Scanning Photoelectron Microscope Research Articles

Scanning photoelectron spectromicroscopy: From static to operando studies of functional materials

The scanning photoelectron microscope (SPEM), developed more than 30 years ago, has undergone numerous technical developments, providing an incredibly vast kind of feasible sample environments, which span from the traditional high spatial resolution core level based chemical analysis to insitu and operando complex experiments, including also electrochemical setups and operational electronic devices at various temperatures. Another important step ahead is overcoming the so-called pressure gap for operando studies, recently extended to near ambient values by building special environmental cells. Using recent results of conventional and unconventional experiments, obtained with SPEM at the ESCA Microscopy beamline at Elettra Sincrotrone Trieste the present review demonstrates the current potential of this type of photoelectron spectromicroscopy to explore the interfacial properties of functional materials with high spatial resolution.

Near ambient pressure photoelectron spectro-microscopy: from gas–solid interface to operando devices

Near ambient pressure scanning photoelectron microscopy adds to the widely used photoemission spectroscopy and its chemically selective capability two key features: (1) the possibility to chemically analyse samples in a more realistic gas pressure condition and (2) the capability to investigate a system at the relevant spatial scale. To achieve these goals the approach developed at the ESCA Microscopy beamline at the Elettra Synchrotron facility combines the submicron lateral resolution of a Scanning Photoelectron Microscope with a custom designed Near Ambient Pressure Cell where a gas pressure up to 0.1 mbar can be achieved. In this manuscript a review of experiments performed with this unique setup will be presented to illustrate its potentiality in both fundamental and applicative research such as the oxidation reactivity and gas sensitivity of metal oxides and semiconductors. In particular, the capability to perform operando experiments with this setup opens the possibility to study operating devices and to properly address the real nature of the studied systems, because if microscopy and spectroscopy are simultaneously combined in a single technique it can yield to more conclusive results.

Introduction to Scanning photoelectron microscope (SPEM) and Scanning transmission x-ray microscope (STXM) based on soft x-rays at the Pohang Light Source (PLS-II)

Introduction to Scanning photoelectron microscope (SPEM) and Scanning transmission x-ray microscope (STXM) based on soft x-rays at the Pohang Light Source (PLS-II)

Spatially Resolved Photoemission and Electrochemical Characterization of a Single-Chamber Solid Oxide Fuel Cell

The present paper pinpoints the feasibility of in operando near-ambient pressure characterization of an operating single chamber solid oxide fuel cell (SC-SOFC) by means of spatially resolved X-ray photoelectron spectroscopy. The results are based on an innovative and unique setup expanding the capabilities of the scanning photoelectron microscopes. In particular, the impact of getting access to the low mbar range on the very observability of chemical-state changes in an LSM cathode have been highlighted. Ex situ and in situ electrochemical measurements at OCP and close circuit cell conditions complemented the photoemission mapping and spectroscopy. The latter has evidenced the evolution of the chemical state of Sr upon the exposure of the typical SC-SOFC CH4–O2 gas feed.

Scanning Photoelectron Spectro‐Microscopy: A Modern Tool for the Study of Materials at the Nanoscale

The advanced properties of modern materials originate from their nanoscale size and shape and from chemical modifications or doping. Special techniques that can measure the chemical state in the nanoscale are required for exploration and understanding the properties of these materials. While X‐ray photoelectron spectroscopy (XPS) can access the necessary chemical information, conventional setups have no spatial resolution. The scanning photoelectron microscope (SPEM) takes in advent the third generation synchrotron radiation facilities and uses a zone plate (ZP) focusing optics that allows spatially resolved XPS measurements in the submicron scale. Several recent examples of investigations of chemically modified or doped nanomaterials are given. The modification of suspended and supported graphene with nitrogen and fluorine is presented as well as the doping dependent position of the Fermi‐level in single GsAs nanowires and the Mott–Hubbard transition in Cr‐doped vanadium oxide. These examples show several peculiar SPEM abilities like a high surface and chemical sensitivity and a submicron spatial resolution proving the capability and importance of this technique to study materials at the nanoscale.

Photoelectron microscopy at Elettra: Recent advances and perspectives

The complementary capabilities of the Scanning PhotoElectron Microscopes (SPEM) and X-ray PhotoEmission Electron Microscopes (XPEEM), operated at Elettra, in terms of imaging and micro-spectroscopy have opened unique opportunities to explore properties of functional materials as a function of their morphology and dimensions and to follow modifications in their properties during their operation. This paper describes the present performance of SPEMs and XPEEMs at Elettra, illustrated by selected recent studies relevant to graphene science. Ongoing efforts for implementing SPEM set-ups allowing for in-situ investigations under realistic operating conditions and PEEM set-up for spin-filtered momentum microscopy are outlined and discussed as well.

Depth-Profiling Electronic and Structural Properties of Cu(In,Ga)(S,Se)2 Thin-Film Solar Cell.

Utilizing a scanning photoelectron microscope (SPEM) and grazing-incidence X-ray powder diffraction (GIXRD), we studied the electronic band structure and the crystalline properties of the pentanary Cu(In,Ga)(S,Se)2 (CIGSSe) thin-film solar cell as a function of sample depth on measuring the thickness-gradient sample. A novel approach is proposed for studying the depth-dependent information on thin films, which can provide a gradient thickness and a wide cross-section of the sample by polishing process. The results exhibit that the CIGSSe absorber layer possesses four distinct stoichiometries. The growth mechanism of this distinctive compositional distribution formed by a two-stage process is described according to the thermodynamic reaction and the manufacturing process. On the basis of the depth-profiling results, the gradient profiles of the conduction and valence bands were constructed to elucidate the performance of the electrical properties (in this case, Voc = 620 mV, Jsc = 34.6 mA/cm(2), and η = 14.04%); the valence-band maxima (VBM) measured with a SPEM in the spectroscopic mode coincide with this band-structure model, except for a lowering of the VBM observed in the surface region of the absorber layer due to the ordered defect compound (ODC). In addition, the depth-dependent texturing X-ray diffraction pattern presents the crystalline quality and the residual stress for each depth of a thin-film device. We find that the randomly oriented grains in the bottom region of the absorber layer and the different residual stress between the underlying Mo and the absorber interface, which can deteriorate the electrical performance due to peeling-off effect. An anion interstitial defect can be observed on comparing the anion concentration of the elemental distribution with crystalline composition; a few excess sulfur atoms insert in interstitial sites at the front side of the absorber layer, whereas the interstitial selenium atoms insert at the back side.

Plasma afterglow-assisted oxidation of iron–copper bilayers

Iron layers with variable thicknesses, deposited onto copper thin films, are oxidized by a plasma afterglow at atmospheric pressure. Such a bilayer arrangement enables the growth of caterpillar-like patterns covered by CuO and Fe2O3 nanostructures. Two main mechanisms are at stake: either copper comes up to the surface through cracks or boundaries between the columns of the coating, or it diffuses through parts of the Fe2O3 layer made permeable by tensile stress. Structures grown by the former mechanisms are characterized by a central channel, whereas those grown by the latter exhibit a plane interface above which stands an equiaxed grain heap. This result was used to localize the growth of nanowires in cracks formed priory to the afterglow-assisted treatment. By resorting to XPS microscopy experiments carried out with the scanning photoelectron microscope at the ESCAMicroscopy beamline of the Elettra synchrotron facility in Trieste, we could gain access to the surface composition of a single isolated pattern.

ChemInform Abstract: Recent Approaches for Bridging the Pressure Gap in Photoelectron Microspectroscopy

AbstractReview: 103 refs.

Recent approaches for bridging the pressure gap in photoelectron microspectroscopy.

Ambient-pressure photoelectron spectroscopy (APPES) and microscopy are at the frontier of modern chemical analysis at liquid-gas, solid-liquid and solid-gas interfaces, bridging science and engineering of functional materials. Complementing the current state-of-the art of the instruments, we survey in this short review several alternative APPES approaches, developed recently in the scanning photoelectron microscope (SPEM) at the Elettra laboratory. In particular, we report on experimental setups for dynamic near-ambient pressure environment, using pulsed-gas injection in the vicinity of samples or reaction cells with very small apertures, allowing for experiments without introducing additional differential pumping stages. The major part of the review is dedicated to the construction and performance of novel environmental cells using ultrathin electron-transparent but molecularly impermeable membranes to isolate the gas or liquid ambient from the electron detector operating in ultra-high vacuum (UHV). We demonstrate that two dimensional materials, such as graphene and derivatives, are mechanically robust to withstand atmospheric - UHV pressure differences and are sufficiently transparent for the photoelectrons emitted from samples immersed in the liquid or gaseous media. There are many unique opportunities for APPES using X-rays over a wide energy range. We show representative results that illustrate the potential of these 'ambient-pressure' approaches. Combined with the ca 100 nm lateral resolution of SPEM, they can overcome the pressure gap challenges and address the evolution of chemical composition and electronic structure at surface and interfaces under realistic operation conditions with unprecedented lateral and spectral resolution.

Electrical control of nanoscale functionalization in graphene by the scanning probe technique

Functionalized graphene is a versatile material that has well-known physical and chemical properties depending on functional groups and their coverage. However, selective control of functional groups on the nanoscale is hardly achievable by conventional methods utilizing chemical modifications. We demonstrate electrical control of nanoscale functionalization of graphene with the desired chemical coverage of a selective functional group by atomic force microscopy (AFM) lithography and their full recovery through moderate thermal treatments. Surprisingly, our controlled coverage of functional groups can reach 94.9% for oxygen and 49.0% for hydrogen, respectively, well beyond those achieved by conventional methods. This coverage is almost at the theoretical maximum, which is verified through scanning photoelectron microscope measurements as well as first-principles calculations. We believe that the present method is now ready to realize ‘chemical pencil drawing’ of atomically defined circuit devices on top of a monolayer of graphene.

Graphene as tunable transparent electrode material on GaN: Layer-number-dependent optical and electrical properties

Graphene has been regarded as a prospective transparent electrode for a GaN-based light-emitting diode (LED), but fundamental knowledge about the intrinsic properties of the graphene/GaN contact is lacking. We have studied the optical and electronic properties of graphene exfoliated on an n-type GaN surface. The graphene visibility was simulated based on Fresnel's law and confirmed with an optical microscope and micro-Raman spectra. The interfacial electronic property was studied with a scanning photoelectron microscope. We found that the Schottky barrier height of the graphene/n-GaN is decreased with decreasing graphene number of layers, yielding an improved GaN-based LED performance.

Dynamic High Pressure: a novel approach toward near ambient pressure photoemission spectroscopy and spectromicroscopy

A Dynamic High Pressure (DHP) system has been developed, tested and implemented in the scanning photoelectron microscope (SPEM) operated at ESCAmicroscopy beamline at Elettra synchrotron. The system consists of a compact gas injection set up that allows experiments with local pressure near the sample several orders of magnitude higher that the allowable pressure for X-ray photoelectron spectroscopy setups. The DHP setup controls the amount of gas injected toward the sample by fine tuning the time and spatial profiles using a pulsed valve and a nozzle, respectively. The DHP functionality and effectiveness has been demonstrated by in operando oxidation experiments of Ru and Si. The obtained results confirmed that using the DHP the gas exposure onto the sample is equivalent to a static pressure between 10−3 and 10−2 mbar, about 3 orders of magnitude higher than the maximum gas pressure for the XPS machines under operation.

三次元走査型光電子顕微鏡 （3D nano-ESCA）

We have developed a scanning photoelectron microscope system with the capability of depth profiling in electron spectroscopy for chemical analysis (ESCA). We call this system “3D nano-ESCA.” The system has been installed at the University-of-Tokyo Materials Science Outstation beamline, BL07LSU, at SPring-8. A total spatial resolution is achieved to be better than 70 nm. A photoelectron analyzer with an acceptance angle of 60 degrees enables us to obtain the angular dependence of the photoelectron spectra for the depth-profile analysis without rotating the sample. In this article, we introduce the capability of the 3D nano-ESCA system and recent research activities on high-k gate insulator, graphene, and metal-nanowire devices using the 3D nano-ESCA system.

Scanning photoelectron microscope for nanoscale three-dimensional spatial-resolved electron spectroscopy for chemical analysis

In order to achieve nondestructive observation of the three-dimensional spatially resolved electronic structure of solids, we have developed a scanning photoelectron microscope system with the capability of depth profiling in electron spectroscopy for chemical analysis (ESCA). We call this system 3D nano-ESCA. For focusing the x-ray, a Fresnel zone plate with a diameter of 200 μm and an outermost zone width of 35 nm is used. In order to obtain the angular dependence of the photoelectron spectra for the depth-profile analysis without rotating the sample, we adopted a modified VG Scienta R3000 analyzer with an acceptance angle of 60° as a high-resolution angle-resolved electron spectrometer. The system has been installed at the University-of-Tokyo Materials Science Outstation beamline, BL07LSU, at SPring-8. From the results of the line-scan profiles of the poly-Si/high-k gate patterns, we achieved a total spatial resolution better than 70 nm. The capability of our system for pinpoint depth-profile analysis and high-resolution chemical state analysis is demonstrated.

(Invited) Synchrotron Radiation Nano-Spectroscopy of Dielectrics for LSI and ReRAM

Metal/high-k gate dielectrics stack structures for LSIs and metal/transition-metal-oxides(TMO)/metal structures for resistance random access memory (ReRAM) have been analyzed using synchrotron radiation nano-spectroscopy from the viewpoint of interfacial chemical and electronic states. We have developed a scanning photoelectron microscope(SPEM) with an angle-resolved electron analyzer and succeeded in obtaining chemicalstate-resolved images and pin-point in-depth profiles of LSI gate patterns with 70 nm lateral resolution. For ReRAM, chemical-state-resolved images of Cu for a planar-type Pt/CuO/Pt resistance switching (RS) device revealed conductive filaments in TMO using photoelectron emission microscope (PEEM). Furthermore, in and out diffusion phenomena of oxygen corresponding to bias polarity for RS were observed for Pt/TaOx/Pt switching devices. Interfacial redox reactions which are common to all ReRAM devices are also observed for Al/TMO interfaces.

Scanning photoelectron microscopy investigation of the initial stages of the electrochemical reduction of Cr(VI) at Pt(1 1 1) electrode

This paper reports on the electrochemical reduction of bichromate from an aqueous solution at a Pt(1 1 1) electrode studied by voltammetry and synchrotron-based photoelectron spectromicroscopy Cathodic reduction is carried out at potentials −1.5 and −2.0 eV in an electrochemical cell attached to the UHV chamber hosting the scanning photoelectron microscope (SPEM), which allowed sample transfer for SPEM analysis without exposure to the air. The Cr 2p and Pt 4f core level spectra are used as fingerprints of the Cr lateral distribution and chemical state after reduction. The Pt 4f and Cr 2p maps show inhomogeneous Cr distribution in microscopic Cr-rich and Cr-poor islands. Analysis of the Pt 4f, Cr 2p photoemission peaks recorded in these islands has disclosed that – under both reduction conditions – Cr(VI) is reduced principally to Cr(III), with ca. 10% of Cr(0) localised in the Cr-rich islands. The presence of an intermediate oxidation state has also been detected, that can be assigned to a transition state from Cr(VI) to Cr(III).

Synchrotron-based photoelectron microscopy

The paper is a brief overview of the operation principles and the potentials of the scanning photoelectron microscopes (SPEM) and X-ray photoemission electron microscopes (XPEEM) operating at synchrotron facilities. Selected results will illustrate the impact of high spatial resolution for micro-characterization of the surface composition and electronic structure, a key issue for analysis of technologically relevant materials and for fundamental understanding of many unexplored surface phenomena.

Scanning photoelectron microscopic study of top-emission organic light-emitting device degradation under high-bias voltage

The degradation process of a top-emission organic light-emitting device (TOLED) under high-bias voltage was investigated using a scanning photoelectron microscope (SPEM). The TOLED was in situ biased to reveal the degraded area inside the SPEM chamber. The SPEM data showed a volcano-type structure inside the degraded area. The overall results of the spectroscopic analysis suggest that strong degradation was accompanied by an eruption underneath the cathode layer. It is posited that the hot gases from the erupted area separated the cathode layer from the organic layer, forming a large bubble, and that, as the bubble exploded, the pressure of the gas blew away the cathode layer.

Degradation mechanism of organic light-emitting device investigated by scanning photoelectron microscopy coupled with peel-off technique

The authors present space-resolved spectroscopic data on organic layers of a degraded organic light-emitting device. The data were obtained using a scanning photoelectron microscope (SPEM) coupled with peel-off technique to directly probe the uncontaminated organic layers, which were covered with cathode layer. The SPEM images of the degraded device show different and small size distributions of tris-8-hydroxy quinoline aluminum (Alq3) and hole-transport layers compared to that of as-prepared device. The analysis indicates that bonding strength between Alq3 and cathode layers and between the Alq3 and hole transport layers becomes weak as the device degrades, presumably due to structural deformation of the organic layers.