagon). The variety of surface reconstructions leads to a rich electronic density of states with several surface states. Using scanning tunneling microscopy and spectroscopy, we have identified the exact origins of these surface states and linked them to either the Ge pentagons or the underlying Ge-Ge bonds. We show that even moderate fluctuations in the positions of the Ge pentagonal units induce large variations in the local density of states. The local density of states modulates in a precise manner, following the geometrical constraints on tiling Ge pentagons. These geometry-correlated electronic states offer a vast configurational landscape that could provide new opportunities in data storage and computing applications., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Vanadium dioxide (VO 2 ) is a popular candidate for electronic and optical switching applications due to its well-known semiconductor-metal transition. Its study is notoriously challenging due to the interplay of long- and short-range elastic distortions, as well as the symmetry change and the electronic structure changes. The inherent coupling of lattice and electronic degrees of freedom opens the avenue toward mechanical actuation of single domains. In this work, we show that we can manipulate and monitor the reversible semiconductor-to-metal transition of VO 2 while applying a controlled amount of mechanical pressure by a nanosized metallic probe using an atomic force microscope. At a critical pressure, we can reversibly actuate the phase transition with a large modulation of the conductivity. Direct tunneling through the VO 2 -metal contact is observed as the main charge carrier injection mechanism before and after the phase transition of VO 2 . The tunneling barrier is formed by a very thin but persistently insulating surface layer of the VO 2 . The necessary pressure to induce the transition decreases with temperature. In addition, we measured the phase coexistence line in a hitherto unexplored regime. Our study provides valuable information on pressure-induced electronic modifications of the VO 2 properties, as well as on nanoscale metal-oxide contacts, which can help in the future design of oxide electronics., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

We have studied decanethiolate self-assembled monolayers on the Au(001) surface. Planar and striped phases, as well as disordered regions, have formed after exposing the Au surface to a decanethiol solution. The planar phases that we observe have a hexagonal symmetry and have not been previously reported for thiols on the Au(001) surface and have lower coverage compared to that of the other known thiol planar phases such as the square α phase. The striped phases that we observe are similar to the previously reported β phase but still feature unit cells that cannot be modeled as the archetype, and the coverage is also somewhat lower. The disordered decanethiolate regions are more dynamic compared to the ordered phases, confirmed with I ( t ) spectroscopy. This suggests that in these regions the coverage is too low in order to form ordered decanethiolate phases. Our findings contribute to the growing family of possible decanethiol formations on the Au(001) surface, for which still less is known compared to the extensive overview present for the Au(111) surface.

We embarked on an in situ low-energy electron microscopy, photo-electron emission microscopy, and selected area low-energy electron diffraction study during the cooling of huge eutectic droplets through the critical stages of the eutectic transition. On this journey through uncharted waters, we revealed an expected initial shrinking of the exposed area of the droplet, followed by an unanticipated expansion. We attribute this behavior to an initial fast amorphization of the interface between the droplet and surface, followed by the recrystallization of Ge expelled from the droplet at the interface. As a major surprise, we discovered the emergence of extensive "spaghetti"-like patterns, which are rationalized in terms of parallel Ge ripples oriented along, mainly, [-554] and [-55-4] directions. They emerge during spinodal decomposition when passing the eutectic temperature of the system. Their sides are defined by Ge{111} and Ge{11-1} vicinals covered with Pt-modified (√3 × √3) superstructures. The distance between adjacent ripples is about 18 nm., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Germanium sulfide (GeS) is a layered monochalcogenide semiconductor with a band gap of about 1.6 eV. To verify the suitability of GeS for field-effect-based device applications, a detailed understanding of the electronic transport mechanisms of GeS-metal junctions is required. In this work, we have used conductive atomic force microscopy (c-AFM) to study charge carrier injection in metal-GeS nanocontacts. Using contact current-voltage spectroscopy, we identified three dominant charge carrier injection mechanisms: thermionic emission, direct tunneling, and Fowler-Nordheim tunneling. In the forward-bias regime, thermionic emission is the dominating current injection mechanism, whereas in the reverse-bias regime, the current injection mechanism is quantum mechanical tunneling. Using tips of different materials (platinum, n-type-doped silicon, and highly doped p-type diamond), we found that the Schottky barrier is almost independent of the work function of the metallic tip, which is indicative of a strong Fermi-level pinning. This strong Fermi-level pinning is caused by charged defects and impurities., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Multi-component fluids with phase transitions show a plethora of fascinating phenomena with rich physics. Here we report on a transition in the growth mode of plasmonic bubbles in binary liquids. By employing high-speed imaging we reveal that the transition is from slow evaporative to fast convective growth and accompanied by a sudden increase in radius. The transition occurs as the three-phase contact line reaches the spinodal temperature of the more volatile component leading to massive, selective evaporation. This creates a strong solutal Marangoni flow along the bubble which marks the beginning of convective growth. We support this interpretation by simulations. After the transition the bubble starts to oscillate in position and in shape. Though different in magnitude the frequencies of both oscillations follow the same power law , which is characteristic of bubble shape oscillations, with the surface tension σ as the restoring force and the bubble's added mass as inertia. The transitions and the oscillations both induce a strong motion in the surrounding liquid, opening doors for various applications where local mixing is beneficial.

The growth of elemental metal single-crystals is usually achieved through classic growth techniques such as the Czochralski or floating zone methods. Drawbacks of these techniques are the susceptibility to contamination from the crucible and thermal stress-induced defects due to contact with the ambient, which can be mitigated by growing in a containerless environment. We discuss the development of a novel crystal growth apparatus that employs electromagnetic levitation in a vacuum to grow metal single-crystals of superior quality and purity. This apparatus enables two growth modes: containerless undercooled crystallization and levitation-based Czochralski growth. We describe the experimental setup in terms of coil design, sample insertion and collection, seed insertion, and sample position and temperature tracking. As a proof of concept, we show the successful growth of copper single-crystals.

Plasmonic bubbles are of great relevance in numerous applications, including catalytic reactions, micro/nanomanipulation of molecules or particles dispersed in liquids, and cancer therapeutics. So far, studies have been focused on bubble nucleation in pure liquids. Here we investigate plasmonic bubble nucleation in ternary liquids consisting of ethanol, water, and trans-anethole oil, which can show the so-called ouzo effect. We find that oil (trans-anethole) droplet plumes are produced around the growing plasmonic bubbles. The nucleation of the microdroplets and their organization in droplet plumes is due to the symmetry breaking of the ethanol concentration field during the selective evaporation of ethanol from the surrounding ternary liquids into the growing plasmonic bubbles. Numerical simulations show the existence of a critical Marangoni number Ma (the ratio between solutal advection rate and the diffusion rate), above which the symmetry breaking of the ethanol concentration field occurs, leading to the emission of the droplet plumes. The numerical results agree with the experimental observation that more plumes are emitted with increasing ethanol-water relative weight ratios and hence Ma. Our findings on the droplet plume formation reveal the rich phenomena of plasmonic bubble nucleation in multicomponent liquids and help to pave the way to achieve enhanced mixing in multicomponent liquids in chemical, pharmaceutical, and cosmetic industries.

The physicochemical hydrodynamics of bubbles and droplets out of equilibrium, in particular with phase transitions, display surprisingly rich and often counterintuitive phenomena. Here we experimentally and theoretically study the nucleation and early evolution of plasmonic bubbles in a binary liquid consisting of water and ethanol. Remarkably, the submillimeter plasmonic bubble is found to be periodically attracted to and repelled from the nanoparticle-decorated substrate, with frequencies of around a few kilohertz. We identify the competition between solutal and thermal Marangoni forces as the origin of the periodic bouncing. The former arises due to the selective vaporization of ethanol at the substrate's side of the bubble, leading to a solutal Marangoni flow toward the hot substrate, which pushes the bubble away. The latter arises due to the temperature gradient across the bubble, leading to a thermal Marangoni flow away from the substrate, which sucks the bubble toward it. We study the dependence of the frequency of the bouncing phenomenon from the control parameters of the system, namely the ethanol fraction and the laser power for the plasmonic heating. Our findings can be generalized to boiling and electrolytically or catalytically generated bubbles in multicomponent liquids., Competing Interests: The authors declare no competing interest.

Water-immersed gold nanoparticles irradiated by a laser can trigger the nucleation of plasmonic bubbles after a delay time of a few microseconds [Wang et al., Proc. Natl. Acad. Sci. USA 122, 9253 (2018)]. Here we systematically investigated the light-vapor conversion efficiency, η, of these plasmonic bubbles as a function of the ambient pressure. The efficiency of the formation of these initial-phase and mainly water-vapor containing bubbles, which is defined as the ratio of the energy that is required to form the vapor bubbles and the total energy dumped in the gold nanoparticles before nucleation of the bubble by the laser, can be as high as 25%. The amount of vaporized water first scales linearly with the total laser energy dumped in the gold nanoparticles before nucleation, but for larger energies the amount of vaporized water levels off. The efficiency η decreases with increasing ambient pressure. The experimental observations can be quantitatively understood within a theoretical framework based on the thermal diffusion equation and the thermal dynamics of the phase transition.

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 d I /d z spectroscopy. The square root of the tunnel barrier height is directly proportional to the local work function and the d I /d z 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 d I /d z 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.

The growth of surface plasmonic microbubbles in binary water/ethanol solutions is experimentally studied. The microbubbles are generated by illuminating a gold nanoparticle array with a continuous wave laser. Plasmonic bubbles exhibit ethanol concentration-dependent behaviors. For low ethanol concentrations ( f e ) of ≲67.5%, bubbles do not exist at the solid-liquid interface. For high f e values of ≳80%, the bubbles behave as in pure ethanol. Only in an intermediate window of 67.5% ≲ f e ≲ 80% do we find sessile plasmonic bubbles with a highly nontrivial temporal evolution, in which as a function of time three phases can be discerned. (1) In the first phase, the microbubbles grow, while wiggling. (2) As soon as the wiggling stops, the microbubbles enter the second phase in which they suddenly shrink, followed by (3) a steady reentrant growth phase. Our experiments reveal that the sudden shrinkage of the microbubbles in the second regime is caused by a depinning event of the three-phase contact line. We systematically vary the ethanol concentration, laser power, and laser spot size to unravel water recondensation as the underlying mechanism of the sudden bubble shrinkage in phase 2.

Hypothesis: The Hansen Solubility Parameters (HSP) derived from Molecular Dynamics (MD) simulations can be used as a fast approach to predict surfactants adsorption on a solid surface. Experiments and simulations: We focused on the specific case of siloxane-based surfactants adsorption on silicon oxide surface (SiO 2 ), encountered in inkjet printing processes. A simplified atomistic model of the SiO 2 surface was designed to enable the computation of its solubility parameter using MD, and to subsequently determine the interactions of the SiO 2 surface with the siloxane-based surfactant and the various solvents employed. Surfactant adsorption was characterized experimentally using contact angle goniometry, ellipsometry, XPS and AFM., Findings: Comparison of the numerical results with experiments showed that the HSP theory allows to identify the range of solvents that are likely to prevent surfactant adsorption on the SiO 2 surface. The proposed approach indicates that polar solvents, such as acetone and triacetin, which are strongly attracted to the silicon oxide surface might form a shield that prevents siloxane-based surfactants adsorption. This simple approach, can guide the selection of adequate solvents for surfaces and surfactants with specific chemical structures, providing opportunities for controlling interfacial adsorption., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier Inc. All rights reserved.)

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 T_{c} given by e^{-(ε_{1}+ε_{2})/2kT_{c}}+e^{-(ε_{2}+ε_{3})/2kT_{c}}+e^{-(ε_{3}+ε_{1})/2kT_{c}}=1, where ε_{1}, ε_{2}, ε_{3} are the nearest-neighbor interaction energies, and ε_{1}+ε_{2}>0, ε_{2}+ε_{3}>0, ε_{3}+ε_{1}>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.

The thermal decomposition of graphene oxide (GO) is a complex process at the atomic level and not fully understood. Here, a subclass of GO, oxo-functionalized graphene (oxo-G), was used to study its thermal disproportionation. We present the impact of annealing on the electronic properties of a monolayer oxo-G flake and correlated the chemical composition and topography corrugation by two-probe transport measurements, XPS, TEM, FTIR and STM. Surprisingly, we found that oxo-G, processed at 300 °C, displays C-C sp 3 -patches and possibly C-O-C bonds, next to graphene domains and holes. It is striking that those C-O-C/C-C sp 3 -separated sp 2 -patches a few nanometers in diameter possess semiconducting properties with a band gap of about 0.4 eV. We propose that sp 3 -patches confine conjugated sp 2 -C atoms, which leads to the local semiconductor properties. Accordingly, graphene with sp 3 -C in double layer areas is a potential class of semiconductors and a potential target for future chemical modifications., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Metal nanoparticles under laser irradiation can produce enormous heat due to surface plasmon resonance. When submerged in a liquid, this can lead to the nucleation of plasmonic bubbles. In the very early stage, the nucleation of a giant vapor bubble was observed with an ultrahigh-speed camera. In this study, the formation of this giant bubble on gold nanoparticles in six binary liquid combinations has been investigated. We find that the time delay between the beginning of the laser heating and the bubble nucleation is determined by the absolute amount of dissolved gas in the liquid. Moreover, the bubble volume mainly depends on the vaporization energy of the liquid, consisting of the latent heat of vaporization and the energy needed to reach the boiling temperature. Our results contribute to controlling the initial giant bubble nucleation and have strong bearings on applications of such bubbles., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

Under continuous laser irradiation, noble metal nanoparticles immersed in water can quickly heat up, leading to the nucleation of so-called plasmonic bubbles. In this work, we want to further understand the bubble nucleation and growth mechanism. In particular, we quantitatively study the effect of the amount of dissolved air on the bubble nucleation and growth dynamics, both for the initial giant bubble, which forms shortly after switching on the laser and is mainly composed of vapor, and for the final life phase of the bubble, during which it mainly contains air expelled from water. We found that the bubble nucleation temperature depends on the gas concentration: the higher the gas concentration, the lower the bubble nucleation temperature. Also, the long-term diffusion-dominated bubble growth is governed by the gas concentration. The radius of the bubbles grows as R ( t ) ∝ t 1/3 for air-equilibrated and air-oversaturated water. In contrast, in partially degassed water, the growth is much slower since, even for the highest temperature we achieve, the water remains undersaturated., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

Evaporation of surfactant-laden sessile droplets is omnipresent in nature and industrial applications such as inkjet printing. Soluble surfactants start to form micelles in an aqueous solution for surfactant concentrations exceeding the critical micelle concentration (CMC). Here, the evaporation of aqueous sodium dodecyl sulfate (SDS) sessile droplets on hydrophobic surfaces was experimentally investigated for SDS concentrations ranging from 0.025 to 1 CMC. In contrast to the constant contact angle of an evaporating sessile water droplet, we observed that, at the same surface, the contact angle of an SDS laden droplet with concentration below 0.5 CMC first decreases, then increases, and finally decreases, resulting in a local contact angle minimum. Surprisingly, the minimum contact angle was found to be substantially lower than the static receding contact angle and decreased with decreasing initial SDS concentration. Furthermore, the bulk SDS concentration at the local contact angle minimum was found to decrease with decrease in the initial SDS concentration. The location of the observed contact angle minimum relative to the normalized evaporation time and its minimum value proved to be independent of both the relative humidity and droplet volume and thus of the total evaporation time. We discuss the observed contact angle dynamics in terms of the formation of a disordered layer of SDS molecules on the substrate at concentrations below 0.5 CMC. The present work underlines the complexity of the evaporation of sessile liquid-surfactant droplets and the influence of surfactant-substrate interactions on the evaporation process.

Here we report on a novel, noninvasive route for operando tailoring of the charge transport properties of metal/WS 2 contacts without the negative impacts to two-dimensional materials arising from conventional doping methods. The doping level of thin WS 2 flakes supported on insulating mica is susceptible to local charge variations induced by the presence of a hydration layer between mica and WS 2 . We demonstrate, via the use of several complementary scanning probe techniques, that the direct control of the state and thickness of this intercalated water film controls the charge injection properties of Pt/WS 2 nanocontacts. A switch from unipolar to ambipolar transport was achieved by environmentally controlling the thickness of the intercalated water. We show that the effect persists even for multilayer flakes and that it is completely reversible, opening a new route toward the realization of novel electronics with environmentally controllable functionalities.

The friction of graphene on mica was studied using lateral force microscopy. We observed that intercalation of alcohol molecules significantly increases the friction of graphene, as compared to water. An increase of 1.8, 2.4, and 5.9 times in friction between the atomic force microscopy tip and  single-layer graphene was observed for methanol, ethanol, and 2-propanol, respectively. Moreover, the friction of graphene is found to be higher for single-layer graphene than for multilayer graphene. We attribute the increase in friction to the additional vibrational modes of alcohol molecules. The significant variation of the frictional characteristics of graphene at the nanoscale by altering the intercalant could open up applications for the next-generation nanolubricants and nanodevices.

Transition metal dichalcogenides (TMDC) have recently attracted much attention as a promising platform for the realization of 2-dimensional (2D) electronic devices. One of the major challenges for their wide-scale application is the control of the potential barrier at the metal/TMDC junction. Using conductive atomic force microscopy (c-AFM) we have investigated modifications of the Schottky barrier height (SBH) across a Pt/WS2 junction by the introduction of thin buffer layers of graphene and MoSe2. While graphene greatly reduces the contact resistance in both bias directions, thin layers of MoSe2 lower the Schottky barrier and leave the rectifying properties of the junction intact. We have studied the dependence of the transport properties on the thickness of the graphene and MoSe2 buffer layers. In both cases, the charge transport characteristics can be tailored by varying the buffer layer thickness. The edge of single layer graphene is observed to form an ohmic contact to the underlying WSe2 substrate. This study demonstrates that the introduction of atomically thin MoSe2 and graphene buffer layers is a feasible and elegant method to control the Schottky barrier when contacting TMDCs. The results are important for the fabrication of devices utilizing 2D materials.

The formation of self-assembled superstructures of cetyltrimethylammonium bromide (CTAB) after drying on a nonwetting highly ordered pyrolytic graphite (HOPG) surface have been investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Although SEM did not reveal coverage of CTAB layers, AFM showed not only CTAB assembly, but also the dynamics of the process on the surface. The self-assembled layers of CTAB molecules on the HOPG terraces prior to nanorod deposition were shown to change the wettability of the surface, and as a result, gold nanorod deposition takes place on nonwetting HOPG terraces.

Understanding the electron transport through transition-metal dichalcogenide (TMDC)-based semiconductor/metal junctions is vital for the realization of future TMDC-based (opto-)electronic devices. Despite the bonding in TMDCs being largely constrained within the layers, strong Fermi-level pinning (FLP) was observed in TMDC-based devices, reducing the tunability of the Schottky barrier height. We present evidence that metal-induced gap states (MIGS) are the origin for the large FLP similar to conventional semiconductors. A variety of TMDCs (MoSe 2 , WSe 2 , WS 2 , and MoTe 2 ) were investigated using high-spatial-resolution surface characterization techniques, permitting us to distinguish between defected and pristine regions. The Schottky barrier heights on the pristine regions can be explained by MIGS, inducing partial FLP. The FLP strength is further enhanced by disorder-induced gap states induced by transition-metal vacancies or substitutionals at the defected regions. Our findings emphasize the importance of defects on the electron transport properties in TMDC-based devices and confirm the origin of FLP in TMDC-based metal/semiconductor junctions., Competing Interests: The authors declare no competing financial interest.

The down-scaling of electrical components requires a proper understanding of the physical mechanisms governing charge transport. Here, we have investigated atomic-scale contacts and their transport characteristics on WS 2 using conductive atomic force microscopy (c-AFM). We demonstrate that c-AFM can provide true atomic resolution, revealing atom vacancies, adatoms, and periodic modulations arising from electronic effects. Moreover, we find a lateral variation of the surface conductivity that arises from the lattice periodicity of WS 2 . Three distinct sites are identified, i.e., atop, bridge, and hollow. The current transport across these atomic metal-semiconductor interfaces is understood by considering thermionic emission and Fowler-Nordheim tunnelling. Current modulations arising from point defects and the contact geometry promise a novel route for the direct control of atomic point contacts in diodes and devices.

HfSe 2 is a very good candidate for a transition metal dichalcogenide-based field-effect transistor owing to its moderate band gap of about 1 eV and its high-κ dielectric native oxide. Unfortunately, the experimentally determined charge carrier mobility is about 3 orders of magnitude lower than the theoretically predicted value. This strong deviation calls for a detailed investigation of the physical and electronic properties of HfSe 2 . Here, we have studied the structure, density, and density of states of several types of defects that are abundant on the HfSe 2 surface using scanning tunneling microscopy and spectroscopy. Compared to MoS 2 and WSe 2 , HfSe 2 exhibits similar type of defects, albeit with a substantially higher density of 9 × 10 11 cm -2 . The most abundant defect is a subsurface defect, which shows up as a dim feature in scanning tunneling microscopy images. These dim dark defects have a substantially larger band gap (1.25 eV) than the pristine surface (1 eV), suggesting a substitution of the Hf atom by another atom. The high density of defects on the HfSe 2 surface leads to very low Schottky barrier heights. Conductive atomic force microscopy measurements reveal a very small dependence of the Schottky barrier height on the work function of the metals, suggesting a strong Fermi-level pinning. We attribute the observed Fermi-level pinning (pinning factor ∼0.1) to surface distortions and Se/Hf defects. In addition, we have also studied the HfSe 2 surface after the exposure to air by scanning tunneling microscopy and conductive atomic force microscopy. Partly oxidized layers with band gaps of 2 eV and Schottky barrier heights of ∼0.6 eV were readily found on the surface. Our experiments reveal that HfSe 2 is very air-sensitive, implying that capping or encapsulating of HfSe 2 , in order to protect it against oxidation, is a necessity for technological applications., Competing Interests: The authors declare no competing financial interest.

High quality graphene nanoribbons epitaxially grown on the sidewalls of silicon carbide (SiC) mesa structures stand as key building blocks for graphene-based nanoelectronics. Such ribbons display 1D single-channel ballistic transport at room temperature with exceptionally long mean free paths. Here, using spatially-resolved two-point probe (2PP) measurements, we selectively access and directly image a range of individual transport modes in sidewall ribbons. The signature of the independently contacted channels is a sequence of quantised conductance plateaus for different probe positions. These result from an interplay between edge magnetism and asymmetric terminations at opposite ribbon edges due to the underlying SiC structure morphology. Our findings demonstrate a precise control of transport through multiple, independent, ballistic tracks in graphene-based devices, opening intriguing pathways for quantum information device concepts.

The formation and evolution of immersed surface micro- and nanobubbles are essential in various practical applications, such as the usage of superhydrophobic materials, drug delivery, and mineral flotation. In this work, we investigate the entrapment of microbubbles on a hydrophobic surface, structured with microwells, when water flow passes along, and the subsequent microbubble dissolution. At entrapment, the microbubble is initially pinned at the edge of the microwell. At some point, the three-phase contact line detaches from one side of the edge and separates from the wall, after which it further recedes. We systematically investigate the evolution of the footprint diameter and the contact angle of the entrapped microbubbles, which reveals that the dissolution process is in the constant contact angle mode. By varying the gas undersaturation level, we quantify how a high gas undersaturation enhances the dissolution process, and compare with simplified theoretical predictions for dissolving bubbles on a plane surface. We find that geometric partial blockage effects of the diffusive flux out of the microbubble trapped in the microwell lead to reduced dissolution rates.

When illuminated by a laser, plasmonic nanoparticles immersed in water can very quickly and strongly heat up, leading to the nucleation of so-called plasmonic vapor bubbles. While the long-time behavior of such bubbles has been well-studied, here, using ultrahigh-speed imaging, we reveal the nucleation and early life phase of these bubbles. After some delay time from the beginning of the illumination, a giant bubble explosively grows, and collapses again within 200 μs (bubble life phase 1). The maximal bubble volume [Formula: see text] remarkably increases with decreasing laser power, leading to less total dumped energy E. This dumped energy shows a universal linear scaling relation with [Formula: see text], irrespective of the gas concentration of the surrounding water. This finding supports that the initial giant bubble is a pure vapor bubble. In contrast, the delay time does depend on the gas concentration of the water, as gas pockets in the water facilitate an earlier vapor bubble nucleation, which leads to smaller delay times and lower bubble nucleation temperatures. After the collapse of the initial giant bubbles, first, much smaller oscillating bubbles form out of the remaining gas nuclei (bubble life phase 2). Subsequently, the known vaporization dominated growth phase takes over, and the bubble stabilizes (life phase 3). In the final life phase 4, the bubble slowly grows by gas expelling due to heating of the surrounding. Our findings on the explosive growth and collapse during the early life phase of a plasmonic vapor bubble have strong bearings on possible applications of such bubbles., Competing Interests: The authors declare no conflict of interest.

The control of the surface wettability is of great interest for technological applications as well as for the fundamental understanding of surface phenomena. In this article, we describe the dissolution behavior of droplets wetting a micropatterned surface consisting of smooth concentric circular grooves. In the experiments, a droplet of alcohol (1-pentanol) is placed onto water-immersed micropatterns. When the drops dissolve, the dynamics of the receding contact line occurs in two different modes. In addition to the stick-jump mode with jumps from one ring to the next inner one, our study reveals a second dissolution mode, which we refer to as zipping-depinning. The velocity of the zipping-depinning fronts is governed by the dissolution rate. At the early stage of the droplet dissolution, our experimental results are in good agreement with the theoretical predictions by Debuisson et al. [ Appl. Phys. Lett. 2011 , 99 , 184101 ]. With an extended model, we can accurately describe the dissolution dynamics in both stick-jump and zipping-depinning modes.

Self-assembled monolayers (SAMs) of alkanethiols on gold are a commonly used platform for nanotechnology owing to their ease of preparation and high surface coverage. Unfortunately, the gold-sulfur bond is oxidized at ambient conditions which alters the stability and structure of the monolayer. We show using scanning tunneling microscopy and X-ray photoelectron spectroscopy that decanethiolate molecules oxidize into decanesulfonates that organize into a hitherto unknown striped phase. Air-exposed SAMs oxidize, as can be determined by a shift of the S 2p peak and the appearance of O 1s photoelectrons as part of the decanethiol monolayer transforms into a lamellae-like decanesulfonate structure when exposed to air. The herringbone structure of the Au(111) surface is preserved, indicating that the interaction between the molecules and the surface is rather weak as these findings are substantiated by density functional theory calculations., Competing Interests: The authors declare no competing financial interest.

Here, we report on the surface conductivity of WSe 2 and Mo x W 1- x Se 2 (0 ≤ x ≤ 1) crystals investigated with conductive atomic force microscopy. We found that stacking faults, defects, and chemical heterogeneities form distinct two-dimensional and one-dimensional conduction paths on the transition metal dichalcogenide surface. In the case of WSe 2 , in addition to step edges, we find a significant amount of stacking faults (formed during the cleaving process) that strongly influence the surface conductivity. These regions are attributed to the alternation of the 2H and 3R polytypism. The stacking faults form regular 2D patterns by alternation of the underlying stacking order, with a periodicity that varies significantly between different regions and samples. In the case of Mo x W 1- x Se 2 , its conductivity has a localized nature, which depends on the underlying chemical composition and the Mo/W ratio. Segregation to W-rich and Mo-rich regions during the growth process leads to nonuniform conduction paths on the surface of the alloy. We found a gradual change of the conductivity moving from one region to the other, reminiscent of lateral band bending. Our results demonstrate the use of C-AFM as a nanoscopic tool to probe the electrical properties of largely inhomogeneous samples and show the complicated nature of the surface conductivity of TMDC alloys.

The classic regelation experiment of Thomson in the 1850s deals with cutting an ice cube, followed by refreezing. The cutting was attributed to pressure-induced melting but has been challenged continuously, and only lately consensus emerged by understanding that compression shortens the O:H nonbond and lengthens the H-O bond simultaneously. This H-O elongation leads to energy loss and lowers the melting point. The hot debate survived well over 150 years, mainly due to a poorly defined heat exchange with the environment in the experiment. In our current experiment, we achieved thermal isolation from the environment and studied the fully reversible ice-liquid water transition for water confined between graphene and muscovite mica. We observe a transition from two-dimensional (2D) ice into a quasi-liquid phase by applying a pressure exerted by an atomic force microscopy tip. At room temperature, the critical pressure amounts to about 6 GPa. The transition is completely reversible: refreezing occurs when the applied pressure is lifted. The critical pressure to melt the 2D ice decreases with temperature, and we measured the phase coexistence line between 293 and 333 K. From a Clausius-Clapeyron analysis, we determine the latent heat of fusion of two-dimensional ice at 0.15 eV/molecule, being twice as large as that of bulk ice.

Direct growth of flat micrometer-sized bilayer graphene islands in between molybdenum disulfide sheets is achieved by chemical vapor deposition of ethylene at about 800°C. The temperature assisted decomposition of ethylene takes place mainly at molybdenum disulfide step edges. The carbon atoms intercalate at this high temperature, and during the deposition process, through defects of the molybdenum disulfide surface such as steps and wrinkles. Post growth atomic force microscopy images reveal that circular flat graphene islands have grown at a high yield. They consist of two graphene layers stacked on top of each other with a total thickness of 0.74nm. Our results demonstrate direct, simple and high yield growth of graphene/molybdenum disulfide heterostructures, which can be of high importance in future nanoelectronic and optoelectronic applications., (Copyright © 2017 Elsevier Inc. All rights reserved.)

We use atomic force microscopy to in situ investigate the dynamic behavior of confined water at the interface between graphene and mica. The graphene is either uncharged, negatively charged, or positively charged. At high humidity, a third water layer will intercalate between graphene and mica. When graphene is negatively charged, the interface fills faster with a complete three layer water film, compared to uncharged graphene. As charged positively, the third water layer dewets the interface, either by evaporation into the ambient or by the formation of three-dimensional droplets under the graphene, on top of the bilayer. Our experimental findings reveal novel phenomena of water at the nanoscale, which are interesting from a fundamental point of view and demonstrate the direct control over the wetting properties of the graphene/water interface.

We report a combined experimental and theoretical study of the growth of sub-monolayer amounts of silicon (Si) on molybdenum disulfide (MoS 2 ). At room temperature and low deposition rates we have found compelling evidence that the deposited Si atoms intercalate between the MoS 2 layers. Our evidence relies on several experimental observations: (1) Upon the deposition of Si on pristine MoS 2 the morphology of the surface transforms from a smooth surface to a hill-and-valley surface. The lattice constant of the hill-and-valley structure amounts to 3.16 Å, which is exactly the lattice constant of pristine MoS 2 . (2) The transitions from hills to valleys are not abrupt, as one would expect for epitaxial islands growing on-top of a substrate, but very gradual. (3) I ( V ) scanning tunneling spectroscopy spectra recorded at the hills and valleys reveal no noteworthy differences. (4) Spatial maps of d I/ d z reveal that the surface exhibits a uniform work function and a lattice constant of 3.16 Å. (5) X-ray photo-electron spectroscopy measurements reveal that sputtering of the MoS 2 /Si substrate does not lead to a decrease, but an increase of the relative Si signal. Based on these experimental observations we have to conclude that deposited Si atoms do not reside on the MoS 2 surface, but rather intercalate between the MoS 2 layers. Our conclusion that Si intercalates upon the deposition on MoS 2 is at variance with the interpretation by Chiappe et al. ( Adv. Mater. 2014 , 26 , 2096-2101) that silicon forms a highly strained epitaxial layer on MoS 2 . Finally, density functional theory calculations indicate that silicene clusters encapsulated by MoS 2 are stable.

Understanding the electronic contact between molybdenum disulfide (MoS 2 ) and metal electrodes is vital for the realization of future MoS 2 -based electronic devices. Natural MoS 2 has the drawback of a high density of both metal and sulfur defects and impurities. We present evidence that subsurface metal-like defects with a density of ∼10 11 cm -2 induce negative ionization of the outermost S atom complex. We investigate with high-spatial-resolution surface characterization techniques the effect of these defects on the local conductance of MoS 2 . Using metal nanocontacts (contact area < 6 nm 2 ), we find that subsurface metal-like defects (and not S-vacancies) drastically decrease the metal/MoS 2 Schottky barrier height as compared to that in the pristine regions. The magnitude of this decrease depends on the contact metal. The decrease of the Schottky barrier height is attributed to strong Fermi level pinning at the defects. Indeed, this is demonstrated in the measured pinning factor, which is equal to ∼0.1 at defect locations and ∼0.3 at pristine regions. Our findings are in good agreement with the theoretically predicted values. These defects provide low-resistance conduction paths in MoS 2 -based nanodevices and will play a prominent role as the device junction contact area decreases in size.

Helium Ion Microscopy is known for its surface sensitivity and high lateral resolution. Here, we present results of a Helium Ion Microscopy based investigation of a surface confined alloy of Ag on Pt(111). Based on a change of the work function of 25meV across the atomically flat terraces we can distinguish Pt rich from Pt poor areas and visualize the single atomic layer high steps between the terraces. Furthermore, dechanneling contrast has been utilized to measure the periodicity of the hcp/fcc pattern formed in the 2-3 layers thick Ag/Pt alloy film. A periodicity of 6.65nm along the ⟨112⟩ surface direction has been measured. In terms of crystallography a hcp domain is obtained through a lateral displacement of a part of the outermost layer by 1/√3 of a nearest neighbor spacing along ⟨112⟩. This periodicity is measured with atomic precision: coincidence between the Ag and the Pt lattices is observed for 23 Ag atoms on 24 Pt atoms. The findings are perfectly in line with results obtained with Low Energy Electron Microscopy and Phase Contrast Atomic Force Microscopy., (Copyright © 2015 Elsevier B.V. All rights reserved.)