Two-dimensional tellurium superstructures on Au(111) surfaces.

Two-dimensional (2D) allotropes of tellurium (Te), recently coined as tellurene, are currently an emerging topic of materials research due to the theoretically predicted exotic properties of Te in its ultrathin form and at the single atomic layer limit. However, a prerequisite for the production of such new and single elemental 2D materials is the development of simple and robust fabrication methods. In the present work, we report three different 2D superstructures of Te on Au(111) surfaces by following an alternative experimental deposition approach. We have investigated the superstructures using low-temperature scanning tunneling microscopy and spectroscopy, Auger electron spectroscopy (AES), and field emission AES. Three superstructures (13 × 13, 8 × 4, and √11 × âˆš11) of 2D Te are observed in our experiments, and the formation of these superstructures is accompanied by the lifting of the characteristic 23 × âˆš3 surface reconstruction of the Au(111) surface. Scanning tunneling spectroscopy reveals a strong dependence of the local electronic properties on the structural arrangement of the Te atoms on the Au(111) support, and we observe superstructure-dependent electronic resonances around the Fermi level and below the Au(111) conduction band. In addition to the appearance of the new electronic resonances, the emergence of band gaps with a p-type charge character has been evidenced for two out of three Te superstructures (13 × 13 and √11 × âˆš11) on the Au(111) support.

Identifying Native Point Defects in the Topological Insulator Bi2Te3.

We successfully identified native point defects that occur in Bi2Te3 crystals by combining high-resolution bias-dependent scanning tunneling microscopy and density functional theory based calculations. As-grown Bi2Te3 crystals contain vacancies, antisites, and interstitial defects that may result in bulk conductivity and therefore may change the insulating bulk character. Here, we demonstrate the interplay between the growth conditions and the density of different types of native near-surface defects. In particular, scanning tunneling spectroscopy reveals the dependence on not only the local atomic environment but also on the growth kinetics and the resulting sample doping from n-type toward intrinsic crystals with the Fermi level positioned inside the energy gap. Our results establish a bias-dependent STM signature of the Bi2Te3 native defects and shed light on the link between the native defects and the electronic properties of Bi2Te3, which is relevant for the synthesis of topological insulator materials and the related functional properties.

Unraveling the atomic structure, ripening behavior, and electronic structure of supported Au20 clusters.

The free-standing Au20 cluster has a unique tetrahedral shape and a large HOMO-LUMO (highest occupied molecular orbital-lowest unoccupied molecular orbital) gap of around 1.8 electron volts. The "magic" Au20 has been intensively used as a model system for understanding the catalytic and optical properties of gold nanoclusters. However, direct real-space ground-state characterization at the atomic scale is still lacking, and obtaining fundamental information about the corresponding structural, electronic, and dynamical properties, is challenging. Here, using cluster-beam deposition and low-temperature scanning tunneling microscopy, atom-resolved topographic images and electronic spectra of supported Au20 clusters are obtained. We demonstrate that individual size-selected Au20 on ultrathin NaCl films maintains its pyramidal structure and large HOMO-LUMO gap. At higher cluster coverages, we find sintering of the clusters via Smoluchowski ripening to Au20n agglomerates. The evolution of the electron density of states deduced from the spectra reveals gap reduction with increasing agglomerate size.

Strongly Hole-Doped and Highly Decoupled Graphene on Platinum by Water Intercalation.

Scanning tunneling microscopy and spectroscopy experiments under ultrahigh vacuum and low-temperature conditions have been performed on water-intercalated graphene on Pt(111). We find that the confined water layer, with a thickness around 0.35 nm, induces a strong hole doping in graphene, i.e., the Dirac point locates at round 0.64 eV above the Fermi level. This can be explained by the presence of a single "puckered bilayer" of ice-Ih, which has not been experimentally found on bare Pt(111), being confined in between graphene and Pt(111) surface. Moreover, the water intercalation makes graphene highly decoupled from the substrate, allowing us to reveal the intrinsic graphene phonons and double Rydberg series of even and odd symmetry image-potential states. Our work not only demonstrates that the electronic properties of graphene can be tuned by the confined water layer between graphene and the substrate, but also provides a generally applicable method to study the intrinsic properties of graphene as well as of other supported two-dimensional materials.

Magnetic orders and origin of exchange bias in Co clusters embedded oxide nanocomposite films.

Magnetic nanoparticles embedded oxide semiconductors are interesting candidates for spintronics in view of combining ferromagnetic (FM) and semiconducting properties. In this work, Co-ZnO and Co-V2O3 nanocomposite thin films are synthesized by Co ion implantation in crystalline thin films. Magnetic orders vary with the implantation fluence in Co-ZnO, where superparamagnetic (SPM) order appears in the low-fluence films (2 × 1016 and 4 × 1016 ions cm-2) and FM order co-exists with the SPM phase in high-fluence films (1 × 1017 ions cm-2). Exchange bias (EB) appears in the high-fluence films, with an EB field of about 100 Oe at 2 K and a blocking temperature of around 100 K. On the other hand, Co-V2O3 thin films with an implantation fluence of 3.5 × 1016 ions cm-2 exhibit a clear antiferromagnetic (AFM) coupling at low temperatures without the EB effect. The different magnetic behavior of the Co-implanted films with different Co content leads us to conclude that the observed EB effect in the Co-ZnO films results from the FM/AFM coupling between sizable Co nanoparticles and their CoO/Co3O4 surroundings in the (Zn,Co)O matrix. On the other hand, the absence of EB effect in Co-V2O3 appears to be due to the small size of the FM Co nanoparticles in spite of an AFM magnetic order. Detailed studies of magnetic orders and EB effect in magnetic nanocomposite semiconductors can pave the way for their application in spintronics.

Controlling Water Intercalation Is Key to a Direct Graphene Transfer.

The key steps of a transfer of two-dimensional (2D) materials are the delamination of the as-grown material from a growth substrate and the lamination of the 2D material on a target substrate. In state-of-the-art transfer experiments, these steps remain very challenging, and transfer variations often result in unreliable 2D material properties. Here, it is demonstrated that interfacial water can insert between graphene and its growth substrate despite the hydrophobic behavior of graphene. It is understood that interfacial water is essential for an electrochemistry-based graphene delamination from a Pt surface. Additionally, the lamination of graphene to a target wafer is hindered by intercalation effects, which can even result in graphene delamination from the target wafer. For circumvention of these issues, a direct, support-free graphene transfer process is demonstrated, which relies on the formation of interfacial water between graphene and its growth surface, while avoiding water intercalation between graphene and the target wafer by using hydrophobic silane layers on the target wafer. The proposed direct graphene transfer also avoids polymer contamination (no temporary support layer) and eliminates the need for etching of the catalyst metal. Therefore, recycling of the growth template becomes feasible. The proposed transfer process might even open the door for the suggested atomic-scale interlocking-toy-brick-based stacking of different 2D materials, which will enable a more reliable fabrication of van der Waals heterostructure-based devices and applications.

Scanning probe microscopy induced surface modifications of the topological insulator Bi2Te3 in different environments.

We investigated the topological insulator (TI) Bi2Te3 in four different environments (ambient, ultra-high vacuum (UHV), nitrogen gas and organic solvent environment) using scanning probe microscopy (SPM) techniques. Upon prolonged exposure to ambient conditions and organic solvent environments the cleaved surface of the pristine Bi2Te3 is observed to be strongly modified during SPM measurements, while imaging of freshly cleaved Bi2Te3 in UHV and nitrogen gas shows considerably less changes of the Bi2Te3 surface. We conclude that the reduced surface stability upon exposure to ambient conditions is triggered by adsorption of molecular species from ambient, including H2O, CO2, etc which is verified by Auger electron spectroscopy. Our findings of the drastic impact of exposure to ambient on the Bi2Te3 surface are crucial for further in-depth studies of the intrinsic properties of the TI Bi2Te3 and for potential applications that include room temperature TI based devices operated under ambient conditions.

Adsorption of Te atoms on Au(1 1 1) and the emergence of an adatom-induced bound state.

We report on the adsorption of Te adatoms on Au(1 1 1), which are identified and investigated relying on scanning tunnelling microscopy, Auger electron spectroscopy, and density functional theory. The Te adatoms lift the 23 × âˆš3 surface reconstruction of the Au(1 1 1) support and their organization is similar to that of previously reported chalcogen adatoms on Au(1 1 1), which are also known to lift the herringbone reconstruction and can adopt a (√3 × âˆš3)R30° structure. The adatoms show strong interaction with the Au(1 1 1) surface, resulting in scattering and confinement of the Au surface state (SS) electrons near the Fermi level. More remarkably, scanning tunnelling spectroscopy reveals the existence of an electronic resonance at high voltages well above the Fermi level. This resonance can be interpreted as a bound state that is split off from the bottom of the Au(1 1 1) bulk conduction band. A similar split-off state may exist for other types of adatoms on metallic surfaces that exhibit a surface band gap.

Lateral Magnetically Modulated Multilayers by Combining Ion Implantation and Lithography.

The combination of lithography and ion implantation is demonstrated to be a suitable method to prepare lateral multilayers. A laterally, compositionally, and magnetically modulated microscale pattern consisting of alternating Co (1.6 µm wide) and Co-CoO (2.4 µm wide) lines has been obtained by oxygen ion implantation into a lithographically masked Au-sandwiched Co thin film. Magnetoresistance along the lines (i.e., current and applied magnetic field are parallel to the lines) reveals an effective positive giant magnetoresistance (GMR) behavior at room temperature. Conversely, anisotropic magnetoresistance and GMR contributions are distinguished at low temperature (i.e., 10 K) since the O-implanted areas become exchange coupled. This planar GMR is principally ascribed to the spatial modulation of coercivity in a spring-magnet-type configuration, which results in 180° Néel extrinsic domain walls at the Co/Co-CoO interfaces. The versatility, in terms of pattern size, morphology, and composition adjustment, of this method offers a unique route to fabricate planar systems for, among others, spintronic research and applications.

Electronically decoupled stacking fault tetrahedra embedded in Au(111) films.

Stacking faults are known as defective structures in crystalline materials that typically lower the structural quality of the material. Here, we show that a particular type of defect, that is, stacking fault tetrahedra (SFTs), exhibits pronounced quantized electronic behaviour, revealing a potential synthetic route to decoupled nanoparticles in metal films. We report on the electronic properties of SFTs that exist in Au(111) films, as evidenced by scanning tunnelling microscopy and confirmed by transmission electron microscopy. We find that the SFTs reveal a remarkable decoupling from their metal surroundings, leading to pronounced energy level quantization effects within the SFTs. The electronic behaviour of the SFTs can be described well by the particle-in-a-box model. Our findings demonstrate that controlled preparation of SFTs may offer an alternative way to achieve well-decoupled nanoparticles of high crystalline quality in metal thin films without the need of thin insulating layers.

Electron-phonon coupling in engineered magnetic molecules.

We probe the electron-phonon coupling for in situ engineered porphyrin-based magnetic molecular layers supported on weakly reactive surfaces. Using high-resolution scanning tunneling microscopy and spectroscopy at 4.5 K we show that the electronic and magnetic properties of the engineered molecules are the result of interplay between many-body spin-flip excitations and electron-phonon interactions.

Annealing-Induced Bi Bilayer on Bi2Te3 Investigated via Quasi-Particle-Interference Mapping.

Topological insulators (TIs) are renowned for their exotic topological surface states (TSSs) that reside in the top atomic layers, and hence, detailed knowledge of the surface top atomic layers is of utmost importance. Here we present the remarkable morphology changes of Bi2Te3 surfaces, which have been freshly cleaved in air, upon subsequent systematic annealing in ultrahigh vacuum and the resulting effects on the local and area-averaging electronic properties of the surface states, which are investigated by combining scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), and Auger electron spectroscopy (AES) experiments with density functional theory (DFT) calculations. Our findings demonstrate that the annealing induces the formation of a Bi bilayer atop the Bi2Te3 surface. The adlayer results in n-type doping, and the atomic defects act as scattering centers of the TSS electrons. We also investigated the annealing-induced Bi bilayer surface on Bi2Te3 via voltage-dependent quasi-particle-interference (QPI) mapping of the surface local density of states and via comparison with the calculated constant-energy contours and QPI patterns. We observed closed hexagonal patterns in the Fourier transform of real-space QPI maps with secondary outer spikes. DFT calculations attribute these complex QPI patterns to the appearance of a "second" cone due to the surface charge transfer between the Bi bilayer and the Bi2Te3. Annealing in ultrahigh vacuum offers a facile route for tuning of the topological properties and may yield similar results for other topological materials.

Atomic resolution of nitrogen-doped graphene on Cu foils.

Atomic-level substitutional doping can significantly tune the electronic properties of graphene. Using low-temperature scanning tunneling microscopy and spectroscopy, the atomic-scale crystalline structure of graphene grown on polycrystalline Cu, the distribution of nitrogen dopants and their effect on the electronic properties of graphene were investigated. Both the graphene sheet growth and nitrogen doping were performed using microwave plasma-enhanced chemical vapor deposition. The results indicated that the nitrogen dopants preferentially sit at the grain boundaries of the graphene sheets and confirmed that plasma treatment is a potential method to incorporate foreign atoms into the graphene lattice to tailor the graphene's electronic properties.

Amyloid beta oligomers induce neuronal elasticity changes in age-dependent manner: a force spectroscopy study on living hippocampal neurons.

Small soluble species of amyloid-beta (Aß) formed during early peptide aggregation stages are responsible for several neurotoxic mechanisms relevant to the pathology of Alzheimer's disease (AD), although their interaction with the neuronal membrane is not completely understood. This study quantifies the changes in the neuronal membrane elasticity induced by treatment with the two most common Aß isoforms found in AD brains: Aß40 and Aß42. Using quantitative atomic force microscopy (AFM), we measured for the first time the static elastic modulus of living primary hippocampal neurons treated with pre-aggregated Aß40 and Aß42 soluble species. Our AFM results demonstrate changes in the elasticity of young, mature and aged neurons treated for a short time with the two Aß species pre-aggregated for 2 hours. Neurons aging under stress conditions, showing aging hallmarks, are the most susceptible to amyloid binding and show the largest decrease in membrane stiffness upon Aß treatment. Membrane stiffness defines the way in which cells respond to mechanical forces in their environment and has been shown to be important for processes such as gene expression, ion-channel gating and neurotransmitter vesicle transport. Thus, one can expect that changes in neuronal membrane elasticity might directly induce functional changes related to neurodegeneration.

Size-Dependent Penetration of Gold Nanoclusters through a Defect-Free, Nonporous NaCl Membrane.

Membranes and their size-selective filtering properties are universal in nature and their behavior is exploited to design artificial membranes suited for, e.g., molecule or nanoparticle filtering and separation. Exploring and understanding penetration and transmission mechanisms of nanoparticles in thin-film systems may provide new opportunities for size selective deposition or embedding of the nanoparticles. Here, we demonstrate an unexpected finding that the sieving of metal nanoparticles through atomically thin nonporous alkali halide films on a metal support is size dependent and that this sieving effect can be tuned via the film thickness. Specifically, relying on scanning tunneling microscopy and spectroscopy techniques, combined with density functional theory calculations, we find that defect-free NaCl films on a Au(111) support act as size-dependent membranes for deposited Au nanoclusters. The observed sieving ability is found to originate from a driving force toward the metal support and from the dynamics of both the nanoparticles and the alkali halide films.

Interplay between magnetocrystalline anisotropy and exchange bias in epitaxial CoO/Co films.

The interplay between magnetocrystalline anisotropy and exchange bias is investigated in CoO/Co bilayer films, which are grown epitaxially on MgO (0 0 1), by magnetization reversal measurements based on the anisotropic magnetoresistance (AMR) effect. While an asymmetric magnetization reversal survives after training for cooling field (CF) along the hard axis, the magnetization reversal becomes symmetric and is dominated in both branches of the hysteresis loop by domain wall motion before and after training for CF along the easy axis. When performing an in-plane hysteresis loop perpendicular to the CF, the hysteresis loop along the easy axis becomes asymmetric: magnetization rotation dominates in the ascending branch, while there is a larger contribution of domain wall motion in the descending branch. Furthermore, the azimuthal angular dependence of the AMR shows two minima after performing a perpendicular hysteresis loop, instead of only one minimum after training. Relying on the extended Fulcomer and Charap model, these effects can be related to an increased deviation of the average uncompensated antiferromagnetic magnetization from the CF direction. This model provides a consistent interpretation of training and asymmetry of the magnetization reversal for epitaxial films with pronounced magnetocrystalline anisotropy as well as for the previously investigated polycrystalline films.

Development of a new direct liquid injection system for nanoparticle deposition by chemical vapor deposition using nanoparticle solutions.

Nanoparticles of different materials are already in use for many applications. In some applications, these nanoparticles need to be deposited on a substrate in a fast and reproducible way. We have developed a new direct liquid injection system for nanoparticle deposition by chemical vapor deposition using a liquid nanoparticle precursor. The system was designed to deposit nanoparticles in a controlled and reproducible way by using two direct liquid injectors to deliver nanoparticles to the system. The nanoparticle solution is first evaporated and then the nanoparticles flow onto a substrate inside the vacuum chamber. To allow injection and evaporation of the liquid, a direct liquid injection and vaporization system are mounted on top of the process chamber. The deposition of the nanoparticles is controlled by parameters such as deposition temperature, partial pressure of the gases, and flow rate of the nanoparticle suspension. The concentration of the deposited nanoparticles can be varied simply by changing the flow rate and deposition time. We demonstrate the capabilities of this system using gold nanoparticles. The selected suspension flow rates were varied between 0.25 and 1 g/min. AFM analysis of the deposited samples showed that the aggregation of gold nanoparticles is well controlled by the flow and deposition parameters.

Moiré superlattices at the topological insulator Bi2Te3.

We report on the observation of complex superlattices at the surface of the topological insulator Bi2Te3. Scanning tunneling microscopy reveals the existence of two different periodic structures in addition to the Bi2Te3 atomic lattice, which is found to strongly affect the local electronic structure. These three different periodicities are interpreted to result from a single small in-plane rotation of the topmost quintuple layer only. Density functional theory calculations support the observed increase in the DOS near the Fermi level, and exclude the possibility that strain is at the origin of the observed Moiré pattern. Exploration of Moiré superlattices formed by the quintuple layers of topological insulators holds great potential for further tuning of the properties of topological insulators.

Co-Rich ZnCoO Nanoparticles Embedded in Wurtzite Zn1-xCoxO Thin Films: Possible Origin of Superconductivity.

Co-rich ZnCoO nanoparticles embedded in wurtzite Zn0.7Co0.3O thin films are grown by pulsed laser deposition on a Si substrate. Local superconductivity with an onset Tc at 5.9 K is demonstrated in the hybrid system. The unexpected superconductivity probably results from Co3+ in the Co-rich ZnCoO nanoparticles or from the interface between the Co-rich nanoparticles and the Zn0.7Co0.3O matrix.

Alkoxylated dehydrobenzo[12]annulene on Au(111): from single molecules to quantum dot molecular networks.

We demonstrate the effective confinement of surface electrons in the pores of molecular networks formed by dehydrobenzo[12]annulene (DBA) molecules with butoxy groups (DBA-OC4) on Au(111). Investigation of the network formation starting from single molecules reveals a considerable interaction of the molecules with the substrate, which is at the origin of the observed confinement.