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.     

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.     

High-precision sample stage for photoemission microscopy of organic films

A high-precision sample stage for photoemission microscopy has been constructed to translate the sample by ±3 mm with accuracy better than 100 nm. The stage is actuated by step motors settled outside the vacuum. The accuracies of the translations were measured by observing a standard patterned sample with a photoemission electron microscope (PEEM) of 50 nm resolution. The accuracy was nearly independent of the distance of each translation step and the error was not accumulated by repeated steps. After round-trip translations up to 0.2 mm, the sample came back to the original position with accuracy of ±50 nm. The performance of the stage was demonstrated by observing growth processes of lead phthalocyanine (PbPc) films formed on graphite.     

Microscopically controlled oxidation of H/Si(1 0 0) by lateral surface electric field studied by emission electron microscopies

The ultrathin oxidation of a H/Si(1 0 0) surface with microfabricated pn-junctions was studied by photoemission electron microscopy (PEEM), mirror electron microscopy (MEM) and microscopic X-ray photoelectron spectroscopy (μ-XPS). The ultrathin oxidation inverts the contrast of the junctions in PEEM images. It is found by analyzing the intensity profiles of images that the potential distribution across the pn-junctions is also inverted by the oxidation. The charging of the oxide by ultraviolet irradiation from a light source of PEEM is attributed as the cause of the inversion of the contrast shown by μ-XPS and MEM.     

Improvement of femtosecond SPPs imaging by two-color laser photoemission electron microscopy

Clear imaging of surface plasmon polaritons (SPPs) is a prerequisite for SPPs-based applications. In this work, we demonstrate an improvement of near-field imaging of SPPs via directly comparing the visibility of the photoemission electron microscopy (PEEM) image of SPPs under one- and two-color laser excitation (also known as one- or two-color laser PEEM). By measuring the photoelectron yield and the contrast of the interference fringes of SPPs, we demonstrate that in addition to enhancing the photoemission yield, two-color laser PEEM can significantly improve the contrast between bright and dark fringes (nearly 4 times higher than that of one-color laser case). By recording the nonlinear order of the photoelectrons ejected from the bright and dark fringes, respectively, the underlying mechanism for the improved visibility is revealed. In addition, the influences of the polarization direction of 400-nm laser on the PEEM images of the SPPs with different wave vector directions are shown. These results can provide technical support for the development of SPPs-based communication devices and catalysis.     

Exploring the magnetic and organic microstructures with photoemission electron microscope

We present photoemission electron microscopy (PEEM) studies on geometrically constrained ferromagnetic, organic, and organics–ferromagnet hybrid structures. Powered by an elliptically polarized undulator, the PEEM at Taiwan Light Source (TLS) is capable of recording polarization enhanced X-ray images and has been employed to examine the domain configurations in a lithographically patterned permalloy film as well as the orientations of pentacene molecules adsorbed on self-assembled monolayers (SAMs) modified gold surfaces. In addition, magnetic images acquired on cobalt/pentacene and pentacene/cobalt bilayers reveal that in hybrid structures the order of thin film deposition can lead to distinct domain configurations. Spectroscopic evidence further suggests that there is significant orbital hybridization at the interface where metallic cobalt was deposited directly on organic pentacene.     

石墨烯的透射电子显微学研究

石墨烯（Graphene）是近几年迅速发展起来的研究热点材料之一.利用透射电子显微镜（TEM）研究Graphene的结构特征和原子动态过程,是 Graphene研究的重要进展.文章评述了利用透射电子衍射方法对Graphene的层数、堆垛方式、取向和表面形貌等结构特征进行的研究工作,介绍了利用高分辨透射电子显微术在Graphene的表面缺陷、边缘结构及吸附原子等研究领域取得的最新结果.     

Tip-induced large-area oxide bumps and composition stoichiometry test via atomic force microscopy

Using atomic force microscope (AFM) tip, local large-area oxide bumps were induced on a native SiO₂ layer applied with a static 10 V in an ambient surrounding. It can be seen in the backscattered electron (BE) images that the oxide bumps were SiO_x layer, not the native SiO₂ layer. Also, the spectra of energy dispersive X-ray spectrometer (EDS) displayed that the oxide bumps contained oxygen more than did the native SiO₂ layer, indicating that the O/Si ratio of the oxide bump is greater than two. A comparison of the growth rates of the point oxide protrusions on the oxide bumps and on the native SiO₂, can be used to directly determined the composition stoichiometry (the O/Si ratio (=x)) of the oxide bumps.     

Determination of 25 elements in the complex oxide mineral zirconolite by analytical electron microscopy

In this paper we describe a technique for the determination of 25 elements in natural zirconolite using energy-dispersive analytical electron microscopy (AEM). The method presented here allows one to quantitatively investigate the chemistry of submicron-scale zones in complex oxide minerals. The effects of electron channeling, thickness variability and variations in detector resolution were minimized by using a controlled set of operating procedures and instrument parameters. To provide a high level of accurayy, k_ATI-factors were determined from standards for most of the 25 elements of interest, including all of the major elements. Each analytical spectrum is reduced to a set of raw peak counts (and errors) using a digital top-hat filter to suppress background followed by multiple least squares fitting of reference spectra. Counting times of 12–15 min per analysis were required to provide suitable counting statistics. Results are presented for zirconolite samples from the contact metamorphic aureole of the Bergell granodiorite intrusion, Switzerland-Italy. A comparison of 43 AEM analyses with 15 analyses obtained by wavelength-dispersive electron probe microanalysis (EPMA) shows that there is excellent agreement between the two data sets in the amounts of individual elements present, chemical trends and overall stoichiometry. An assessment of the combined data set shows that the major substitution mechanisms in the Bergell samples are coupled substitutions involving the M5,6- and M8-sites of the zirconolite structure: ^M8Ca²⁺ + ^M5,6Ti⁴⁺→^M8REE³⁺ + ^M5,6(Al,Fe)³⁺ and ^M8Ca²⁺ + ^M5,6Ti⁴⁺→^M8(Th,U)⁴⁺ + ^M5,6 (Mg,Fe)²⁺.     

Microspectroscopy and spectromicroscopy with photoemission electron microscopy using a new kind of imaging energy filter

The use of an imaging retarding field analyser attached to the FOCUS IS-PEEM is described. This kind of energy filter is a simple, powerful tool to obtain microspectra from areas of down to about 1 μm using (V)UV and X-ray excitation sources. First results of microspectroscopy measured by excitation with a laboratory as well as a synchrotron X-ray source are presented.     

Analytical electron microscopy of a reaction-bonded Si3N4-based ceramic containing oxide additions

The microstructure of a silicon nitride (Si₃N₄)-based ceramic, prepared by a process combining direct nitridation and reactive liquid phase sintering of silicon/ceramic oxide powder compacts, has been characterised using analytical transmission electron microscopy. The presence of the reactive liquid phase, promoted by the addition of oxides from the CaO-Al₂O₃-SiO₂ ternary system, resulted in an as-fired microstructure containing a mixture of crystalline phases based on -Si₃N₄, β-Si₃N₄ and Si₂ N₂O, and distinct amorphous regions rich in Si, Al and Ca. X-ray microanalysis revealed the calcium to be wholly partitioned to the glassy phase, while significant concentrations of aluminium were detected in both β-Si₃N₄ and Si₂N₂O. The observed compositions of these phases, together with measured lattice parameters systematically in excess of those of the pure compounds, imply that they are in fact β- and O-sialons respectively. Semi-quantitative energy dispersive X-ray spectroscopy, using an ultra-thin window detector, is demonstrated to be capable of distinguishing clearly between these phases according to their oxygen content and of determining the aluminium content of both phases to within ± 1 equ.%, even at concentration levels of <5 equ.%.     

Transmission electron microscopy of unstained hybrid Au nanoparticles capped with PPAA (plasma-poly-allylamine): Structure and electron irradiation effects

Hybrid (organic shell–inorganic core) nanoparticles have important applications in nanomedicine. Although the inorganic components of hybrid nanoparticles can be characterized readily using conventional transmission electron microscopy (TEM) techniques, the structural and chemical arrangement of the organic molecular components remains largely unknown. Here, we apply TEM to the physico-chemical characterization of Au nanoparticles that are coated with plasma-polymerized-allylamine, an organic compound with the formula C₃H₅NH₂. We discuss the use of energy-filtered TEM in the low-energy-loss range as a contrast enhancement mechanism for imaging the organic shells of such particles. We also study electron-beam-induced crystallization and amorphization of the shells and the formation of graphitic-like layers that contain both C and N. The resistance of the samples to irradiation by high-energy electrons, which is relevant for optical tuning and for understanding the degree to which such hybrid nanostructures are stable in the presence of biomedical radiation, is also discussed.     

采用高分辨电镜分析Cu掺杂聚-4-甲基-1-戊烯泡沫材料采用高分辨电镜分析Cu掺杂聚-4-甲基-1-戊烯泡沫材料

利用物理掺杂的方法,制备了铜掺杂聚-4-甲基-1-戊烯(PMP)低密度泡沫材料,采用高分辨扫描电子显微镜和透射电子显微镜,分析了泡沫材料的微观结构、成分及微区成分分布。结果表明：与PMP泡沫相比,铜掺杂PMP泡沫的孔洞直径和网络骨架尺寸变大;铜颗粒镶嵌在PMP泡沫的有机骨架上且有团聚现象;泡沫材料中除碳、铜外,还残留有杂质元素氧;铜颗粒被PMP泡沫包裹,与碳网络骨架之间接触紧密。     

Phase change of CoTi and Co3Ti induced by MeV-scale electron irradiation

This study investigates equilibrium-to-nonequilibrium solid phase transitions induced by MeV-scale electron irradiation in B2-CoTi and L1₂-Co₃Ti intermetallic compounds by means of high-voltage electron microscopy. Under MeV-scale electron irradiation, B2-CoTi transforms into a body-centered cubic solid solution through chemical disordering and eventually transforms into an amorphous phase. The critical temperature for amorphisation is found to be 110 K. L1₂-Co₃Ti also exhibits chemical disordering at temperatures below 700 K. However, its amorphisation does not occur even at a low temperature of 20 K. The dominant factor in these solid phase transitions is discussed in terms of the Gibbs free energy.     

Local thermal conductivity of polycrystalline AlN ceramics measured by scanning thermal microscopy and complementary scanning electron microscopy techniques

The local thermal conductivity of polycrystalline aluminum nitride (AlN) ceramics is measured and imaged by using a scanning thermal microscope (SThM) and complementary scanning electron microscope (SEM) based techniques at room temperature. The quantitative thermal conductivity for the AlN sample is gained by using a SThM with a spatial resolution of sub-micrometer scale through using the 3ω method. A thermal conductivity of 308 W/m·K within grains corresponding to that of high-purity single crystal AlN is obtained. The slight differences in thermal conduction between the adjacent grains are found to result from crystallographic misorientations, as demonstrated in the electron backscattered diffraction. A much lower thermal conductivity at the grain boundary is due to impurities and defects enriched in these sites, as indicated by energy dispersive X-ray spectroscopy.     

Size of three‐dimensional objects measured by means of photoemission electron microscopy

Pb particles on a Si(111) substrate were investigated using a photoemission electron microscope (PEEM). The electrons have been excited by a linearly polarised femtosecond laser beam with a wavelength of λ = 400 nm. The PEEM images exhibit an unusually high contrast. They arise due to photoemission being of a nontrivial nature because the photon energy is lower than the work function of the sample. It may be caused by the following processes: two‐ or multi‐photon absorption, tunnel‐photoeffect induced by a strong lowering of the potential barrier owing to enhancement of the electrical field of the powerful incident light wave on a rough surface, generation of second harmonic with its following absorption, or electron gas heating. Images obtained with orthogonal directions of the photon polarisation were compared to estimate the shape of different Pb particles. The size of the islands was determined by two methods, either from the shape of the spatial brightness distribution or from the area under the curve of this distribution.     

Imaging polycrystalline and smoke MgO surfaces with atomic force microscopy: a case study of high resolution image on a polycrystalline oxide

Atomic force microscopy in contact, non-contact and in high resolution modes have been used to image MgO powder samples, obtained at different degree of sintering, starting from Mg(OH)₂ decomposition or obtained in form of smoke. From high resolution AFM images of MgO smoke, the lattice periodicity on regular surfaces has been revealed for the first time, under ambient conditions. The high surface perfection of the microcrystals has been further confirmed by HRTEM analysis. To obtain more information on the local structure of the single faces, in terms of type and distribution of the surface active sites, the adsorption of a simple probe molecule (CO) on such surfaces has been investigated by means of FTIR spectroscopy.     

Interaction of copper with sulfur on the sulfur-terminated Si(1 1 1)-(7 × 7) surface

The adsorption of S₂ on the Si(1 1 1)-(7 × 7) surface and the interaction of copper and sulfur on this sulfur-terminated Si(1 1 1) surface have been studied using synchrotron irradiation photoemission spectroscopy and scanning tunneling microscopy. The adsorption of S₂ at room temperature results in the passivation of silicon dangling bonds of Si(1 1 1)-(7 × 7) surface. Excessive sulfur forms S_n species on the surface. Copper atoms deposited at room temperature directly interact with S-adatoms through the formations of Cu-S bonds. Upon annealing the sample at 300 °C, CuS_x nanocrystals were produced on the sulfur-terminated Si(1 1 1) surface.     

Multipulse irradiation of silicon by femtosecond laser pulses: Variation of surface morphology

The multipulse interaction of ultraviolet femtosecond laser pulses with silicon and generation of surface structures in a large area spot (?1 mm²) has been studied. The evolution of multiscale structures at the constant fluence strongly depends on the number of pulses, N. For N < 200, the “carpet-like” pattern of nano-, and micro-spikes is generated by the bubble explosion in a thin surface foam layer. The accumulation of bubbles and their explosion due to repetition of laser pulses cause damped membrane-like oscillations of the silicon surface. For 200 ≤ N, bifurcation of surface morphology takes place: (i) the surface tension waves of the wavelength ∼200 μm appear in the peripheral region of the spot. Generated by the surface thermal gradient in the liquid foam layer, they spread from the hot centerline towards the periphery of the spot. The change of their wavelength with propagation distance indicates onset of the Eckhaus instability caused by the phase modulation in multipulse interaction. (ii) Deep caverns appear in a highly superheated silicon layer in the central region of the spot due to the fast gas-liquid phase separation and the fragmentation process.     

Lattice imaging of close-packed structures by high resolution electron microscopy: ABO3 perovskite polytypes

Lattice imaging technique of high resolution electron microscopy has been employed to examine 4H, 6H and 9R ABO₃ perovskite polytypes. The lattice images can be correlated with the lattice periodicity and the stacking sequence of AO₃ layers and BO₆ octahedra. The study shows the utility and validity of the lattice imaging technique for the study of relatively close-packed systems. Commonwealth Visiting Professor, University of Oxford (1974–75).