Scanning Photoemission Research Articles

Designing advanced high-Cr ferrous alloys for next-generation energy applications through cryogenic processing

Excellent properties (durability, wear and corrosion resistance) and long service life under extreme conditions are essential for the successful application of metallic materials in the energy sector. In particular, for future fusion applications, high Cr ferrous alloys (in our case Eurofer) are of great interest. Importantly, modified microstructure with higher dimensional stability improves corrosion and wear resistance properties. In this study, we successfully manipulate the desired type of microstructure, which could provide a solution to current challenges in such a high temperature, highly corrosive and highly irradiated environment, using a novel technique of cryogenic processing (CP). The research identifies the CP-driven changes not only to the microstructure, but also to the local chemistry and bonding state of the key alloying elements. The correlations and individual phenomena associated with CP have been evaluated using state-of-the-art techniques such as atom probe tomography and synchrotron-based in-situ scanning photoemission spectroscopy. This novel process and its novel microstructural manipulation opens up new possibilities for materials processing for future energy applications.

Crater-free monolayer graphene above the 2D Si film on SiC(0001) formed via SiSn cointercalation and Sn deintercalation

When Si atoms are intercalated under the graphene-like zero layer (ZL) generated on the SiC(0001) substrate, the resulting quasi-free-standing monolayer graphene (QFMLG) has lots of crater-like defects due to a strong Si-C reaction. Here, a method for creating crater-free QFMLG above a two-dimensional Si film is investigated using scanning tunneling microscopy and photoemission spectroscopy. The method involves forming a SiSn interfacial film as a precursor via cointercalation performed by sequential Sn and Si deposition on the ZL at room temperature and annealing at 650–700 °C. The Sn atoms prevent reactive Si atoms from directly contacting the ZL, which would otherwise cause SiC defects. The sample is then annealed at 750 °C to selectively remove the Sn atoms from the SiSn interfacial film, leaving a well-ordered Si film. The SiSn film composed of a bottom Si layer and top Sn atoms has a short-range-ordered “2 × 2” or a long-range-ordered 2×7 superstructure depending on the annealing temperature and the Sn coverage. Both the superstructures are semiconducting and induce less n-doped QFMLG than the pure Si film.

Stripe-Like hBN Monolayer Template for Self-Assembly and Alignment of Pentacene Molecules.

Metallic surfaces with unidirectional anisotropy are often used to guide the self-assembly of organic molecules along a particular direction. Such supports thus offer an avenue for the fabrication of hybrid organic-metal interfaces with tailored morphology and precise elemental composition. Nonetheless, such control often comes at the expense of detrimental interfacial interactions that might quench the pristine properties of molecules. Here, hexagonal boron nitride grown on Ir(100) is introduced as a robust platform with several coexisting 1D stripe-like moiré superstructures that effectively guide unidirectional self-assemblies of pentacene molecules, concomitantly preserving their pristine electronic properties. In particular, highly-aligned longitudinal arrays of equally-oriented molecules are formed along two perpendicular directions, as demonstrated by comprehensive scanning tunneling microscopy and photoemission characterization performed at the local and non-local scale, respectively. The functionality of the template is demonstrated by photoemission tomography, a surface-averaging technique requiring a high degree of orientational order of the probed molecules. The successful identification of pentacene's pristine frontier orbitals underlines that the template induces excellent long-range molecular ordering via weak interactions, preventing charge transfer.

Imaging Interface and Particle Size Effects by In Situ Correlative Microscopy of a Catalytic Reaction.

The catalytic behavior of Rh particles supported by three different materials (Rh, Au, and ZrO2) in H2 oxidation has been studied in situ by correlative photoemission electron microscopy (PEEM) and scanning photoemission electron microscopy (SPEM). Kinetic transitions between the inactive and active steady states were monitored, and self-sustaining oscillations on supported Rh particles were observed. Catalytic performance differed depending on the support and Rh particle size. Oscillations varied from particle size-independent (Rh/Rh) via size-dependent (Rh/ZrO2) to fully inhibited (Rh/Au). For Rh/Au, the formation of a surface alloy induced such effects, whereas for Rh/ZrO2, the formation of substoichiometric Zr oxides on the Rh surface, enhanced oxygen bonding, Rh-oxidation, and hydrogen spillover onto the ZrO2 support were held responsible. The experimental observations were complemented by micro-kinetic simulations, based on variations of hydrogen adsorption and oxygen binding. The results demonstrate how correlative in situ surface microscopy enables linking of the local structure, composition, and catalytic performance.

Study of Phase Composition in TiFe + 4 wt.% Zr Alloys by Scanning Photoemission Microscopy

The alloy TiFe is widely used as hydrogen storage material. However, the first hydrogenation is difficult. It was found that the addition of zirconium greatly improves the kinetic of first hydrogenation, but the mechanism is not well understood. In this paper, we report the use of scanning photoemission microscopy to investigate the composition and chemical state of the various phases present in this alloy and how they change upon hydrogenation/dehydrogenation. We found the presence of different oxide phases that were not seen by conventional SEM investigation. The nature of these oxides phases seems to change upon hydrogenation/dehydrogenation cycle. This indicates that oxide phases may play a more significant role in the hydrogen absorption as what was previously believed.

Defect pairing in Fe-doped SnS van der Waals crystals: a photoemission and scanning tunneling microscopy study.

We investigate the effect of low concentrations of iron on the physical properties of SnS van der Waals crystals grown from the melt. By means of scanning tunneling microscopy (STM) and photoemission spectroscopy we study Fe-induced defects and observe an electron doping effect in the band structure of the native p-type SnS semiconductor. Atomically resolved and bias dependent STM data of characteristic defects are compared to ab initio density functional theory simulations of vacancy (VS and VSn), Fe substitutional (FeSn), and Fe interstitial (Feint) defects. While native SnS is dominated by acceptor-like VSn vacancies, our results show that Fe preferentially occupies donor-like interstitial Feint sites in close proximity to VSn defects along the high-symmetry c-axis of SnS. The formation of such well-defined coupled (VSn, Feint) defect pairs leads to local compensation of the acceptor-like character of VSn, which is in line with a reduction of p-type carrier concentrations observed in our Hall transport measurements.

Electronically Tunable Transparent Conductive Thin Films for Scalable Integration of 2D Materials with Passive 2D–3D Interfaces

AbstractA novel transparent conductive support structure for scalable integration of 2D materials is demonstrated, providing an electronically passive 2D–3D interface while also enabling facile interfacial charge transport. This structure, which comprises an evaporated nanocrystalline carbon (nc‐C) film beneath nanometer‐thin atomic layer deposited AlOx, is thermally stable and allows direct chemical vapor deposition of 2D materials onto the surface. The combination of spatial uniformity, enhanced charge screening, and low interface defect concentrations yields a tenfold enhancement of MoS2 photoluminescence intensity compared to flakes on conventional Si/SiO2, while also retaining the strong optical contrast for monolayer flakes. Tunneling across the ultrathin AlOx enables facile interfacial charge injection, which is utilized for high‐resolution scanning electron microscopy and photoemission electron microscopy with no detectable charging. Thus, this combination of scalable fabrication and electronic conductivity across a weakly interacting 2D–3D interface opens up new opportunities for device integration and characterization of 2D materials.

Atomic-scale growth, imaging, spectroscopy, and electronic transport properties of metal-oxide films and interfaces

Metal-oxide thin films and interfaces exhibit numerous fascinating electronic transport properties that are not found in conventional semiconductor materials. There has been much interest in engineering them to improve their functionalities, and an improved fundamental understanding of the phenomena that occur in oxide films and heterostructures is critical. In this review, an innovative approach to strontium titanate and zinc oxide-based heterostructures using state-of-the-art scanning tunneling microscopy and photoemission spectroscopy systems, as well as electrical measurements are presented. The results show that atomic-scale bottom-up processes with greater care provide excellent opportunities for improving material properties and classifying complicated conductivity.

Zooming in on heavy fermions in Kondo lattice models

Resolving the heavy fermion band in the conduction electron momentum resolved spectral function of the Kondo lattice model is challenging since, in the weak coupling limit, its spectral weight is exponentially small. In this article we consider a composite fermion operator, consisting of a conduction electron dressed by spin fluctuations that shares the same quantum numbers as the electron operator. Using approximation free auxiliary field quantum Monte Carlo simulations we show that for the SU(2) spin-symmetric model on the square lattice at half filling, the composite fermion acts as a magnifying glass for the heavy fermion band. In comparison to the conduction electron residue that scales as $e^{-W/J_k}$ with $W$ the bandwidth and $J_k$ the Kondo coupling, the residue of the composite fermion tracks $J_k$. This result holds down to $J_k/W = 0.05$, and confirms the point of view that magnetic ordering, present below $J_k/W = 0.18$, does not destroy the heavy quasiparticle. We furthermore investigate the spectral function of the composite fermion in the ground state and at finite temperatures, for SU($N$) generalizations of the Kondo lattice model, as well as for ferromagnetic Kondo couplings, and compare our results to analytical calculations in the limit of high temperatures, large-$N$, large-$S$, and large $J_k$. Based on these calculations, we conjecture that the composite fermion operator provides a unique tool to study the destruction of the heavy fermion quasiparticle in Kondo breakdown transitions. The relation of our results to scanning tunneling spectroscopy and photoemission experiments is discussed.

Thermal Phase Control of Two-Dimensional Pt-Chalcogenide (Se and Te) Ultrathin Epitaxial Films and Nanocrystals

The controlled synthesis and modification of the composition of layered compounds are essential prerequisites for their deployment in electronic or chemical applications. Pt-chalcogenides exhibit various compositional phases. Here, we investigate how Pt-selenide and Pt-telluride phases can be obtained as ultrathin films or as supported nanocrystals by physical vapor deposition and thermal treatment. The films are characterized by scanning tunneling microscopy and spectroscopy, scanning transmission electron microscopy, and photoemission and Raman spectroscopy. In all cases, Pt-dichalcogenides are obtained by Pt and chalcogen codeposition at growth temperatures below 300 °C. These films can be grown by van der Waals epitaxy in a layer-by-layer fashion, enabling the characterization of the pronounced layer-dependent electronic properties of these compounds. Pt-telluride growth at elevated temperatures (above 400 °C) results in the formation of Pt-monotelluride. Interestingly, the thin film Pt-dichalcogenides can also be transformed into different phases with lower chalcogen concentration by post-growth vacuum annealing. Annealing-induced loss of chalcogen results in new composites. With this thermal process, an intermittent layered compound of Pt3Te4 is synthesized, which consists of alternating PtTe2 and PtTe van der Waals layers. By thermal treatment of PtSe2, we obtain a non-layered Pt-monoselenide in nanocrystalline form. PtSe is not reported in the bulk Pt-Se phase diagram, but its structure is analogue to the known Pt-monosulfide with a tetragonal unit cell. This PtSe phase is semiconducting with a band gap of ∼0.9 eV. The nanocrystalline PtSe phase is, however, unstable and easily loses more Se and eventually converts into Pt. Thus, it is demonstrated that post-growth thermally induced transformation of Pt-dichalcogenides films enables the synthesis of new Pt-chalcogenide phases as ultrathin films or nanocrystals.

Indium-contacted van der Waals gap tunneling spectroscopy for van der Waals layered materials

The electrical phase transition in van der Waals (vdW) layered materials such as transition-metal dichalcogenides and Bi2Sr2CaCu2O8+x (Bi-2212) high-temperature superconductor has been explored using various techniques, including scanning tunneling and photoemission spectroscopies, and measurements of electrical resistance as a function of temperature. In this study, we develop one useful method to elucidate the electrical phases in vdW layered materials: indium (In)-contacted vdW tunneling spectroscopy for 1T-TaS2, Bi-2212 and 2H-MoS2. We utilized the vdW gap formed at an In/vdW material interface as a tunnel barrier for tunneling spectroscopy. For strongly correlated electron systems such as 1T-TaS2 and Bi-2212, pronounced gap features corresponding to the Mott and superconducting gaps were respectively observed at T = 4 K. We observed a gate dependence of the amplitude of the superconducting gap, which has potential applications in a gate-tunable superconducting device with a SiO2/Si substrate. For In/10 nm-thick 2H-MoS2 devices, differential conductance shoulders at bias voltages of approximately ± 0.45 V were observed, which were attributed to the semiconducting gap. These results show that In-contacted vdW gap tunneling spectroscopy in a fashion of field-effect transistor provides feasible and reliable ways to investigate electronic structures of vdW materials.

Surface Electronic States and Inclining Surfaces in MoTe2 Probed by Photoemission Spectromicroscopy

The electronic structure of MoTe2 undergoing a monoclinic–orthorhombic transition around 250 K has been investigated by means of scanning photoemission spectromicroscopy (SPEM), angle-resolved phot...

Studying the heterogeneity of the CrxTi1-xCh2 (Ch = S, Se) single crystals using X-ray scanning photoemission microscopy

The morphology of the heterogeneous CrxTi1-xSe2 and CrxTi1-xS2 single crystals has been studied using X-ray scanning photoemission microscopy (SPEM) and angular resolved photoemission spectroscopy (ARPES). A direct method of SPEM provided us the insight into the origin of the blurred ARPES images for Cr0.78Ti0.36Se2 single crystal. Using SPEM, we confirmed the formation of the CrSe2-based structural fragments inside the CrxTi1-xSe2 single crystals with x ≥ 0.75. The chemical composition of the forming structural fragments depends on the chalcogen (S, Se) forming the crystal lattice.

Visualization of graphene grain boundaries through oxygen intercalation

Efficient control over the grain boundaries (GBs) is a vital aspect in optimizing the graphene growth conditions. A number of methods for visualization of GBs were developed for graphene grown on weakly interacting surfaces. Here, we utilize oxygen intercalation to reveal GBs and study their morphology for graphene strongly bound to the cobalt surface. We demonstrate that upon the intercalation of oxygen, GBs in polycrystalline graphene become easily detectable due to graphene cracking and selective oxidation of the substrate, thus giving a direct insight into the graphene micro- and nanostructure by means of different electron microscopy methods, including scanning electron microscopy, photoemission microscopy and low-energy electron microscopy.

Charge-Promoted Self-Metalation of Porphyrins on an Oxide Surface.

Metalation and self‐metalation reactions of porphyrins on oxide surfaces have recently gained interest. The mechanism of porphyrin self‐metalation on oxides is, however, far from being understood. Herein, we show by a combination of results obtained with scanning tunneling microscopy, photoemission spectroscopy, and DFT computations, that the self‐metalation of 2H‐tetraphenylporphyrin on the surface of ultrathin MgO(001) films is promoted by charge transfer. By tuning the work function of the MgO(001)/Ag(001) substrate, we are able to control the charge and the metalation state of the porphyrin molecules on the surface.

How the anisotropy of surface oxide formation influences the transient activity of a surface reaction

Scanning photoelectron microscopy (SPEM) and photoemission electron microscopy (PEEM) allow local surface analysis and visualising ongoing reactions on a µm-scale. These two spatio-temporal imaging methods are applied to polycrystalline Rh, representing a library of well-defined high-Miller-index surface structures. The combination of these techniques enables revealing the anisotropy of surface oxidation, as well as its effect on catalytic hydrogen oxidation. In the present work we observe, using locally-resolved SPEM, structure-sensitive surface oxide formation, which is summarised in an oxidation map and quantitatively explained by the novel step density (SDP) and step edge (SEP) parameters. In situ PEEM imaging of ongoing H2 oxidation allows a direct comparison of the local reactivity of metallic and oxidised Rh surfaces for the very same different stepped surface structures, demonstrating the effect of Rh surface oxides. Employing the velocity of propagating reaction fronts as indicator of surface reactivity, we observe a high transient activity of Rh surface oxide in H2 oxidation. The corresponding velocity map reveals the structure-dependence of such activity, representing a direct imaging of a structure-activity relation for plenty of well-defined surface structures within one sample.

In situ observation of oscillatory redox dynamics of copper

How a catalyst behaves microscopically under reaction conditions, and what kinds of active sites transiently exist on its surface, is still very much a mystery to the scientific community. Here we present an in situ study on the red-ox behaviour of copper in the model reaction of hydrogen oxidation. Direct imaging combined with on-line mass spectroscopy shows that activity emerges near a phase boundary, where complex spatio-temporal dynamics are induced by the competing action of simultaneously present oxidizing and reducing agents. Using a combination of in situ imaging with in situ X-ray absorption spectroscopy and scanning photoemission microscopy, we reveal the relation between chemical and morphological dynamics and demonstrate that a static picture of active sites is insufficient to describe catalytic function of redox-active metal catalysts. The observed oscillatory redox dynamics provide a unique insight on phase-cooperation and a convenient and general mechanism for constant re-generation of transient active sites.

Compositional Phase Change of Early Transition Metal Diselenide (VSe2 and TiSe2) Ultrathin Films by Postgrowth Annealing

AbstractThe transition metal selenides M1+ySe2 (M = V, Ti) have intriguing quantum properties, which make them target materials for controlling properties by thinning them to the ultrathin limit. An appropriate approach for the synthesis of such ultrathin films is by molecular beam epitaxy. Here, it is shown that such synthesized V‐ and Ti‐Se2 films can undergo a compositional change by vacuum annealing. Combined scanning tunneling and photoemission spectroscopy is used to determine compositional and structural changes of ultrathin films as a function of annealing temperature. Loss of selenium from the film is accompanied by a morphology change of monolayer height islands to predominantly bilayer height. In addition, crystal periodicity and atomic structure changes are observed. These changes are consistent with a transition from a layered transition metal dichalcogenide (TMDC) to ordered intercalation compounds with V or Ti intercalated in between two layers of their respective TMDCs. These observations may clear up misconception of the nature of previously reported high‐temperature grown transition metal selenides. More significantly, the demonstrated control of the formation of intercalation compounds is a key step toward modifying properties in van der Waals systems and toward expanding material systems for van der Waals heterostructures.

New Frontiers in Electrocatalyst Characterization – Three Dimensional Atomic-Scale Insights By Atom Probe Tomography

Developing electrocatalysts with enhanced properties requires a fundamental understanding of the processes that occur during operation as well as side reactions during the synthesis. Many of those processes, e.g. solute segregation to defects [1], the hydroxylation of near-surface regions [2], or the preferential oxidation/reduction of certain regions, are often governed by the local microstructure. Such phenomena commonly result in significant chemical heterogeneities within the material at the nanoscale, affecting the potential distribution across the surface during operation. This way, localized heterogeneities can control the local binding energetics for reactants, intermediates and products, and determine the overall reactivity and stability of the material.Atom probe tomography (APT) offers the opportunity to measure the composition of localized chemical fluctuations at the near-atomic scale and in three dimensions. Targeted APT specimen preparation of regions-of-interest, e.g. at specific grains or grain boundaries, enables the correlation of local structure and local composition. Recent method developments have enabled the measurement of free surfaces with APT [2,3], offering a new perspective into the first few atomic layers of electrocatalytic materials. APT thereby provides the chance to elucidate chemical processes within the near-surface region which underpin the electrochemical performance of the material.In this contribution, we showcase how APT can be instrumental to the precise characterization of various electrocatalytic materials. In a first example, we demonstrate how APT revealed the structural features in hydrous Ir oxides that are responsible for an accelerated degradation of the catalyst during the oxygen evolution reaction, due to release of molecular oxygen from the lattice [4]. Secondly, we present how APT can be combined with scanning photoemission electron microscopy to obtain spatially correlated chemical state information of the surface investigated with APT [1,3]. And finally, we show how APT enables the investigation of trace-element distribution in nanostructured materials, such as nanoparticles [5] or nanorods [6]. For example, APT can shed light on the incorporation of B, Na and N during the hydrothermal synthesis and partial reduction of hollow TiO2 nanorods, that are commonly used as a photocatalyst or catalyst support. Trace amounts of such light elements often remain undetected with other methods but may have a dramatic effect on the functionality of the material.

AP-XPS beamline, a platform for operando science at Pohang Accelerator Laboratory.

Beamline 8A (BL 8A) is an undulator-based soft X-ray beamline at Pohang Accelerator Laboratory. This beamline is aimed at high-resolution ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), soft X-ray absorption spectroscopy (soft-XAS) and scanning photoemission microscopy (SPEM) experiments. BL 8A has two branches, 8A1 SPEM and 8A2 AP-XPS, that share a plane undulator, the first mirror (M1) and the monochromator. The photon beam is switched between the two branches by changing the refocusing mirrors after the monochromator. The acceptance angle of M1 is kept glancing at 1.2°, and Pt is coated onto the mirrors to achieve high reflectance, which ensures a wide photon energy range (100-2000 eV) with high resolution at a photon flux of ∼1013 photons s-1. In this article, the main properties and performance of the beamline are reported, together with selected experiments performed on the new beamline and experimental system.