Photoemission Electron Microscopy Research Articles

Watching (De)Intercalation of 2D Metals in Epitaxial Graphene: Insight into the Role of Defects.

Intercalation forms heterostructures, and over 25 elements and compounds are intercalated into graphene, but the mechanism for this process is not well understood. Here, the de-intercalation of 2D Ag and Ga metals sandwiched between bilayer graphene and SiC are followed using photoemission electron microscopy (PEEM) and atomistic-scale reactive molecular dynamics simulations. By PEEM, de-intercalation "windows" (or defects) are observed in both systems, but the processes follow distinctly different dynamics. Reversible de- and re-intercalation of Ag is observed through a circular defect where the intercalation velocity front is 0.5nm s-1 ± 0.2nm s.-1 In contrast, the de-intercalation of Ga is irreversible with faster kinetics that are influenced by the non-circular shape of the defect. Molecular dynamics simulations support these pronounced differences and complexities between the two Ag and Ga systems. In the de-intercalating Ga model, Ga atoms first pile up between graphene layers until ultimately moving to the graphene surface. The simulations, supported by density functional theory, indicate that the Ga atoms exhibit larger binding strength to graphene, which agrees with the faster and irreversible diffusion kinetics observed. Thus, both the thermophysical properties of the metal intercalant and its interaction with defective graphene play a key role in intercalation.

Observation and formation mechanism of 360° domain wall rings in synthetic anti-ferromagnets with interlayer chiral interactions

The interlayer Dzyaloshinskii–Moriya interaction (IL-DMI) chirally couples spins in different ferromagnetic layers of multilayer heterostructures. So far, samples with IL-DMI have been investigated utilizing magnetometry and magnetotransport techniques, where the interaction manifests as a tunable chiral exchange bias field. Here, we investigate the nanoscale configuration of the magnetization vector in a synthetic anti-ferromagnet (SAF) with IL-DMI, after applying demagnetizing field sequences. We add different global magnetic field offsets to the demagnetizing sequence in order to investigate the states that form when the IL-DMI exchange bias field is fully or partially compensated. For magnetic imaging and vector reconstruction of the remanent magnetic states, we utilize x-ray magnetic circular dichroism photoemission electron microscopy, evidencing the formation of 360° domain wall rings of typically 0.5–3.0 μm in diameter. These spin textures are only observed when the exchange bias field due to the IL-DMI is not perfectly compensated by the magnetic field offset. From a combination of micromagnetic simulations, magnetic charge distribution, and topology arguments, we conclude that a non-zero remanent effective field with components both parallel and perpendicular to the anisotropy axis of the SAF is necessary to observe the rings. This work shows how the exchange bias field due to IL-DMI can lead to complex metastable spin states during reversal, important for the development of future spintronic devices.

Nondestructive imaging of breakdown process in ferroelectric capacitors using in situ laser-based photoemission electron microscopy

HfO2-based ferroelectrics are one of the most actively developed functional materials for memory devices. However, in HfO2-based ferroelectric devices, dielectric breakdown is a main failure mechanism during repeated polarization switching. Elucidation of the breakdown process may broaden the scope of applications for the ferroelectric HfO2. Here, we report direct observations of a breakdown process in HfO2-based ferroelectric capacitors, by in situ laser-based photoemission electron microscopy. We have not only clearly visualized the hard dielectric breakdown (HDB) spot but also observed the regions responsible for the soft dielectric breakdown (SDB), which is a precursor phenomenon to HDB. It was found that the low-resistance region formed after SDB is wider than the conduction path formed after HDB. Furthermore, our spectromicroscopic analysis revealed that the photoelectron spectrum after SDB shows an enhancement in intensity without spectral-shape modulation, interpreted that the initially existed defects are increased. In the HDB spot, however, an additional shoulder structure was observed. These results provide spectroscopic evidence that the electronic states responsible for the conduction path after SDB are different from those after HDB. Through this work, we propose this microscopic approach as a versatile tool for studying buried materials as they are, accelerating the development of material engineering for advanced electronic devices.

Reveal Ultrafast Electron Relaxation across Sub-bands of Tellurium by Time- and Energy-Resolved Photoemission Microscopy.

Exploring ultrafast carrier dynamics is crucial for the materials' fundamental properties and device design. In this work, we employ time- and energy-resolved photoemission electron microscopy with tunable pump wavelengths from visible to near-infrared to reveal the ultrafast carrier dynamics of the elemental semiconductor tellurium. We find that two discrete sub-bands around the Γ point of the conduction band are involved in excited-state electron ultrafast relaxation and reveal that hot electrons first go through ultrafast intra sub-band cooling on a time scale of about 0.3 ps and then transfer from the higher sub-band to the lower one on a time scale of approximately 1 ps. Additionally, theoretical calculations reveal that the lower one has flat-band characteristics, possessing a large density of states and a long electron lifetime. Our work demonstrates that TR- and ER-PEEM with broad tunable pump wavelengths are powerful techniques in revealing the details of ultrafast carrier dynamics in time and energy domains.

Aurophilic Molecules on Surfaces. Part II. (NapNC)AuCl on Au(111).

Although aurophilicity is a well-known phenomenon in structural gold chemistry and is found in many crystals of Au(I) complexes, its potential for self-assembly in thin films is not yet explored. This paper is Part II of a study, in which we investigated the ultrathin film formation of chlorido(2-naphthyl isonitrile) gold(I) on gold surfaces. Here, we present the data for the growth of (NapNC)AuCl on isotropic Au(111) surfaces. Already during physical vapor deposition, the condensation of ultrathin films is monitored by photoelectron emission microscopy (PEEM) and incremental and spectrally resolved changes in the optical reflectance (DDRS). Additional structural data obtained by scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) reveal that the "crossed swords" packing motif known from the bulk is also present in thin films.

Cyclohexane Oxidative Dehydrogenation on Graphene-Oxide-Supported Cobalt Ferrite Nanohybrids: Effect of Dynamic Nature of Active Sites on Reaction Selectivity.

In this work, we investigated cyclohexane oxidative dehydrogenation (ODH) catalyzed by cobalt ferrite nanoparticles supported on reduced graphene oxide (RGO). We aim to identify the active sites that are specifically responsible for full and partial dehydrogenation using advanced spectroscopic techniques such as X-ray photoelectron emission microscopy (XPEEM) and X-ray photoelectron spectroscopy (XPS) along with kinetic analysis. Spectroscopically, we propose that Fe3+/Td sites could exclusively produce benzene through full cyclohexane dehydrogenation, while kinetic analysis shows that oxygen-derived species (O*) are responsible for partial dehydrogenation to form cyclohexene in a single catalytic sojourn. We unravel the dynamic cooperativity between octahedral and tetrahedral sites and the unique role of the support in masking undesired active (Fe3+/Td) sites. This phenomenon was strategically used to control the abundance of these species on the catalyst surface by varying the particle size and the wt % content of the nanoparticles on the RGO support in order to control the reaction selectivity without compromising reaction rates which are otherwise extremely challenging due to the much favorable thermodynamics for complete dehydrogenation and complete combustion under oxidative conditions.

Spectromicroscopic study of the transformation with low energy ions of a hematite thin film into a magnetite/hematite epitaxial bilayer

The search of new properties in novel oxide heterostructures requires the exploration of new fabrication methods and the study, at the microscopic level, of the processes involved during the synthesis. We present a synchrotron-based spectromicroscopic investigation of a magnetite/hematite bilayer on Pt(111) grown in a two-step process by thermal evaporation and Low Energy Ion Bombardment (LEIB). The characterization includes the study of structural, electronic, chemical, and magnetic properties using X-ray Absorption Spectroscopy (XAS), Low Energy Electron Microscopy (LEEM), Photoemission Electron Microscopy (PEEM), or X-ray Magnetic Circular Dichroism (XMCD). The aim is to obtain microscopic information of the thin film before, during, and after the ion bombardment. Ion bombardment gradually transforms the topmost layers of the hematite thin film into a defective sub-oxide, where magnetite nuclei grow and coalesce with increasing ion doses. Two rotational domains of magnetite coexist, which are typically a few tens of nanometres large and do not grow significantly with temperature annealings. The incoherent growth of the magnetite nuclei favours the formation of stable twin boundaries (TBs) and antiphase boundaries (APBs). Dichroic spectra show the characteristics of the ferrimagnetic (FiM) order of magnetite, and the spatial distribution of magnetic domains shows no apparent correlation with the structural image, displaying smooth domains separated by diffuse frontiers. These findings illustrate the importance of a spectromicroscopic characterization of novel oxide heterostructures for potential future applications.

Real-space observation of ergodicity transitions in artificial spin ice

Ever since its introduction by Ludwig Boltzmann, the ergodic hypothesis became a cornerstone analytical concept of equilibrium thermodynamics and complex dynamic processes. Examples of its relevance range from modeling decision-making processes in brain science to economic predictions. In condensed matter physics, ergodicity remains a concept largely investigated via theoretical and computational models. Here, we demonstrate the direct real-space observation of ergodicity transitions in a vertex-frustrated artificial spin ice. Using synchrotron-based photoemission electron microscopy we record thermally-driven moment fluctuations as a function of temperature, allowing us to directly observe transitions between ergodicity-breaking dynamics to system freezing, standing in contrast to simple trends observed for the temperature-dependent vertex populations, all while the entropy features arise as a function of temperature. These results highlight how a geometrically frustrated system, with thermodynamics strictly adhering to local ice-rule constraints, runs back-and-forth through periods of ergodicity-breaking dynamics. Ergodicity breaking and the emergence of memory is important for emergent computation, particularly in physical reservoir computing. Our work serves as further evidence of how fundamental laws of thermodynamics can be experimentally explored via real-space imaging.

Near- and far-field study of polarization-dependent surface plasmon resonance in bowtie nano-aperture arrays.

Bowtie nano-apertures can confine light into deep subwavelength volumes with extreme field enhancement, making them a useful tool for various applications such as optical trapping, deep subwavelength imaging, nanolithography, and sensors. However, the correlation between the near- and far-field properties of bowtie nano-aperture arrays has yet to be fully explored. In this study, we experimentally investigated the polarization-dependent surface plasmon resonance in bowtie nano-aperture arrays using both optical transmission spectroscopy and photoemission electron microscopy. The experimental results reveal a nonlinear redshift in the transmission spectra as the gap size of the bowtie nanoaperture decreases for vertically polarized light, while the transmission spectra remain unchanged with different gap sizes for horizontally polarized light. To elucidate the underlying mechanisms, we present simulated charge and current distributions, revealing how the electrons respond to light and generate the plasmonic fields. These near-field distributions were verified by photoemission electron microscopy. This study provides a comprehensive understanding of the plasmonic properties of bowtie nano-aperture, enabling their further applications, one of which is the optical switching of the resonance wavelength in the widely used visible spectral region without changing the geometry of the nanostructure.

Ultrafast Electronic Dynamics in Anisotropic Indirect Interlayer Excitonic States of Monolayer WSe2/ReS2 Heterojunctions.

Understanding ultrafast electronic dynamics of the interlayer excitonic states in atomically thin transition metal dichalcogenides is of importance in engineering valleytronics and developing excitonic integrated circuits. In this work, we experimentally explored the ultrafast dynamics of indirect interlayer excitonic states in monolayer type II WSe2/ReS2 heterojunctions using time-resolved photoemission electron microscopy, which reveals its anisotropic behavior. The ultrafast cooling and decay of excited-state electrons exhibit significant linear dichroism. The ab initio theoretical calculations provide unambiguous evidence that this linear dichroism result is primarily associated with the anisotropic nonradiative recombination of indirect interlayer excitonic states. Measuring time-resolved photoemission energy spectra, we have further revealed the ultrafast evolution of excited-state electrons in anisotropic indirect interlayer excitonic states. The findings have important implications for controlling the interlayer moiré excitonic effects and designing anisotropic optoelectronic devices.

Probing electron and lattice dynamics by ultrafast electron microscopy: Principles and applications

AbstractMicroscale charge and energy transfer is an ultrafast process that can determine the photoelectrochemical performance of devices. However, nonlinear and nonequilibrium properties hinder our understanding of ultrafast processes; thus, the direct imaging strategy has become an effective means to uncover ultrafast charge and energy transfer processes. Due to diffraction limits of optical imaging, the obtained optical image has insufficient spatial resolution. Therefore, electron beam imaging combined with a pulse laser showing high spatial–temporal resolution has become a popular area of research, and numerous breakthroughs have been achieved in recent years. In this review, we cover three typical ultrafast electron beam imaging techniques, namely, time‐resolved photoemission electron microscopy, scanning ultrafast electron microscopy, and ultrafast transmission electron microscopy, in addition to the principles and characteristics of these three techniques. Some outstanding results related to photon–electron interactions, charge carrier transport and relaxation, electron–lattice coupling, and lattice oscillation are also reviewed. In summary, ultrafast electron beam imaging with high spatial–temporal resolution and multidimensional imaging abilities can promote the fundamental understanding of physics, chemistry, and optics, as well as guide the development of advanced semiconductors and electronics.

Modulating above-room-temperature magnetism in Ga-implanted Fe5GeTe2 van der Waals magnets

The creation of van der Waals (vdW) ferromagnets with tunable Curie temperature (TC) and magnetic anisotropy is essential in developing vdW magnet-based devices. Here, we report an effective and reliable method for modulating the magnetic properties of vdW Fe5GeTe2 by site-specific Ga+ implantation. In this study, we report an easy axis in the ab-plane for bulk Fe5GeTe2 (TC = 310 K) and an axis out of the plane for thin Fe5GeTe2 flakes (TC = 290 K). Combining element-resolved photoemission electron microscopy and spatially resolved magneto-optic Kerr microscopy, we find that the implantation of a tiny amount of 10−3 Ga+·Å−3 in Fe5GeTe2 greatly enhances the TC from 290 to 360 K and switches the magnetic easy axis from the out-of-plane c axis to the ab-plane. The room-temperature x-ray magnetic circular dichroism signal is enhanced from 0% to 9% at an implantation level of 10−2 Ga+·Å−3. These results provide new opportunities for tailoring the magnetic properties of vdW materials beyond room temperature.

Ultrafast Electronic Relaxation Dynamics of Atomically Thin MoS2 Is Accelerated by Wrinkling.

Strain engineering is an attractive approach for tuning the local optoelectronic properties of transition metal dichalcogenides (TMDs). While strain has been shown to affect the nanosecond carrier recombination dynamics of TMDs, its influence on the sub-picosecond electronic relaxation dynamics is still unexplored. Here, we employ a combination of time-resolved photoemission electron microscopy (TR-PEEM) and nonadiabatic ab initio molecular dynamics (NAMD) to investigate the ultrafast dynamics of wrinkled multilayer (ML) MoS2 comprising 17 layers. Following 2.41 eV photoexcitation, electronic relaxation at the Γ valley occurs with a time constant of 97 ± 2 fs for wrinkled ML-MoS2 and 120 ± 2 fs for flat ML-MoS2. NAMD shows that wrinkling permits larger amplitude motions of MoS2 layers, relaxes electron-phonon coupling selection rules, perturbs chemical bonding, and increases the electronic density of states. As a result, the nonadiabatic coupling grows and electronic relaxation becomes faster compared to flat ML-MoS2. Our study suggests that the sub-picosecond electronic relaxation dynamics of TMDs is amenable to strain engineering and that applications which require long-lived hot carriers, such as hot-electron-driven light harvesting and photocatalysis, should employ wrinkle-free TMDs.

Revealing low-loss dielectric near-field modes of hexagonal boron nitride by photoemission electron microscopy

Low-loss dielectric modes are important features and functional bases of fundamental optical components in on-chip optical devices. However, dielectric near-field modes are challenging to reveal with high spatiotemporal resolution and fast direct imaging. Herein, we present a method to address this issue by applying time-resolved photoemission electron microscopy to a low-dimensional wide-bandgap semiconductor, hexagonal boron nitride (hBN). Taking a low-loss dielectric planar waveguide as a fundamental structure, static vector near-field vortices with different topological charges and the spatiotemporal evolution of waveguide modes are directly revealed. With the lowest-order vortex structure, strong nanofocusing in real space is realized, while near-vertical photoemission in momentum space and narrow spread in energy space are simultaneously observed due to the atomically flat surface of hBN and the small photoemission horizon set by the limited photon energies. Our approach provides a strategy for the realization of flat photoemission emitters.

Aurophilic Molecules on Surfaces. Part I. (NapNC)AuCl on Au(110).

Aurophilicity is a well-known phenomenon in structural gold chemistry and is found in many crystals of Au(I) complexes. However, these attractive dispersion forces between and within complexes containing Au(I) moieties have not been well studied in ultrathin films. In this paper, we elucidate the interaction of chlorido(2-naphthyl isonitrile)gold(I) on and with Au(110) surfaces. Already during physical vapor deposition, the condensation of ultrathin films is monitored by photoelectron emission microscopy (PEEM) and by incremental and spectrally resolved changes in the optical reflectance (DDRS). Additional structural data obtained by STM and LEED reveal that the "crossed swords" packing motif known from the bulk is also present in thin films. The molecular arrangement changes several times during thin-film deposition.

Imaging and Controlling Ultrafast Electron Pulses Emitted from Plasmonic Nanostructures.

We experimentally study photoemission from gold nanodisk arrays using space-, time-, and energy-resolved photoemission electron microscopy. When excited by a plasmonic resonant infrared (IR) laser pulse, plasmonic hotspots are generated owing to local surface plasmon resonance. Photoelectrons emitted from each plasmonic hotspot form a nanoscale and ultrashort electron pulse. When the system is excited by an extreme ultraviolet (EUV) laser pulse, a uniformly distributed photoelectron cloud is formed across the sample surface. When excited by the IR and EUV laser pulses together, both the photoemission image and kinetic energy vary significantly for the IR laser-generated electrons depending on the time delay between the two laser pulses. These observations are well explained by the Coulomb interaction with the EUV laser-generated electron cloud. Our study offers a feasible approach to manipulate the energy of electron pulse emitted from a plasmonic nanostructure on an ultrafast time scale.

Photoemission Electron Microscopy of Blue and UV Surface Plasmons on Nanostructured Aluminum Films

We image surface plasmons on aluminum surfaces in the ultraviolet and blue spectral range with photoemission electron microscopy (PEEM). Plasmon excitation is mediated by light incident on straight aluminum ridges with subwavelength cross section on flat aluminum films. We observe interference patterns due to light/plasmon interaction, with distinct periodicity and orientation depending on the light in-plane incidence angle with respect to the ridge orientation. From the interference patterns, we deduce the surface plasmon propagation directions and decay lengths. The latter are remarkably high with 2.8 μ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\mu$$\\end{document}m and 8.4 μ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\mu$$\\end{document}m for excitation wavelengths of 273 nm and 410 nm, respectively. Our results extend PEEM imaging of surface plasmons into the ultraviolet region.

Spin dynamics, loop formation and cooperative reversal in artificial quasicrystals with tailored exchange coupling

Aperiodicity and un-conventional rotational symmetries allow quasicrystalline structures to exhibit unusual physical and functional properties. In magnetism, artificial ferromagnetic quasicrystals exhibited knee anomalies suggesting reprogrammable magnetic properties via non-stochastic switching. However, the decisive roles of short-range exchange and long-range dipolar interactions have not yet been clarified for optimized reconfigurable functionality. We report broadband spin-wave spectroscopy and X-ray photoemission electron microscopy on different quasicrystal lattices consisting of ferromagnetic Ni81Fe19 nanobars arranged on aperiodic Penrose and Ammann tilings with different exchange and dipolar interactions. We imaged the magnetic states of partially reversed quasicrystals and analyzed their configurations in terms of the charge model, geometrical frustration and the formation of flux-closure loops. Only the exchange-coupled lattices are found to show aperiodicity-specific collective phenomena and non-stochastic switching. Both, exchange and dipolarly coupled quasicrystals show magnonic excitations with narrow linewidths in minor loop measurements. Thereby reconfigurable functionalities in spintronics and magnonics become realistic.

Methodology and implementation of a tunable deep-ultraviolet laser source for photoemission electron microscopy

Photoemission electron microscopy (PEEM) is a unique and powerful tool for studying the electronic properties of materials and surfaces. However, it requires intense and well-controlled light sources with photon energies ranging from the UV to soft X-rays for achieving high spatial resolution and image contrast. Traditionally, many PEEMs were installed at synchrotron light sources to access intense and tunable soft X-rays. More recently, the maturation of solid-state lasers has opened a new avenue for laboratory-based PEEMs using laser-based UV light at lower photon energies. Here, we report on the characteristics of a laser-based UV light source that was recently integrated with a PEEM instrument. The system consists of a high repetition rate, tunable wavelength laser coupled to a harmonics generation module, which generates deep-UV radiation from 192 nm to 210 nm. We comment on the spectral characteristics and overall laser system stability, as well as on the effects of space charge within the PEEM microscope at high UV laser fluxes. Further, we show an example of imaging on gallium nitride, where the higher UV photon energy and flux of the laser provides considerably improved image quality, compared to a conventional light source. These results demonstrate the capabilities of laser-based UV light sources for advancing laboratory-based PEEMs.

2D imaging spin-filter for NanoESCA based on Au/Ir(001) or Fe(001)-p(1×1)O

A two-dimensional imaging spin-filter for photo-emission electron microscopy is described. The spin-filter is capable of imaging the electron spin polarization of either real space or momentum space electron distributions. As a scattering target either Au/Ir(001) comes into use, where spin sensitivity results from using spin–orbit scattering or Fe(001)-p(1×1)O that exploits exchange interaction. Both scattering targets were characterized with respect to their working points and Sherman function in a separate setup. Spin-polarization images of secondary electrons from the magnetic domains of a poly-crystalline iron sample are shown using both scattering targets. Images with a spin-filter using Au/Ir(001) show more than 104 discrete detection channels which increases the effective two-dimensional figure-of-merit (FoM) of this spin-filter by four orders of magnitude compared to single-channel spin detectors. Using the exchange scattering target two spin-components have been imaged for the first time. A method to detect all three spin-components is also outlined.