The recent development of optical technology has enabled the practical use of a carrier-envelope phase-controlled monocycle electric field in the terahertz (THz) regime. By combining this technique with metal nanostructures such as nanotips, which induce near-field enhancement, the development of novel applications is anticipated. In particular, THz scanning tunneling microscopy (THz-STM) is a promising technique for probing ultrafast dynamics with the spatial resolution of STM. However, the modulation of the THz waveform is generally accompanied by an enhancement of the electric field, which is unknown in actual measurement environments. Here, we present a method enabling direct evaluation of the enhanced near field in the tunnel junction in THz-STM in the femtosecond range, which is essential for the use of the THz near field. In the tunneling regime, it was also demonstrated that the transient electronic state excited by an optical pulse can be evaluated using the THz-STM, and the ultrafast carrier dynamics in 2H-MoTe2 excited by an optical pulse was reproducibly probed.

Light-field-driven processes occurring under conditions far beyond the diffraction limit of the light can be manipulated by harnessing spatiotemporally tunable near fields. A tailor-made carrier envelope phase in a tunnel junction formed between nanogap electrodes allows precisely controlled manipulation of these processes. In particular, the characterization and active control of near fields in a tunnel junction are essential for advancing elaborate manipulation of light-field-driven processes at the atomic-scale. Here, we demonstrate that desirable phase-controlled near fields can be produced in a tunnel junction via terahertz scanning tunneling microscopy (THz-STM) with a phase shifter. Measurements of the phase-resolved subcycle electron tunneling dynamics revealed an unexpected large carrier-envelope phase shift between far-field and near-field single-cycle THz waveforms. The phase shift stems from the wavelength-scale feature of the tip-sample configuration. By using a dual-phase double-pulse scheme, the electron tunneling was coherently manipulated over the femtosecond time scale. Our new prescription-in situ tailoring of single-cycle THz near fields in a tunnel junction-will offer unprecedented control of electrons for ultrafast atomic-scale electronics and metrology.

Studying the microscopic behavior of free carriers in materials at an ultrashort time scale is critical to developing semiconductor, optoelectronic, and other technologies satisfying the ever-increasing requirements for smaller sizes and higher speeds. Understanding the effect of local potential modulations and localized states due to nanoscale microstructures on carrier dynamics is essential to realize these requirements. Here, we used time-resolved scanning tunneling microscopy/spectroscopy (STM/STS) combined with a carrier-envelope phase (CEP)-controlled subcycle THz electric field, THz-STM, to probe the ultrafast motion of electrons photoinjected into C 60 multilayer structures grown on Au substrate. We have succeeded in demonstrating the time-resolved measurement of ultrafast electron dynamics with sub-nanoscale spatial resolution and subcycle time resolution for the first time and successfully visualized the electron motion triggered by the spatial variation in the lowest unoccupied molecular orbital (LUMO). The difference in the effects of molecular defects, such as a molecular vacancy and orientational disorder, was also clearly distinguished with single-molecular-level spatial resolution. This method is expected to play an important role in the precise evaluation of local electronic structures and dynamics for the future development of new functional materials and device elements.

A two-dimensional nanocarbon, graphene, has attracted substantial interest due to its excellent properties. The reduction of graphene oxide (GO) has been investigated for the mass production of graphene used in practical applications. Different reduction processes produce different properties in graphene, affecting the performance of the final materials or devices. Therefore, an understanding of the mechanisms of GO reduction is important for controlling the properties of functional two-dimensional systems. Here, we determined the average structure of reduced GO prepared via heating and photoexcitation and clearly distinguished their reduction mechanisms using ultrafast time-resolved electron diffraction, time-resolved infrared vibrational spectroscopy, and time-dependent density functional theory calculations. The oxygen atoms of epoxy groups are selectively removed from the basal plane of GO by photoexcitation (photon mode), in stark contrast to the behavior observed for the thermal reduction of hydroxyl and epoxy groups (thermal mode). The difference originates from the selective excitation of epoxy bonds via an electronic transition due to their antibonding character. This work will enable the preparation of the optimum GO for the intended applications and expands the application scope of two-dimensional systems.