Time-resolved Scanning Tunneling Microscopy Research Articles

Time-resolved force microscopy using the delay-time modulation method

We developed a time-resolved force microscopy technique by integrating atomic force microscopy using a tuning-fork-type cantilever with the delay time modulation method for optical pump-probe light. We successfully measured the dynamics of surface recombination and diffusion of photoexcited carriers in bulk WSe2, which is challenging owing to the effect of the tunneling current in time-resolved scanning tunneling microscopy. The obtained results were comprehensively explained with the model based on the dipole-dipole interaction induced by photo illumination.

Imaging surfaces at the space–time limit: New perspectives of time-resolved scanning tunneling microscopy for ultrafast surface science

Many fundamental processes in nature occur on ultrashort time scales within picoseconds to attoseconds, and on intrinsic length scales from nanometers to picometers. The structure of crystalline solids is dictated by long range order and the periodic arrangement of atoms, but the elementary excitations that define its interaction with the environment may vary locally at the atomic scale. Multiple domains and phases can coexist on length scales down to a few nanometer, and impurities and defects can influence the collective many-body response of solids at the single-atom level. Ultrafast pump–probe techniques provide valuable information about fundamental many-body interactions in solids and at surfaces, but spatially average over macroscopic spot sizes such that the influence of local order or disorder at angstrom scales is not directly accessible. Therefore, real-space observation of ultrafast dynamics with atomic spatial resolution is highly desirable, and motivates the development of time-resolved ultrafast scanning tunneling microscopy (USTM) since the early 1990’s. Tremendous progress has been made in this field in the past decade, and a number of breakthrough achievements have significantly advanced our possibilities to add ultrafast time resolution to the angstrom spatial resolution of STM. This article reviews new technical approaches and developments in the field of USTM. A particular focus will be the classification of light-matter interaction in tunnel junctions, based on the criteria for adiabatic tunneling from Keldysh's theory of strong-field ionization and a tunneling time as defined by Büttiker and Landauer, and on Tucker's definition of quantum detection in a tunnel junction mixer. Moreover, various mechanisms to generate an ultrafast tunneling current in USTM are discussed and are to some extent related to those from other techniques such as optical spectroscopy or photoemission spectroscopy. The resulting new possibilities for imaging the ultrafast dynamics of electronic and vibrational excitations at surfaces with USTM will be highlighted. Finally, the article outlines possible future directions of USTM for studying ultrafast processes and light-induced phenomena at surfaces and in quantum materials.

Enhanced cutoff energies for direct and rescattered strong-field photoelectron emission of plasmonic nanoparticles

Abstract The efficient generation, accurate detection, and detailed physical tracking of energetic electrons are of applied interest for high harmonics generation, electron-impact spectroscopy, and femtosecond time-resolved scanning tunneling microscopy. We here investigate the generation of photoelectrons (PEs) by exposing plasmonic nanostructures to intense laser pulses in the infrared (IR) spectral regime and analyze the sensitivity of PE spectra to competing elementary interactions for direct and rescattered photoemission pathways. Specifically, we measured and numerically simulated emitted PE momentum distributions from prototypical spherical gold nanoparticles (NPs) with diameters between 5 and 70 nm generated by short laser pulses with peak intensities of 8.0 × 1012 and 1.2 × 1013 W/cm2, demonstrating the shaping of PE spectra by the Coulomb repulsion between PEs, accumulating residual charges on the NP, and induced plasmonic electric fields. Compared to well-understood rescattering PE cutoff energies for strong-field photoemission from gaseous atomic targets (10× the ponderomotive energy), our measured and simulated PE spectra reveal a dramatic cutoff-energy increase of two orders of magnitude with a significantly higher contribution from direct photoemission. Our findings indicate that direct PEs reach up to 93 % of the rescattered electron cutoff energy, in contrast to 20 % for gaseous atoms, suggesting a novel scheme for the development of compact tunable tabletop electron sources.

Ultrafast Dynamics Revealed with Time-Resolved Scanning Tunneling Microscopy: A Review.

A scanning tunneling microscope (STM) capable of performing pump-probe spectroscopy integrates unmatched atomic-scale resolution with high temporal resolution. In recent years, the union of electronic, terahertz, or visible/near-infrared pulses with STM has contributed to our understanding of the atomic-scale processes that happen between milliseconds and attoseconds. This time-resolved STM (TR-STM) technique is evolving into an unparalleled approach for exploring the ultrafast nuclear, electronic, or spin dynamics of molecules, low-dimensional structures, and material surfaces. Here, we review the recent advancements in TR-STM; survey its application in measuring the dynamics of three distinct systems, nucleus, electron, and spin; and report the studies on these transient processes in a series of materials. Besides the discussion on state-of-the-art techniques, we also highlight several emerging research topics about the ultrafast processes in nanoscale objects where we anticipate that the TR-STM can help broaden our knowledge.

On the progress of ultrafast time-resolved THz scanning tunneling microscopy

Scanning tunneling microscopy combined with terahertz (THz) electromagnetic pulses and its related technologies have developed remarkably. This technology has atomic-level spatial resolution in an ultrahigh vacuum and low-temperature environment, and it measures the electrical dynamical behavior of a sample’s surface with femtosecond temporal resolution. In particular, it has been used to image the diffusion and relaxation dynamics of electrons in real time and real space and even instantaneously control molecular motions. In this Perspective, we focus on recent progress in research and development of ultrafast time-resolved THz scanning tunneling microscopy and its application to materials research.

Structural Stability of Physisorbed Air-Oxidized Decanethiols on Au(111)

We have studied the dynamic behavior of decanethiol and air-oxidized decanethiol self-assembled monolayers (SAMs) on Au(111) using time-resolved scanning tunneling microscopy at room temperature. T...

The Importance of Topological Defects in Photoexcited Phase Transitions Including Memory Applications

Photoinduced phase transitions have become a very important field of study with the advent of diverse time-resolved experimental techniques whose time resolution matches the electron, lattice, and spin relaxation dynamics associated with elementary excitations in quantum materials. Most techniques currently available rely on stroboscopic data-averaging over multiple transition outcomes. However, each time a transition takes place, fluctuations close to the time of the transition ensure that the phase transition outcome is different, with the emergence of different topological defect textures. In this paper, we briefly review the non-perturbative processes in selected charge-ordered quantum systems and the methods for their observation with different time-resolved techniques and scanning tunneling microscopy, which avoids the problem of averaging. The topological defect dynamics are seen to play an essential role in stabilizing emergent states in non-equilibrium transitions, appearing on different timescales as well as determining the emergent properties of the system. The phenomena are fundamentally important for understanding the fabric of matter in the Universe, as well as for possible applications in non-volatile memory devices.

RECENT ADVANCES IN ULTRAFAST TIME-RESOLVED SCANNING TUNNELING MICROSCOPY

Making smaller and faster functional devices has led to an increasing demand for a microscopic technique that allows the investigation of carrier and phonon dynamics with both high spatial and temporal resolutions. Traditional optical pump–probe methods can achieve femtosecond temporal resolution but fall short in the spatial resolution due to the diffraction limit. Scanning tunneling microscopy (STM), on the contrary, has realized atomic-scale spatial resolution relying on the high sensitivity of the tunneling current to the tip-sample distance. However, limited by the electronics bandwidth, STM can only push the temporal resolution to the microseconds scale, restricting its applications to probe various ultrafast dynamic processes. The combination of these two methods takes advantages of optical pump–probe techniques and highly localized tunneling currents of STM, providing one viable solution to track atomic-scale ultrafast dynamics in single molecules and low-dimensional materials. In this review, we will focus on several ultrafast time-resolved STM methods by coupling the tunneling junctions with pulsed electric waves, THz, near-infrared and visible laser. Their applications to probe the carrier dynamics, spin dynamics, and molecular motion will be highlighted. In the end, we will present an outlook on the challenges and new opportunities in this field.

All-electronic Nanosecond-resolved Scanning Tunneling Microscopy: Facilitating the Investigation of Single Dopant Charge Dynamics.

The miniaturization of semiconductor devices to scales where small numbers of dopants can control device properties requires the development of new techniques capable of characterizing their dynamics. Investigating single dopants requires sub-nanometer spatial resolution, which motivates the use of scanning tunneling microscopy (STM). However, conventional STM is limited to millisecond temporal resolution. Several methods have been developed to overcome this shortcoming, including all-electronic time-resolved STM, which is used in this study to examine dopant dynamics in silicon with nanosecond resolution. The methods presented here are widely accessible and allow for local measurement of a wide variety of dynamics at the atomic scale. A novel time-resolved scanning tunneling spectroscopy technique is presented and used to efficiently search for dynamics.

All-electronic Nanosecond-resolved Scanning Tunneling Microscopy: Facilitating the Investigation of Single Dopant Charge Dynamics

The miniaturization of semiconductor devices to scales where small numbers of dopants can control device properties requires the development of new techniques capable of characterizing their dynamics. Investigating single dopants requires sub-nanometer spatial resolution, which motivates the use of scanning tunneling microscopy (STM). However, conventional STM is limited to millisecond temporal resolution. Several methods have been developed to overcome this shortcoming, including all-electronic time-resolved STM, which is used in this study to examine dopant dynamics in silicon with nanosecond resolution. The methods presented here are widely accessible and allow for local measurement of a wide variety of dynamics at the atomic scale. A novel time-resolved scanning tunneling spectroscopy technique is presented and used to efficiently search for dynamics.

Time-Resolved Scanning Tunneling Microscopy

Time-Resolved Scanning Tunneling Microscopy

Resolving and Tuning Carrier Capture Rates at a Single Silicon Atom Gap State.

We report on tuning the carrier capture events at a single dangling bond (DB) midgap state by varying the substrate temperature, doping type, and doping concentration. All-electronic time-resolved scanning tunneling microscopy (TR-STM) is employed to directly measure the carrier capture rates on the nanosecond time scale. A characteristic negative differential resistance (NDR) feature is evident in the scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) measurements of DBs on bothn- and p-type doped samples. We find that a common model accounts for both observations. Atom-specific Kelvin probe force microscopy (KPFM) measurements confirm the energetic position of the DB's charge transition levels, corroborating STS studies. We show that under different tip-induced fields the DB can be supplied with electrons from two distinct reservoirs: the bulk conduction band and/or the valence band. We measure the filling and emptying rates of the DBs in the energy regime where electrons are supplied by the bulk valence band. We show that adding point charges in the vicinity of a DB shifts observed STS and NDR features due to Coulombic interactions.

Atomic structure of self-organizing iridium induced nanowires on Ge(001)

The atomic structure of self-organizing iridium (Ir) induced nanowires on Ge(001) is studied by density functional theory (DFT) calculations and variable-temperature scanning tunneling microscopy. The Ir induced nanowires are aligned in a direction perpendicular to the Ge(001) substrate dimer rows, have a width of two atoms and are completely kink-less. Density functional theory calculations show that the Ir atoms prefer to dive into the Ge(001) substrate and push up the neighboring Ge substrate atoms. The nanowires are composed of Ge atoms and not Ir atoms as previously assumed. The regions in the vicinity of the nanowires are very dynamic, even at temperatures as low as 77K. Time-resolved scanning tunneling microscopy measurements reveal that this dynamics is caused by buckled Ge substrate dimers that flip back and forth between their two buckled configurations.

Time-Resolved Imaging of Negative Differential Resistance on the Atomic Scale.

Negative differential resistance remains an attractive but elusive functionality, so far only finding niche applications. Atom scale entities have shown promising properties, but the viability of device fabrication requires a fuller understanding of electron dynamics than has been possible to date. Using an all-electronic time-resolved scanning tunneling microscopy technique and a Green's function transport model, we study an isolated dangling bond on a hydrogen terminated silicon surface. A robust negative differential resistance feature is identified as a many body phenomenon related to occupation dependent electron capture by a single atomic level. We measure all the time constants involved in this process and present atomically resolved, nanosecond time scale images to simultaneously capture the spatial and temporal variation of the observed feature.

Time-resolved single dopant charge dynamics in silicon.

As the ultimate miniaturization of semiconductor devices approaches, it is imperative that the effects of single dopants be clarified. Beyond providing insight into functions and limitations of conventional devices, such information enables identification of new device concepts. Investigating single dopants requires sub-nanometre spatial resolution, making scanning tunnelling microscopy an ideal tool. However, dopant dynamics involve processes occurring at nanosecond timescales, posing a significant challenge to experiment. Here we use time-resolved scanning tunnelling microscopy and spectroscopy to probe and study transport through a dangling bond on silicon before the system relaxes or adjusts to accommodate an applied electric field. Atomically resolved, electronic pump-probe scanning tunnelling microscopy permits unprecedented, quantitative measurement of time-resolved single dopant ionization dynamics. Tunnelling through the surface dangling bond makes measurement of a signal that would otherwise be too weak to detect feasible. Distinct ionization and neutralization rates of a single dopant are measured and the physical process controlling those are identified.

Vibron-assisted spin relaxation at a metal/organic interface

Inspired by recent experiments for hybrid organic-ferromagnet interfaces, we propose a spin-relaxation mechanism which does not depend on either the spin-orbit or the hyperfine interaction. This takes place when a molecule with initial spin imbalance is weakly coupled to a metal surface and can be excited in various vibrational states. In such a situation the electron-vibron interaction promotes the exchange of spin-polarized electrons between the molecule and the surface, serving as an energy and angular momentum reservoir. This process leads to an effective spin relaxation of the electron population in the molecule. We suggest that this nonequilibrium mechanism can be investigated through time-resolved spin-polarized scanning tunneling microscopy experiments.

Dynamics of oligo(phenylene-ethynylene) self-assembled monolayers on Au(1 1 1)

Oligo(phenylene-ethynylene), self-assembled monolayers on Au(111) have been studied with scanning tunneling microscopy. The oligo(phenylene-ethynylene) molecules are adsorbed in a flat-lying orientation. Time-resolved scanning tunneling microscopy measurements reveal that the molecules continuously switch back and forth between two nearly degenerate configurations. The energy difference between the two configurations is 22±5meV and the activation barrier for the transition from the low-energy configuration to the high-energy configuration is 0.65±0.03eV. A statistical analysis of the residence times revealed that the switching process is stochastic. We propose that the two level switching is due to a torsional mode of the central phenyl ring.

High-resolution tunnel fluctuoscopy

Electron tunneling spectroscopy pioneered by Esaki and Giaever offered a powerful tool for studying electronic spectra and density of states (DOS) in superconductors. This led to important discoveries that revealed, in particular, the pseudogap in the tunneling spectrum of superconductors above their critical temperatures. However, the phenomenological approach of Giaever and Megerle does not resolve the fine structure of low-bias behavior carrying significant information about electron scattering, interactions, and decoherence effects. Here we construct a complete microscopic theory of electron tunneling into a superconductor in the fluctuation regime. We reveal a non-trivial low-energy anomaly in tunneling conductivity due to Andreev-like reflections of injected electrons from superconducting fluctuations. Our findings enable real-time observation of fluctuating Cooper pairs dynamics by time-resolved scanning tunneling microscopy measurements and open new horizons for quantitative analysis of the fluctuation electronic spectra of superconductors.

Femtosecond time-resolved STM : the present and future

Femtosecond time-resolved STM : the present and future

Nonlinear femtosecond laser induced scanning tunneling microscopy

We demonstrate ultrafast laser driven nonlinear scanning tunneling microscopy (STM), under ambient conditions. The design is an adaptation of the recently introduced cross-polarized double beat method, whereby z-polarized phase modulated fields are tightly focused at a tunneling junction consisting of a sharp tungsten tip and an optically transparent gold film as substrate. We demonstrate the prerequisites for ultrafast time-resolved STM through an operative mechanism of nonlinear laser field-driven tunneling. The spatial resolution of the nonlinear laser driven STM is determined by the local field intensity. Resolution of 0.3 nm-10 nm is demonstrated for the intensity dependent, exponential tunneling range. The demonstration is carried out on a junction consisting of tungsten tip and gold substrate. Nano-structured gold is used for imaging purposes, to highlight junction plasmon controlled tunneling in the conductivity limit.