Photoemission Electron Microscopy Research Articles

Imaging Thermally Fluctuating Néel Vectors in van der Waals Antiferromagnet NiPS3.

Studying antiferromagnetic domains is essential for fundamental physics and potential spintronics applications. Despite their importance, few systematic studies have been performed on antiferromagnet (AFM) domains with high spatial resolution in van der Waals (vdW) materials, and direct probing of the Néel vectors remains challenging. In this work, we found multidomain states in the vdW AFM NiPS3, a material extensively investigated for its unique magnetic exciton. We employed photoemission electron microscopy combined with the X-ray magnetic linear dichroism (XMLD-PEEM) to image the NiPS3's magnetic structure. The nanometer-spatial resolution of XMLD-PEEM allows us to determine local Néel vector orientations and discover thermally fluctuating Néel vectors that are independent of the crystal symmetry even at 65 K, well below the TN of 155 K. We demonstrate that an in-plane orbital moment of the Ni ion is responsible for the weak magnetocrystalline anisotropy. The observed thermal fluctuations of the antiferromagnetic domains may explain the broadening of magnetic exciton peaks at higher temperatures.

Spatially resolved work-function manipulation of azobenzene-functionalized self-assembled monolayers by optical stimulation

Strongly differing static dipole moments of the trans and cis isomers of photochromic azobenzene allow for optical switching of the work function of azobenzene-functionalized self-assembled monolayers (SAMs). We apply these properties in a fundamental experiment to manipulate the area size of the switched SAM. Azobenzene molecules were excited by ultraviolet laser illumination, and the transient isomerization profile of the SAM was spatially resolved recording photoemission electron microscopy images. Thereby, we demonstrate the spatial tuning of the SAM's work function and discuss the role of the laser spot profile in generating sharp edges or gradual changes of the work function.

Exploring the Mineral Composition, Structure, and Function of a Freshwater Bivalve Adhesive

AbstractEtheria elliptica is a freshwater oyster that produces an adhesive that hardens underwater, allowing them to attach to other oysters, rocks, wood, and other natural substrates, producing complex oyster bed communities. Despite the importance of the adhesive in oyster bed formation, little is known about its chemical composition, structure, or mechanical properties. Through a combination of scanning electron microscopy (SEM), x‐ray photoemission electron microscopy (X‐PEEM), infrared (IR) spectroscopy, microhardness testing, and nanoindentation, it is found that the oyster adhesive consists entirely of aragonite nanoparticles that clump together into crystallites of varied shape, size, and orientation. The crystallite clumping density varies from the exterior of the adhesive to the interior, with the adhesive closest to the prismatic layer generally being denser. With this variation in density comes a variation in material properties with the exterior adhesive layer being softer and more flexible and the interior adhesive layer being harder and less elastic, or more similar to the prismatic and nacre shell structures produced by the E. elliptica. The resultant material exhibits varied materials properties, despite similar mineral composition.

The fate of graphene on copper: Intercalation / de-intercalation processes and the role of silicon

Intercalation and de-intercalation processes below graphene (g) grown by chemical vapor deposition (CVD) on Cu foils (g/Cu) were investigated in a combined low-energy electron microscopy and X-ray photoemission electron microscopy study. Exposure of g/Cu to air induces oxygen and water intercalation which can be removed by annealing in vacuum leading to clean and well-ordered graphene on Cu. However, prolonged air exposure leads to intercalation of large amounts of oxygen, most likely inducing the formation of copper oxides. If sufficient intercalated oxygen remains at the interface when exceeding 320 °C, graphene is oxidized and burned off. Cu foils can be loaded with silicon on purpose during foil pre-treatment or accidently during long growth time when applying high temperatures at elevated H2 pressure inducing the reactive removal of Si species from the quartz reactor wall. Due to the dissolution of Si in the Cu bulk, the Si surface concentration remains below detection limit and graphene of equal crystalline quality is grown as if the Cu foil was silicon-free. However, oxygen intercalation underneath graphene on Si-containing Cu foils can induce Si segregation towards the surface and formation of intercalated silica without attacking the covering graphene. Even at high temperatures, segregating Si acts as oxygen scavenger so that graphene resists oxidation. The observed effect explains the usefulness of certain synthesis protocols and paves the way towards large-scale fabrication of electronically decoupled graphene. The effect can be used to immobilize adsorbing oxygen at the interface and image the initial steps of intercalation below graphene in-situ.

Unveiling nano-scale chemical inhomogeneity in surface oxide films formed on V- and N-containing martensite stainless steel by synchrotron X-ray photoelectron emission spectroscopy/microscopy and microscopic X-ray absorption spectroscopy

Nano-scale chemical inhomogeneity in surface oxide films formed on a V- and N-containing martensite stainless steel and tempering heating induced changes are investigated by a combination of synchrotron- based hard X-ray Photoelectron emission spectroscopy (HAXPES) and microscopy (HAXPEEM) as well as microscopic X-ray absorption spectroscopy (m-XAS) techniques. The results reveal the inhomogeneity in the oxide films on the micron-sized Cr2N- and VN-type particles, while the inhomogeneity on the martensite matrix phase exists due to localised formation of nano-sized tempering nitride particles at 600 °C. The oxide film formed on Cr2N-type particles is rich in Cr2O3 compared with that on the martensite matrix and VN-type particles. With the increase of tempering temperature, Cr2O3 formation is faster for the oxidation of Cr in the martensite matrix than the oxidation of Cr nitride-rich particles.

Momentum space separation of quantum path interferences between photons and surface plasmon polaritons in nonlinear photoemission microscopy

Abstract Quantum path interferences occur whenever multiple equivalent and coherent transitions result in a common final state. Such interferences strongly modify the probability of a particle to be found in that final state, a key concept of quantum coherent control. When multiple nonlinear and energy-degenerate transitions occur in a system, the multitude of possible quantum path interferences is hard to disentangle experimentally. Here, we analyze quantum path interferences during the nonlinear emission of electrons from hybrid plasmonic and photonic fields using time-resolved photoemission electron microscopy. We experimentally distinguish quantum path interferences by exploiting the momentum difference between photons and plasmons and through balancing the relative contributions of their respective fields. Our work provides a fundamental understanding of the nonlinear photon–plasmon–electron interaction. Distinguishing emission processes in momentum space, as introduced here, could allow nano-optical quantum-correlations to be studied without destroying the quantum path interferences.

Structural, chemical, and magnetic investigation of a graphene/cobalt/platinum multilayer system on silicon carbide

We investigate the magnetic interlayer coupling and domain structure of ultra-thin ferromagnetic (FM) cobalt (Co) layers embedded between a graphene (G) layer and a platinum (Pt) layer on a silicon carbide (SiC) substrate (G/Co/Pt on SiC). Experimentally, a combination of x-ray photoemission electron microscopy with x-ray magnetic circular dichroism has been carried out at the Co L-edge. Furthermore, structural and chemical properties of the system have been investigated using low energy electron diffraction (LEED) and x-ray photoelectron spectroscopy (XPS). In situ LEED patterns revealed the crystalline structure of each layer within the system. Moreover, XPS confirmed the presence of quasi-freestanding graphene, the absence of cobalt silicide, and the appearance of two silicon carbide surface components due to Pt intercalation. Thus, the Pt-layer effectively functions as a diffusion barrier. The magnetic structure of the system was unaffected by the substrate’s step structure. Furthermore, numerous vortices and anti-vortices were found in all samples, distributed all over the surfaces, indicating Dzyaloshinskii–Moriya interaction. Only regions with a locally increased Co-layer thickness showed no vortices. Moreover, unlike in similar systems, the magnetization was predominantly in-plane, so no perpendicular magnetic anisotropy was found.

Direct Hot-Electron Transfer at the Au Nanoparticle/Monolayer Transition-Metal Dichalcogenide Interface Observed with Ultrahigh Spatiotemporal Resolution.

Plasmon-induced hot-electron transfer at the metallic nanoparticle/semiconductor interface is the basis of plasmon-enhanced photocatalysis and energy harvesting. However, limited by the nanoscale size of hot spots and femtosecond time scale of hot-electron transfer, direct observation is still challenging. Herein, by using spatiotemporal-resolved photoemission electron microscopy with a two-color pump-probe beamline, we directly observed such a process with a concise system, the Au nanoparticle/monolayer transition-metal dichalcogenide (TMD) interface. The ultrafast hot-electron transfer from Au nanoparticles to monolayer TMDs and the plasmon-enhanced transfer process were directly measured and verified through an in situ comparison with the Au film/TMD interface and free TMDs. The lifetime at the Au nanoparticle/MoSe2 interface decreased from 410 to 42 fs, while the photoemission intensities exhibited a 27-fold increase compared to free MoSe2. We also measured the evolution of hot electrons in the energy distributions, indicating the hot-electron injection and decay happened in an ultrafast time scale of ∼50 fs without observable electron cooling.

Determination of optimal experimental conditions for accurate 3D reconstruction of the magnetization vector via XMCD-PEEM.

This work presents a detailed analysis of the performance of X-ray magnetic circular dichroism photoemission electron microscopy (XMCD-PEEM) as a tool for vector reconstruction of magnetization. For this, 360° domain wall ring structures which form in a synthetic antiferromagnet are chosen as the model to conduct the quantitative analysis. An assessment is made of how the quality of the results is affected depending on the number of projections that are involved in the reconstruction process, as well as their angular distribution. For this a self-consistent error metric is developed which allows an estimation of the optimum azimuthal rotation angular range and number of projections. This work thus proposes XMCD-PEEM as a powerful tool for vector imaging of complex 3D magnetic structures.

Direct imaging of the magnetoelectric coupling in multiferroic BaTiO3/La0.9Ba0.1MnO3

We report the direct imaging of the magnetic response of a 4.8 nm La0.9Ba0.1MnO3 film to the voltage applied across a 5 nm BaTiO3 film in a BaTiO3/La0.9Ba0.1MnO3 multiferroic heterostructure using x-ray photoemission electron microscopy (XPEEM). Specifically, we have written square ferroelectric domains on the BaTiO3 layer with an atomic force microscope in contact mode and imaged the corresponding magnetic contrast through the x-ray circular dichroic effect at the Mn L-edge with high spatial lateral resolution using XPEEM. We find a sudden decrease in the magnetic contrast for positive writing voltages above +6 V associated with the switching of the ferroelectric polarization of the BaTiO3, consistent with the presence of a magnetoelectric effect through changes in the hole carrier density at the BaTiO3/La0.9Ba0.1MnO3 interface. Temperature-dependent measurements show a decrease in the Curie temperature and magnetic moment in the areas where a positive voltage above +6 V was applied, corresponding to the hole depletion state and suggesting the onset of a spin-canted state of bulk La0.9Ba0.1MnO3. Our results are the first direct imaging of magnetoelectric coupling in such multiferroic heterostructure.

Dielectric breakdown behavior of ferroelectric HfO2 capacitors by constant voltage stress studied by in situ laser-based photoemission electron microscopy

In situ laser-based photoemission electron microscopy observations with time-dependent dielectric breakdown measurements of TiN/Hf0.5Zr0.5O2(HZO)/TiN ferroelectric capacitors were performed to reveal the dielectric breakdown (DB) mechanism. We succeeded in visualizing the hard DB spots through the top electrode. We found that capacitors with short- and long-lifetime distributions were broken down near and far from the edge of the capacitors, respectively. This indicates that the DB is either topography-dependent or film-quality-dependent. This work demonstrates an effective method of detecting DB in a non-destructive manner to provide an insight for achieving higher endurance HfO2-based ferroelectric capacitors.

Ferroelastic Twin Angles at the Surface of CaTiO_{3} Quantified by Photoemission Electron Microscopy.

We use photoemission electron microscopy to measure the ferroelastic twin wall angles at the surface of CaTiO_{3} (001) and deduce the strain ordering. We analyze the angular dependence of the photoelectron emission from different domain surfaces, each with its own characteristic tilt angle in the factory rooflike topography. By considering the surface topography as a field perturbation, the offset in the photoemission threshold can be directly related to the tilt angles. With knowledge of the symmetry allowed twin walls we quantify the twin angles between 179.1° to 180.8°.

EUV-induced hydrogen desorption as a step towards large-scale silicon quantum device patterning

Atomically precise hydrogen desorption lithography using scanning tunnelling microscopy (STM) has enabled the development of single-atom, quantum-electronic devices on a laboratory scale. Scaling up this technology to mass-produce these devices requires bridging the gap between the precision of STM and the processes used in next-generation semiconductor manufacturing. Here, we demonstrate the ability to remove hydrogen from a monohydride Si(001):H surface using extreme ultraviolet (EUV) light. We quantify the desorption characteristics using various techniques, including STM, X-ray photoelectron spectroscopy (XPS), and photoemission electron microscopy (XPEEM). Our results show that desorption is induced by secondary electrons from valence band excitations, consistent with an exactly solvable non-linear differential equation and compatible with the current 13.5 nm (~92 eV) EUV standard for photolithography; the data imply useful exposure times of order minutes for the 300 W sources characteristic of EUV infrastructure. This is an important step towards the EUV patterning of silicon surfaces without traditional resists, by offering the possibility for parallel processing in the fabrication of classical and quantum devices through deterministic doping.

Spatiotemporal imaging and manipulation of surface plasmons

Abstract Surface plasmon polaritons (SPPs) are travelling surface waves that have shown promise for applications in nanophotonics as they provide a direct route toward photon-mediated electrical signal generation – a central paradigm for speeding up and scaling down photonic elements. SPP waves have also generated fundamental interest due to their high-field strength and sub-wavelength confinement, properties that have enabled the surface-enhanced Raman effect. Over the last decade, photoemission electron microscopy (PEEM) has emerged as a pioneering technique for imaging surface electric fields through ultrashort laser pulse mediated electron emission and has therefore become an indispensable tool for characterizing plasmonic phenomena at interfaces in a variety of materials. PEEM offers nanometer spatial resolution and femtosecond temporal resolution, allowing SPPs to be prepared, monitored, and manipulated on the nanometer-femtosecond scale. Through a brief review of recent reports, we aim to introduce PEEM-based SPP imaging and manipulation modalities and highlight their utility in the context of emerging nanoscale and quantum materials science advancements.

Ultrafast Charge Transfer and Recombination Dynamics in Monolayer-Multilayer WSe2 Junctions Revealed by Time-Resolved Photoemission Electron Microscopy.

The ultrafast carrier dynamics of junctions between two chemically identical, but electronically distinct, transition metal dichalcogenides (TMDs) remains largely unknown. Here, we employ time-resolved photoemission electron microscopy (TR-PEEM) to probe the ultrafast carrier dynamics of a monolayer-to-multilayer (1L-ML) WSe2 junction. The TR-PEEM signals recorded for the individual components of the junction reveal the sub-ps carrier cooling dynamics of 1L- and 7L-WSe2, as well as few-ps exciton-exciton annihilation occurring on 1L-WSe2. We observe ultrafast interfacial hole (h) transfer from 1L- to 7L-WSe2 on an ∼0.2 ps time scale. The resultant excess h density in 7L-WSe2 decays by carrier recombination across the junction interface on an ∼100 ps time scale. Reminiscent of the behavior at a depletion region, the TR-PEEM image reveals the h density accumulation on the 7L-WSe2 interface, with a decay length ∼0.60 ± 0.17 μm. These charge transfer and recombination dynamics are in agreement with ab initio quantum dynamics. The computed orbital densities reveal that charge transfer occurs from the basal plane, which extends over both 1L and ML regions, to the upper plane localized on the ML region. This mode of charge transfer is distinctive to chemically homogeneous junctions of layered materials and constitutes an additional carrier deactivation pathway that should be considered in studies of 1L-TMDs found alongside their ML, a common occurrence in exfoliated samples.

Layer-dependent ultrafast carrier dynamics of PdSe2 investigated by photoemission electron microscopy.

For atomically thin two-dimensional materials, variations in layer thickness can result in significant changes in the electronic energy band structure and physicochemical properties, thereby influencing the carrier dynamics and device performance. In this work, we employ time- and energy-resolved photoemission electron microscopy to reveal the ultrafast carrier dynamics of PdSe2 with different layer thicknesses. We find that for few-layer PdSe2 with a semiconductor phase, an ultrafast hot carrier cooling on a timescale of approximately 0.3 ps and an ultrafast defect trapping on a timescale of approximately 1.3 ps are unveiled, followed by a slower decay of approximately tens of picoseconds. However, for bulk PdSe2 with a semimetal phase, only an ultrafast hot carrier cooling and a slower decay of approximately tens of picoseconds are observed, while the contribution of defect trapping is suppressed with the increase of layer number. Theoretical calculations of the electronic energy band structure further confirm the transition from a semiconductor to a semimetal. Our work demonstrates that TR- and ER-PEEM with ultrahigh spatiotemporal resolution and wide-field imaging capability has great advantages in revealing the intricate details of ultrafast carrier dynamics of nanomaterials.

Surface Degradation of NMC Electrodes Exposed to Air and Impact on Subsequent Cycling

To meet the ambitious international emissions commitments laid out in the Paris climate agreement making the transition of society from being dependent on fossil fuels towards increased use of renewable energy sources possible, lithium-ion batteries (LIBs) are a key enabling technology. Even though LIBs are already extensively used in portable electronics and the rapidly expanding market of hybrid- and full-electric vehicles, more extensive deployment requires longer cycle-lifetimes, enhancements in energy density, and reductions in cost. In electric vehicles one of the most common materials for the positive electrodes is based on the lithium nickel manganese cobalt oxide (LixNi1-y-zMnyCozO2, NMC) compound with different ratios of transition metals. The NMC materials are well known for consisting of reasonably abundant materials, their high energy density and good cyclebility. In order to decrease the price while also further improving the energy density, it has become more popular during the last few years to increase the nickel content, being responsible for the redox process thereby contributing to a larger capacity. By increasing the nickel content, the quantity of cobalt required will decrease further, reducing the price. However it is also well known that in materials where the nickel content is high the surface side reactions will be augmented leading to more degradation and shorter cycle life. A high nickel content will not only affect the electrochemical side reactions during cycling, it has also been found that as NMC materials are exposed to air they will react differently, with more reactions for the nickel rich materials.It has been found that the NMC can react with H2O to form a LiOH layer and that once the layer is thick enough further side reactions would be prevented.1 It was assumed that the passivation was caused by the deintercalation of lithium, where the thin disordered rock salt layer would mitigate the Li+-water reactions through decreasing the amount of lithium deintercalation.1 Furthermore, the surface impurities formed during the air exposure have been observed to directly impact electrochemical performance during the first couple of cycles. Hatsukade et al. used isotopic labelling in order to measure the CO2 formation during the first cycles originating from the oxidative decomposition of these impurities.2 Air exposure has been shown to affect not only the first few cycles but also long term cycling as well.3 The degradation of the NMC has been found to be caused by phase transformation into rock salt and spinel structure, leading to nickel reduction and as a result formation of inter granular cracks, eventually leading to isolation of the active particles and increased charge transfer resistance.4 In this study the surface interactions at NMC electrodes during air exposure will be presented, showing both how the interactions take place as well as how the air exposure will affect the electrode-electrolyte interfaces during cycling. The NMC surface is analysed by x-ray photoelectron spectroscopy (XPS), photoemission electron microscopy (PEEM) and x-ray absorption spectroscopy (XAS). Zou, L. et al. Unlocking the passivation nature of the cathode–air interfacial reactions in lithium ion batteries. Nat. Commun. 11, (2020).Hatsukade, T., Schiele, A., Hartmann, P., Brezesinski, T. & Janek, J. Origin of Carbon Dioxide Evolved during Cycling of Nickel-Rich Layered NCM Cathodes. ACS Appl. Mater. Interfaces 10, 38892–38899 (2018).Meatza, I. De, Landa-medrano, I., Sananes-israel, S. & Eguia-barrio, A. Powder and Electrodes on the Electrochemical Performance in Li-ion Technology. Batteries 8, 1–18 (2022).Busà, C., Belekoukia, M. & Loveridge, M. J. The effects of ambient storage conditions on the structural and electrochemical properties of NMC-811 cathodes for Li-ion batteries. Electrochim. Acta 366, (2021).

Carrier Trapping Deactivation by Halide Alloying in Formamidinium‐Based Lead Iodide Perovskites

AbstractFormamidinium lead iodide (FAPbI3) is the benchmark material for the most efficient near‐infrared perovskite light‐emitting diodes (LEDs) and a promising gain medium for perovskite‐based coherent light sources. Thus, it is crucial to understand and control its defect chemistry to harness the full potential of its exceptional radiative recombination properties. Here, this topic is addressed by tailoring the I− to Br− ratio in the perovskite composition. It is found that introducing small Br− quantities improves the yield of radiative recombination with a beneficial impact on both spontaneous and amplified spontaneous emission (ASE) and improves the semiconductor photostability leading to reduced luminescence efficiency roll‐off and enhanced radiance in LEDs. By employing photoemission electron microscopy (PEEM), this improvement in optoelectronic performance can be directly correlated to a reduced hole‐trapping activity achieved by replacing iodide with bromide, thus, providing a convenient yet powerful synthetic approach to control the defect chemistry of the material and fostering its implementation in advanced photonic platforms.

Time‐Resolved Photoemission Electron Microscopy on a ZnO Surface Using an Extreme Ultraviolet Attosecond Pulse Pair

AbstractElectrons photoemitted by extreme ultraviolet attosecond pulses derive spatially from the first few atomic surface layers and energetically from the valence band and highest atomic orbitals. As a result, it is possible to probe the emission dynamics from a narrow 2D region in the presence of optical fields, as well as obtain elemental specific information. However, combining this with spatially‐resolved imaging is a long‐standing challenge because of the large inherent spectral width of attosecond pulses, as well as the difficulty of making them at high repetition rates. Here, this work demonstrates an attosecond interferometry experiment on a zinc oxide (ZnO) surface using spatially and energetically resolved photoelectrons. Photoemission electron microscopy is combined with near‐infrared pump ‐ extreme ultraviolet probe laser spectroscopy and the instantaneous phase of an infrared field is resolved with high spatial resolution. Results show how the core level states with low binding energy of ZnO are well suited to perform spatially resolved attosecond interferometry experiments. A distinct phase shift of the attosecond beat signal is observed across the laser focus which is attributed to wavefront differences between the pump and the probe fields at the surface. This work demonstrates a clear pathway for attosecond interferometry with high spatial resolution at atomic scale surface regions opening up for a detailed understanding of nanometric light‐matter interaction.

Compositional Evolution of Individual CoNPs on Co/TiO2 during CO and Syngas Treatment Resolved through Soft XAS/X-PEEM.

The nanoparticle (NP) redox state is an important parameter in the performance of cobalt-based Fischer-Tropsch synthesis (FTS) catalysts. Here, the compositional evolution of individual CoNPs (6-24 nm) in terms of the oxide vs metallic state was investigated in situ during CO/syngas treatment using spatially resolved X-ray absorption spectroscopy (XAS)/X-ray photoemission electron microscopy (X-PEEM). It was observed that in the presence of CO, smaller CoNPs (i.e., ≤12 nm in size) remained in the metallic state, whereas NPs ≥ 15 nm became partially oxidized, suggesting that the latter were more readily able to dissociate CO. In contrast, in the presence of syngas, the oxide content of NPs ≥ 15 nm reduced, while it increased in quantity in the smaller NPs; this reoxidation that occurs primarily at the surface proved to be temporary, reforming the reduced state during subsequent UHV annealing. O K-edge measurements revealed that a key parameter mitigating the redox behavior of the CoNPs were proximate oxygen vacancies (Ovac). These results demonstrate the differences in the reducibility and the reactivity of Co NP size on a Co/TiO2 catalyst and the effect Ovac have on these properties, therefore yielding a better understanding of the physicochemical properties of this popular choice of FTS catalysts.