Femtosecond spectroscopic imaging by time-of-flight photoemission electron microscopy

Advances in electron optics and fast-pulsed light sources have enabled the imaging of nanoscale structures with simultaneous energy and time resolutions. We present the results obtained from a time-resolved time-of-flight photoemission electron microscopy (TR-TOF-PEEM) system. This system combined the spatial resolution of conventional PEEM with the time resolution of a femtosecond-pulsed laser and the energy resolution of a TOF energy analyzer. The TOF-PEEM system consists of three electrostatic lenses in front, a drift tube for the measurement of TOF, and a delay line detector (DLD) at the end of the optics. The excitation source is femtosecond pulses from a cavity-dumped Ti:sapphire oscillator that is frequency-doubled to 400 nm using a β-barium borate (BBO) crystal. Using a pump-probe two-photon photoemission technique, we demonstrate an example of sub-100 nm space-resolved ultrafast time evolution of the electron energy spectra for the plasmon resonance of an Ag-coated Si nanostructure, which exhibited unexpectedly intense high energy photoemission signals that show different time evolution between bright and dark regions in a PEEM image.     

Electron optics for high throughput low energy electron microscopy

Novel electron-optical components and concepts aiming at improving the throughput and extending the applications of a low energy electron microscope (LEEM) have been developed. An immersion magnetic objective lens can substantially reduce e-e interactions and the associated blur, as electrons do not form a sharp crossover in the back-focal plane. The resulting limited field of view of the immersion objective lens in mirror mode can be eliminated by immersing the cathode of the electron gun in a magnetic field. A dual illumination beam approach is used to mitigate the charging effects when the LEEM is used to image insulating surfaces. The negative charging effect, created by a partially absorbed mirror beam, is compensated by the positive charging effect of the secondary beam with an electron yield exceeding 1. On substrates illuminated with a tilted beam near glancing incidence, large shadows are formed on even the smallest topographic features, easing their detection. On magnetic substrates, the magnetic flux leaking above the surface can be detected with tilted illumination and used to image domain walls with high contrast.     

Low energy electron microscopy and photoemission electron microscopy investigation of graphene

Low energy electron microscopy (LEEM) and photoemission electron microscopy (PEEM) are two powerful techniques for the investigation of surfaces, thin films and surface supported nanostructures. In this review, we examine the contributions of these microscopy techniques to our understanding of graphene in recent years. These contributions have been made in studies of graphene on various metal and SiC surfaces and free-standing graphene. We discuss how the real-time imaging capability of LEEM facilitates a deeper understanding of the mechanisms of dynamic processes, such as growth and intercalation. Numerous examples also demonstrate how imaging and the various available complementary measurement capabilities, such as selected area or micro low energy electron diffraction (μLEED) and micro angle resolved photoelectron spectroscopy (μARPES), allow the investigation of local properties in spatially inhomogeneous graphene samples.     

The EIGER detector for low‐energy electron microscopy and photoemission electron microscopy

EIGER is a single‐photon‐counting hybrid pixel detector developed at the Paul Scherrer Institut, Switzerland. It is designed for applications at synchrotron light sources with photon energies above 5 keV. Features of EIGER include a small pixel size (75 µm × 75 µm), a high frame rate (up to 23 kHz), a small dead‐time between frames (down to 3 µs) and a dynamic range up to 32‐bit. In this article, the use of EIGER as a detector for electrons in low‐energy electron microscopy (LEEM) and photoemission electron microscopy (PEEM) is reported. It is demonstrated that, with only a minimal modification to the sensitive part of the detector, EIGER is able to detect electrons emitted or reflected by the sample and accelerated to 8–20 keV. The imaging capabilities are shown to be superior to the standard microchannel plate detector for these types of applications. This is due to the much higher signal‐to‐noise ratio, better homogeneity and improved dynamic range. In addition, the operation of the EIGER detector is not affected by radiation damage from electrons in the present energy range and guarantees more stable performance over time. To benchmark the detector capabilities, LEEM experiments are performed on selected surfaces and the magnetic and electronic properties of individual iron nanoparticles with sizes ranging from 8 to 22 nm are detected using the PEEM endstation at the Surface/Interface Microscopy (SIM) beamline of the Swiss Light Source.     

A spatially resolved investigation of oxygen adsorption on polycrystalline copper and titanium by means of photoemission electron microscopy

The interaction of oxygen with polycrystalline copper and titanium surfaces was studied by means of photoemission electron microscopy. Variations in the image brightness were used to determine the work function of different Cu crystallites. The change of the work function was monitored during oxygen adsorption on both, Cu and Ti. Those changes are smooth for Cu whereas different Ti crystallites exhibit a rather complicated behavior during oxygen adsorption. The transformation of brightness versus exposure curves into work function versus coverage curves allows to determine the initial dipole moment of the adsorbed oxygen atoms. A value of about 20 mD was found for O on Cu(1 1 0). Variations of the initial sticking probability of oxygen on different copper crystallites were directly mapped.     

扫描多光谱显微成像

文本描述了一种新的显微成像方法,它把光学扫描显微成像技术与成像多光谱技术巧妙地结合在一起,形成扫描多光谱显微成像技术.文中叙述了系统的结构及工作原理,介绍了所采用的图像处理系统,给出了实验结果,并进行了分析讨论.     

Analysis of the injection layer of PTCDA in OLEDs using x-ray photoemission spectroscopy and atomic force microscopy

Through the investigation of the sample surface and interface of 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA)/indium-tin-oxide (ITO) thin films using atomic force microscopy, it has been found that the surface is complanate, the growth is uniform and the defects cover basically the surface of ITO. Furthermore, the number of pinholes is small. The analysis of the sample surface and interface further verifies this result by using x-ray photoemission spectroscopy . At the same time, PTCDA is found to have the ability of restraining the diffusion of chemical constituents from ITO to the hole transport layer, which is beneficial to the improvement of the performance and the useful lifetime of the organic light emitting diodes (OLEDs).     

The use of electron microscopy for the study of phase transitions

Two examples of the study of phase transitions by means of electron diffraction and electron microscopy are discussed.     

Characterization of the photo-irradiation effects on polystyrene ultrathin films with ultraviolet photoemission spectroscopy

The synchrotron-radiation-induced structural degradation in polystyrene thin films was analyzed by comparing measured ultraviolet photoemission spectroscopy (UPS) spectra with model molecular orbital calculations. The analysis confirms degradation of the phenyl pendant groups and the generation of conjugated double-bonds in the degraded polymer. The observed degradation in polystyrene is found to be very similar to one from polyethylene previously investigated.     

Surface and interface of Ti(film)/SiC(substrate) system: a soft X-ray emission and photoemission electron microscopy study

We have conducted a soft X-ray emission spectroscopy (SXES) and a photoemission electron microscopy (PEEM) study on the heat-treated Ti/4H–SiC system. This spectro-microscopy approach is an ideal surface and interface characterization techniques due to the non-destructive nature of SXES and the real-time surface imaging of PEEM.

The Si L_2,3 and C K soft X-ray emission spectra, which reflect Si (s+d) states and C p states, respectively, revealed formations of Ti₅Si₃ and TiC in the reacted interfacial region of Ti (50 nm)/4H–SiC(0 0 0 1) sample.

The surface of the Ti films on 4H–SiC samples during heat-treatment up to 850 °C was investigated by PEEM. The variation in brightness in the image of the sample was attributed to the surface deoxidation in the early stage of the treatment and to the formation of reacted region at the later stage. The darkening of the surface could be attributed to the formation of TiC and/or excess C atoms that could have migrated to the surface.     

Element-selective mapping of magnetic moments in ultrathin magnetic films using a photoemission microscope

We combine X-ray magnetic circular dichroism (XMCD) and photoelectron emission microscopy to obtain locally resolved magnetic information on a microscopic scale. Scanning the photon energy across elemental absorption edges and recording microscopic images of the local secondary electron intensity for both photon helicities at each photon energy step allows to analyze local XMCD spectra at any position of the imaged area of the sample. With the help of magnetic sum-rules local quantitative information about magnetic moments can be extracted from such microspectroscopic measurements. The full power of XMCD as a spectroscopic tool is so maintained, while microscopic spatial resolution is added.     

Interaction of cesium with charged oxide under UV irradiation imaged by photoemission electron microscopy

We report the first observation of electron transfer from charged SiO₂/Si(1 0 0) by ion-implantation via internal photoemission from Si by photoemission electron microscopy (PEEM) for the purpose of the microscopic control of promotion of catalyst by electron transfer from oxide support. The contrast of the PEEM image varies with the amount and kind of the implanted ion and the deposition of Cs through the formation of electrical double layer consisting of Cs⁺ and trapped electrons at trapping centers created by the implantation. It is then firmly established that oxide charging can be microscopically tuned by ion-implantation.     

Estimation of diffusion coefficient by photoemission electron microscopy in ion-implanted nanostructures

We have fabricated parallel stripes of nanostructures in an n-type Si substrate by implanting 30 keV Ga⁺ ions from a focused ion beam (FIB) source. Two sets of implantation were carried out. In one case, during implantation the substrate was held at room temperature and in the other case at 400 °C. Photoemission electron microscopy (PEEM) was carried out on these samples. The implanted parallel stripes, each with a nominal dimension of 4000 nm × 100 nm, appear as bright regions in the PEEM image. Line scans of the intensities from the PEEM image were recorded along and across these stripes. The intensity profile at the edges of a line scan is broader for the implantation carried out at 400 °C compared to room temperature. From the analysis of this intensity profile, the lateral diffusion coefficient of Ga in silicon was estimated assuming that the PEEM intensity is proportional to Ga concentration. The diffusion coefficient at 400 °C has been estimated to be ∼1.3 × 10⁻¹⁵ m²/s. Across the stripes an asymmetric diffusion profile has been observed, which has been related to the sequence of implantation of these stripes and the associated defect distribution due to lateral straggling of the implanted ions.     

Binding energy shift in photoemission spectroscopy study of Ni clusters deposited on rutile TiO2 surfaces

Cluster-size-dependent binding energy (BE) shifts of Ni 2p_3/2 spectra in Ni clusters with respect to bulk Ni metal have been studied as a function of Ni coverage on clean rutile TiO₂(0 0 1) surfaces at room temperature. Auger parameter (AP) analysis of photoelectron spectra has been employed and revealed an obvious initial state contribution at the coverage of 0.5 monolayers (ML). The initial state effect was demonstrated to be strongly affected by the substrate and was assigned to a combination of eigenvalue shift in surface core-level shift (SCLS) and charge transfer between the metal clusters and substrates. The TiO₂(0 0 1) surface stoichiometry was found to introduce different charge transfer behaviors. Our results experimentally present that the Ni clusters are charged positively on stoichiomtric TiO₂ surface and less positively or even negatively on various reduced surfaces.     

A low voltage time of flight electron emission microscope

This paper presents the design of a low voltage time of flight electron emission microscope (TOF-EEM), which should in principle be capable of acquiring spectral chemical information at nano-metre spatial resolution. The system will be able to operate as a photoelectron emission microscope (PEEM), an X-ray photoemission electron microscope (XPEEM), or a secondary electron emission microscope (SEEM). For each pixel in its highly magnified topographic image, the TOF-EEM column should be able to provide the emission spectrum with milli-electron-volt resolution. The system is designed to operate at secondary electron beam voltages of typically less than 100 V, and has the possibility of dynamically correcting for chromatic aberration. Provisional simulation results predict that the TOF-EEM column should be able to provide an image resolution of better than 2 nm.     

A photoemission study of the interaction of Ga with CeO2(1 1 1) thin films

The interaction of gallium with CeO₂(1 1 1) layers was studied using standard and resonant photoelectron spectroscopy, by means of both a laboratory X-ray source and tunable synchrotron light. Firstly a 1.5-nm thick CeO₂ film was grown on a Cu(1 1 1) substrate. Secondly Ga was deposited in six steps up to a thickness of 0.35 nm, at room temperature. The interaction of gallium with the oxide layer induced partial CeO₂ reduction, and gallium oxidation. The photoemission data suggest that a mixed Ga-Ce-O oxide was established similarly to the Sn-Ce-O case for Sn deposited on cerium oxide layers. As a consequence, gallium-induced weakening of Ce-O bonds provides a higher number of active sites on the surface that play a major role in its catalytic behaviour.     

Computing electron energy loss spectra with the Discontinuous Galerkin Time-Domain method

In this work, we demonstrate how to extract electron energy loss spectra of metallic nano-particles from time-domain computations. Specifically, we employ the Discontinuous Galerkin Time-Domain (DGTD) method in order to model the excitation of individual metallic nano-spheres and dimers of spheres by a tightly focussed electron beam. The resulting electromagnetic fields that emanate from the particles act back on the electrons and the accumulated effect determines the electrons’ total energy loss. We validate this approach by comparing with analytical results for single spheres. For dimers, we find that the electron beam allows for an efficient excitation of dark modes that are inaccessible for optical spectroscopy. In addition, our time-domain approach provides a basis for dealing with materials that exhibit a significant nonlinear response.     

电子显微学进展及其在材料科学中的应用

文章简要介绍了高分辨电子显微学方法和电子能量损失谱的进展.文中特别指出,随着电子显微技术的发展,原子分辨电子显微图像对结构问题的深入研究有重要作用.装备有能量单色器的新一代电子显微镜,可以直接给出高能量分辨率的电子能量损失谱(优于 0.1eV).这些先进技术方法的应用,推动了晶体结构学、材料科学、物理学、纳米科学及生命科学的发展,也为解决很多重要结构问题奠定了基础.文章重点讨论了几个典型功能材料体系的结构问题：利用大角度会聚束电子衍射技术,分析了应变硅器件中的应变分布;利用原位电子显微技术,研究了新型电子铁电体LuFe2O4电荷序和物理性能的关系;深入探讨了强关联体系中电子关联效应对电子能量损失谱和电子结构的影响.     

Core level photoemission and STM characterization of Ta/Si(1 1 1)-7 × 7 interfaces

We present the results of scanning tunneling microscopy (STM) and photoemission spectroscopy (PES) of the Ta/Si(1 1 1)-7 × 7 system after deposition of Ta at substrate temperatures from 300 to 1250 K. The coverage of Ta varied from 0.05 up to 2.5 of a monolayer (ML). STM shows that at 300 K and coverage less than 1 ML, a disordered chemisorbed phase is formed. Deposition on a hot surface (above 500 K) produces round 3D clusters randomly distributed on the surface. Cluster height and their diameter are found to change drastically with annealing temperature and the Ta coverage. Analysis of photoemission data of the Si 2p core levels shows that at room temperature and at coverage ?1 ML core level binding energy shifts and intensity variations of Si surface related components are observed, which clearly indicate that the reaction starts already at 300 K. Shifts in the binding energy, changes of the peak shapes and intensity of the Ta 4f doublet at higher temperatures can be explained by the formation of stable silicide on the surface.