Variable-temperature Scanning Tunneling Microscopy Research Articles

Exceptionally Stable Cobalt Nanoclusters on Functionalized Graphene

To improve reactivity and achieve a higher material efficiency, catalysts are often used in the form of clusters with nanometer dimensions, down to single atoms. Since the corresponding properties are highly structure‐dependent, a suitable support is thus required to ensure cluster stability during operating conditions. Herein, an efficient method to stabilize cobalt nanoclusters on graphene grown on nickel substrates, exploiting the anchoring effect of nickel atoms incorporated in the carbon network is presented. The anchored nanoclusters are studied by in situ variable temperature scanning tunneling microscopy at different temperatures and upon gas exposure. Cluster stability upon annealing up to 200 °C and upon CO exposure at least up to 1 × 10−6 mbar CO partial pressure is demonstrated. Moreover, the dimensions of the cobalt nanoclusters remain surprisingly small (<3 nm diameter) with a narrow size distribution. Density functional theory calculations demonstrate that the interplay between the low diffusion barrier on graphene on nickel and the strong anchoring effect of the nickel atoms leads to the increased stability and size selectivity of these clusters. This anchoring technique is expected to be applicable also to other cases, with clear advantages for transition metals that are usually difficult to stabilize.

Visualizing the gas-sensitive structure of the CuZn surface in methanol synthesis catalysis

Methanol formation over Cu/ZnO catalysts is linked with a catalytically active phase created by contact between Cu nanoparticles and Zn species whose chemical and structural state depends on reaction conditions. Herein, we use variable-temperature scanning tunneling microscopy at elevated pressure conditions combined with X-ray photoelectron spectroscopy measurements to investigate the surface structures and chemical states that evolve when a CuZn/Cu(111) surface alloy is exposed to reaction gas mixtures. In CO2 hydrogenation conditions, Zn stays embedded in the CuZn surface, but once CO gas is added to the mixture, the Zn segregates onto the Cu surface. The Zn segregation is CO-induced, and establishes a new dynamic state of the catalyst surface where Zn is continually exchanged at the Cu surface. Candidates for the migrating few-atom Zn clusters are further identified in time-resolved imaging series. The findings point to a significant role of CO affecting the distribution of Zn in the multiphasic ZnO/CuZn/Cu catalysts.

Variable-temperature lightwave-driven scanning tunneling microscope with a compact, turn-key terahertz source.

We report on a lightwave-driven scanning tunneling microscope based on a home-built microscope and a compact, commercial, and cost-effective terahertz-generation unit with a repetition rate of 100MHz. The measurements are performed in an ultrahigh vacuum at temperatures between 8.5 and 300K. The cross-correlation of the pump and probe pulses indicates a temporal resolution on the order of a picosecond. In terms of spatial resolution, CO molecules, step edges, and atomically resolved terraces are readily observed in terahertz images, with sometimes better contrast than in the topographic and (DC) current channels. The utilization of a compact, turn-key terahertz-generation system requires only limited experience with optics and terahertz generation, which may facilitate the deployment of the technique to further research groups.

Hysteretic electronic phase transitions in correlated charge density wave state of 1T−TaS2

The layered transition metal dichalcogenide $1T\text{\ensuremath{-}}{\mathrm{TaS}}_{2}$ has evoked great interest owing to its particularly rich electronic phase diagram including different charge density wave (CDW) phases. However, few studies have focused on its hysteretic electronic phase transitions based on the in-depth discussion of the delicate interplay among temperature-dependent electronic interactions. Here, we report a sequence of spatial electronic phase transitions in the hysteresis temperature range (160--230 K) of $1T\text{\ensuremath{-}}{\mathrm{TaS}}_{2}$ via variable-temperature scanning tunneling microscopy. Several emergent electronic states are investigated at multiscale during the commensurate CDW--triclinic CDW (CCDW-TCDW) phase transitions: a spotty-CDW state above $\ensuremath{\sim}160\phantom{\rule{0.28em}{0ex}}\mathrm{K}$, a network-CDW (NCDW) state above $\ensuremath{\sim}180\phantom{\rule{0.28em}{0ex}}\mathrm{K}$ during the warmup process, a belt-TCDW state below $\ensuremath{\sim}230\phantom{\rule{0.28em}{0ex}}\mathrm{K}$, a NCDW state below $\ensuremath{\sim}200\phantom{\rule{0.28em}{0ex}}\mathrm{K}$, and finally a mosaic-CDW state below $\ensuremath{\sim}160\phantom{\rule{0.28em}{0ex}}\mathrm{K}$ during cooldown from the TCDW phase. These emergent electronic states are associated with the delicate temperature-dependent competition and/or cooperation of stacking-dependent interlayer interactions, intralayer electron-electron correlations, and electron-phonon ($e\text{\ensuremath{-}}ph$) coupling of $1T\text{\ensuremath{-}}{\mathrm{TaS}}_{2}$. Our results not only provide insight to understand the hysteretic electronic phase transitions in the correlated CDW state, but also pave a way to realize more exotic quantum states by accurately and effectively tuning various interior interactions in correlated materials.

Real-Space Observation of Unidirectional Charge Density Wave and Complex Structural Modulation in the Pnictide Superconductor Ba1–xSrxNi2As2

Here we use low-temperature and variable-temperature scanning tunneling microscopy to study the pnictide superconductor, Ba1-xSrxNi2As2. In the low-temperature phase (triclinic phase) of BaNi2As2, we observe the unidirectional charge density wave (CDW) with Q = 1/3 on both the Ba and NiAs surfaces. On the NiAs surface of the triclinic BaNi2As2, there are structural-modulation-induced chain-like superstructures with distinct periodicities. In the high-temperature phase (tetragonal phase) of BaNi2As2, the NiAs surface appears as the periodic 1 × 2 superstructure. Interestingly, in the triclinic phase of Ba0.5Sr0.5Ni2As2, the unidirectional CDW is suppressed on both the Ba/Sr and NiAs surfaces, and the Sr substitution stabilizes the periodic 1 × 2 superstructure on the NiAs surface, which enhance the superconductivity in Ba0.5Sr0.5Ni2As2. Our results provide important microscopic insights for the interplay among the unidirectional CDW, structural modulation, and superconductivity in this class of pnictide superconductors.

Molecular Diffusion and Self-Assembly: Quantifying the Influence of Substrate hcp and fcc Atomic Stacking

Molecular diffusion is a fundamental process underpinning surface-confined molecular self-assembly and synthesis. Substrate topography influences molecular assembly, alignment, and reactions with the relationship between topography and diffusion linked to the thermodynamic evolution of such processes. Here, we observe preferential adsorption sites for tetraphenylporphyrin (2H-TPP) on Au(111) and interpret nucleation and growth of molecular islands at these sites in terms of spatial variation in diffusion barrier driven by local atomic arrangements of the Au(111) surface (the 22× √3 “herringbone” reconstruction). Variable-temperature scanning tunnelling microscopy facilitates characterization of molecular diffusion, and Arrhenius analysis allows quantitative characterization of diffusion barriers within fcc and hcp regions of the surface reconstruction (where the in-plane arrangement of the surface atoms is identical but the vertical stacking differs). The higher barrier for diffusion within fcc locations underpins the ubiquitous observation of preferential island growth within fcc regions, demonstrating the relationship between substrate-structure, diffusion, and molecular self-assembly.

Surface Diffusion Aided by a Chirality Change of Self-Assembled Oligomers under 2D Confinement.

Chirality switching of self-assembled molecular structures is of potential interest for designing functional materials but is restricted by the strong interaction between the embedded molecules. Here, we report on an unusual approach based on reversible chirality changes of self-assembled oligomers using variable-temperature scanning tunneling microscopy supported by quantum mechanical calculations. Six functionalized diazomethanes each self-assemble into chiral wheel-shaped oligomers on Ag(111). At 130 K, a temperature far lower than expected, the oligomers change their chirality even though the molecules reside in an embedded self-assembled structure. Each chirality change is accompanied by a slight center-of-mass shift. We show how the identical activation energies of the two processes result from the interplay of the chirality change with surface diffusion, findings that open the possibility of implementing various functional materials from self-assembled supramolecular structures.

Increased Molecular Conductance in Oligo[n]phenylene Wires by Thermally Enhanced Dihedral Planarization.

Coherent tunneling electron transport through molecular wires has been theoretically established as a temperature-independent process. Although several experimental studies have shown counter examples, robust models to describe this temperature dependence have not been thoroughly developed. Here, we demonstrate that dynamic molecular structures lead to temperature-dependent conductance within coherent tunneling regime. Using a custom-built variable-temperature scanning tunneling microscopy break-junction instrument, we find that oligo[n]phenylenes exhibit clear temperature-dependent conductance. Our calculations reveal that thermally activated dihedral rotations allow these molecular wires to have a higher probability of being in a planar conformation. As the tunneling occurs primarily through π-orbitals, enhanced coplanarization substantially increases the time-averaged tunneling probability. These calculations are consistent with the observation that more rotational pivot points in longer molecular wires leads to larger temperature-dependence on conductance. These findings reveal that molecular conductance within coherent and off-resonant electron transport regimes can be controlled by manipulating dynamic molecular structure.

A high-speed variable-temperature ultrahigh vacuum scanning tunneling microscope with spiral scan capabilities.

We present the design and development of a variable-temperature high-speed scanning tunneling microscope (STM). The setup consists of a two-chamber ultra-high vacuum system, including a preparation and a main chamber. The preparation chamber is equipped with standard preparation tools for sample cleaning and film growth. The main chamber hosts the STM that is located within a continuous flow cryostat for counter-cooling during high-temperature measurements. The microscope body is compact, rigid, and highly symmetric to ensure vibrational stability and low thermal drift. We designed a hybrid scanner made of two independent tube piezos for slow and fast scanning, respectively. A commercial STM controller is used for slow scanning, while a high-speed Versa Module Eurocard bus system controls fast scanning. Here, we implement non-conventional spiral geometries for high-speed scanning, which consist of smooth sine and cosine signals created by an arbitrary waveform generator. The tip scans in a quasi-constant height mode, where the logarithm of the tunneling current signal can be regarded as roughly proportional to the surface topography. Scan control and data acquisition have been programmed in the experimental physics and industrial control system framework. With the spiral scans, we atomically resolved diffusion processes of oxygen atoms on the Ru(0001) surface and achieved a time resolution of 8.3 ms per frame at different temperatures. Variable-temperature measurements reveal an influence of the temperature on the oxygen diffusion rate.

In-situ measurements of reconstructed anatase TiO2(001) surface by variable-temperature STM

The catalytic performance of metal oxide surface mainly depends on its atomic surface structure, which usually changes under various treatment conditions and during catalytic reactions. Therefore, it is quite important to acquire the atomic geometries of the surfaces under different treatments for further understanding the catalytic mechanisms in the surfaces with complicated reconstructions. Here, we report the investigation on the evolution of surface geometries of the Ar+-ion-sputtered anatase TiO2(001) films followed by heating treatments at various temperatures, characterized using variable-temperature scanning tunneling microscopy. Our experimental results reveal the different surface morphologies at different heating temperatures. During the heating treatment, the migrations of O atoms from the bulk to the surface of TiO2(001) play an important role in the reoxidation of the Ti2+ and Ti3+ states for the formation of (1×4) reconstruction. The atomic-resolution images of the ridges show asymmetric features, which well support the fully oxidized structural model of the reconstructed TiO2(001)-(1×4) surface.

Rotation in an Enantiospecific Self-Assembled Array of Molecular Raffle Wheels.

Tailored nano‐spaces can control enantioselective adsorption and molecular motion. We report on the spontaneous assembly of a dynamic system—a rigid kagome network with each pore occupied by a guest molecule—employing solely 2,6‐bis(1H‐pyrazol‐1‐yl)pyridine‐4‐carboxylic acid on Ag(111). The network cavity snugly hosts the chemically modified guest, bestows enantiomorphic adsorption and allows selective rotational motions. Temperature‐dependent scanning tunnelling microscopy studies revealed distinct anchoring orientations of the guest unit switching with a 0.95 eV thermal barrier. H‐bonding between the guest and the host transiently stabilises the rotating guest, as the flapper on a raffle wheel. Density functional theory investigations unravel the detailed molecular pirouette of the guest and how the energy landscape is determined by H‐bond formation and breakage. The origin of the guest's enantiodirected, dynamic anchoring lies in the specific interplay of the kagome network and the silver surface.

Thermal Dynamics of Charge Density Wave Pinning in ZrTe_{3}.

Impurity pinning has long been discussed to have a profound effect on the dynamics of an incommensurate charge density wave (CDW), which would otherwise slide through the lattice without resistance. Here, we visualize the impurity pinning evolution of the CDW in ZrTe_{3} using the variable temperature scanning tunneling microscopy. At low temperatures, we observe a quasi-1D incommensurate CDW modulation moderately correlated to the impurity positions, indicating a weak impurity pinning. As we raise the sample temperature, the CDW modulation gets progressively weakened and distorted, while the correlation with the impurities becomes stronger. Above the CDW transition temperature, short-range modulations persist with the phase almost all pinned by impurities. The evolution from weak to strong impurity pinning through the CDW transition can be understood as a result of losing phase rigidity.

Quantifying the Ultraslow Desorption Kinetics of 2,6-Naphthalenedicarboxylic Acid Monolayers at Liquid-Solid Interfaces.

Kinetic effects in monolayer self-assembly at liquid-solid interfaces are not well explored but can provide unique insights. We use variable-temperature scanning tunneling microscopy (STM) to quantify the desorption kinetics of 2,6-naphthalenedicarboxylic acid (NDA) monolayers at nonanoic acid-graphite interfaces. Quantitative tracking of the decline of molecular coverages by STM between 57.5 and 65.0 °C unveiled single-exponential decays over the course of days. An Arrhenius plot of rate constants derived from fits results in a surprisingly high energy barrier of 208 kJ mol-1 that strongly contrasts with the desorption energy of 16.4 kJ mol-1 with respect to solution as determined from a Born-Haber cycle. This vast discrepancy indicates a high-energy transition state. Expanding these studies to further systems is the key to pinpointing the molecular origin of the remarkably large NDA desorption barrier.

Entropy-controlled fully reversible nanostructure formation of Ge on miscut vicinal Si(001) surfaces

Entropy effects substantially modify the growth of self-assembled Ge nanostructures on vicinal Si (001) surfaces. As shown by variable temperature scanning tunneling microscopy, this leads to new types of one dimensional nanostructures that are not only tunable in size and shape but can be fully reversible erased and reformed without changes in final sizes and shapes. This unique behavior is caused by the free surface energy renormalization caused by the large step entropy of vicinal surfaces. In thermodynamic equilibrium, this favors the formation of a planar 2D surface at higher temperatures, where-as the nanostructured surface is the preferred low-temperature configuration. Taking the step entropy into account, the critical phase transition temperature is derived by free energy calculations and is shown to scale nearly linearly with the Ge coverage, in excellent agreement with the experiments. Due to self-limitation, the nanowire size is solely controlled by the Ge coverage and vicinal angle, completely independent of the growth or an-nealing conditions. Thus, highly reproducible nanostructures with tunable geometries are obtained. This opens new avenues for controlled nanostructure formation for practical de-vice applications.

Temperature-dependent change of the fractal dimension of Cu dendrites on Cu(111)

We investigate the shape of monatomic high Cu islands on a Cu(111) surface by variable-temperature scanning tunneling microscopy between 110 K and 240 K. Low temperature dendrites evolve towards more compact shapes at increasing temperature; finally reaching the equilibrium shape of a hexagon with rounded corners. Time-lapsed imaging at increasing temperature reveals the onset of shape change to be at ≈170 K, corresponding to the onset of edge and corner diffusion of atoms along the island’s borders. Despite a substantial variation for individual islands at each temperature, the mean fractal dimension increases monotonously between 170 K up to 240 K, from the smallest to the largest values feasible for islands grown on surfaces.

A beetle-type, variable-temperature scanning tunneling microscope for video-rate imaging

A setup is described that combines video-rate imaging with temperature variability for a beetle-type scanning tunneling microscope (STM). The STM is operated in the constant height mode. Sinusoidal driving voltages are used for the scan lines; the resulting image distortions are corrected by a straightforward mathematical operation. A phase shifter is used to compensate the time lag between the driving voltage and the tip motion. A preamplifier with a bandwidth of 300 kHz and an rms noise of ∼0.1 nA has been developed. Software has been written for data acquisition rates of up to 2 MHz and for saving movies of more than 3700 STM images of 200 × 200 pixels. Frame rates between 10 and 50 frames s−1 have been achieved, where the highest line rates are above the lowest resonance frequency of the STM. The accessible temperature range of 50–500 K is not impaired by the video mode.

Growth Kinetics of Two-Dimensional Hexagonal Boron Nitride Layers on Pd(111).

Using in situ variable-temperature scanning tunneling microscopy (300-673 K) during chemical vapor deposition of two-dimensional hexagonal boron nitride (hBN) on Pd(111) from borazine precursor at pressures up to 10-6 mbar, we identify the mechanisms leading to carpetlike uphill or downhill growth across the Pd steps. Deposition at a higher rate and lower temperature promotes uphill growth via preferential attachment at the ascending and descending step-edges, whereas a lower deposition rate and higher temperature lead to downhill growth via nucleation and growth of islands on Pd terraces. We attribute this unusual growth behavior to differences in temperature-dependent rates of hBN deposition at the steps versus on the Pd terraces. Our results illustrate how growth mechanisms can be activated by a pair of parameters (substrate temperature and partial pressure of borazine) and provide new insights into the mechanisms underlying carpetlike growth of hBN and other layered materials.

Operando atomic-scale study of graphene CVD growth at steps of polycrystalline nickel

An operando investigation of graphene growth on (100) grains of polycrystalline nickel (Ni) surfaces was performed by means of variable-temperature scanning tunneling microscopy complemented by density functional theory simulations. A clear description of the atomistic mechanisms ruling the graphene expansion process at the stepped regions of the substrate is provided, showing that different routes can be followed, depending on the height of the steps to be crossed. When a growing graphene flake reaches a monoatomic step, it extends jointly with the underlying Ni layer; for higher Ni edges, a different process, involving step retraction and graphene landing, becomes active. At step bunches, the latter mechanism leads to a peculiar ‘staircase formation’ behavior, where terraces of equal width form under the overgrowing graphene, driven by a balance in the energy cost between C–Ni bond formation and stress accumulation in the carbon layer. Our results represent a step towards bridging the material gap in searching new strategies and methods for the optimization of chemical vapor deposition graphene production on polycrystalline metal surfaces.

In Situ Variable-Temperature Scanning Tunneling Microscopy Studies of Graphene Growth Using Benzene on Pd(111).

Using a combination of in situ ultrahigh-vacuum variable-temperature scanning tunneling microscopy, ex situ Raman spectroscopy, and scanning electron microscopy, we investigated the growth of graphene using benzene on Pd(111) at temperatures up to 1100 K. Benzene adsorbs readily on Pd(111) at room temperature and forms an ordered superstructure upon annealing at 473 K. Exposure to benzene at 673 K enhances Pd step motion and yields primarily amorphous carbon upon cooling to room temperature. Monolayer graphene domains, 10-30 nm in size, appear during annealing this sample at 873 K. Dosing benzene at 1100 K results in graphene domains with varying degrees of crystallinity, while post-deposition annealing at 1100 K for 1200 s yields monolayer graphene domains larger than 150 × 150 nm2. Our results, which indicate that graphene growth on Pd(111) using benzene requires deposition/annealing temperatures higher than 673 K, are in striking contrast with the reported growth of graphene using benzene at temperatures as low as 373 K on relatively inert Cu surfaces.

A variable-temperature scanning tunneling microscope operated in a continuous flow cryostat.

We present a continuous flow cryostat scanning tunneling microscope (STM) which can be operated at temperatures between 4.9 K and 300 K. A variable temperature insert with 20 mm aperture is installed in the cryostat. A base temperature of 4.9 K at the STM head was achieved with helium exchange gas cooling. By using a novel design of zirconia structure, the size of the STM head was minimized to 9.2 mm in outer diameter. The high compactness and rigidity of the STM head make it less sensitive to vibrations, contributing to the high stability of the tip-sample junction. The drifting rates of the STM at 4.9 K in the X-Y plane and Z direction are 1.96 and 3.05 pm/min, respectively. The performance of the STM was demonstrated by atomically resolved imaging of graphite and NbSe2 without using external vibrational isolation. Furthermore, the dI/dV spectra of NbSe2 were resolved near its critical temperature, illustrating the formation process of the superconducting gap as a function of temperature. This STM is ultrahigh vacuum and strong magnetic field compatible, making it promising for direct application in the extreme conditions involving water-cooled magnets and hybrid magnets.