Vector potential photoelectron microscopy

A new class of electron microscope has been developed for the chemical microanalysis of a wide range of real world samples using photoelectron spectroscopy. Highly structured, three-dimensional samples, such as fiber mats and fracture surfaces can be imaged, as well as insulators and magnetic materials. The new microscope uses the vector potential field from a solenoid magnet as a spatial reference for imaging. A prototype instrument has demonstrated imaging of uncoated silk, magnetic steel wool, and micron-sized single strand tungsten wires.     

Characterizing voltage contrast in photoelectron emission microscopy

A non‐destructive technique for obtaining voltage contrast information with photoelectron emission microscopy is described. Samples consisting of electrically isolated metal lines were used to quantify voltage contrast in photoelectron emission microscopy. The voltage contrast behaviour is characterized by comparing measured voltage contrast with calculated voltage contrast from two electrostatic models. Measured voltage contrast was found to agree closely with the calculated voltage contrast, demonstrating that voltage contrast in photoelectron emission microscopy can be used to probe local voltage information in microelectronic devices in a non‐intrusive fashion.     

Prospects in high resolution X-ray photoelectron microscopy

After a brief review of the present state of the art in X-ray photoelectron microscopy, the prospects to improve the nominal value of the spatial resolution are described. Progress in this method is also related to the development of dense X-ray sources, but possible radiation damage effects have to be considered.     

Enhanced spatial resolution in vector potential photoelectron microscopy

The spatial resolution of the vector potential photoelectron microscope is determined by the maximum size of the cyclotron orbits of the imaged electrons at the surface of a sample. It is straightforward to calculate the spatial resolution for any imaged electron energy given the magnetic field strength. However, in low‐energy secondary photoelectron images from an aluminium–calcium metal matrix alloy, we find the apparent spatial resolution is significantly higher than expected. A possible explanation for the enhanced resolution is that the low‐energy cyclotron orbits are distorted when passing from one area of work function to another and the image is dependent on the surface field distribution.     

Emission microscopy and related techniques: resolution in photoelectron microscopy, low energy electron microscopy and mirror electron microscopy.

A unified treatment of the resolution of three closely related techniques is presented: emission electron microscopy (particularly photoelectron microscopy, PEM), low energy electron microscopy (LEEM), and mirror electron microscopy (MEM). The resolution calculation is based on the intensity distribution in the image plane for an object of finite size rather than for a point source. The calculations take into account the spherical and chromatic aberrations of the accelerating field and of the objective lens. Intensity distributions for a range of energies in the electron beam are obtained by adding the single-energy distributions weighted according to the energy distribution function. The diffraction error is taken into account separately. A working resolution is calculated that includes the practical requirement for a finite exposure time, and hence a finite non-zero current in the image. The expressions for the aberration coefficients are the same in PEM and LEEM. The calculated aberrations in MEM are somewhat smaller than for PEM and LEEM. The resolution of PEM is calculated to be about 50 A, assuming conventional UV excitation sources, which provide current densities at the specimen of 5 x 10(-5) A/cm2 and emission energies ranging up to 0.5 eV. A resolution of about 70 A has been demonstrated experimentally. The emission current density at the specimen is higher in LEEM and MEM because an electron gun is used in place of a UV source. For a current density of 5 x 10(-4) A/cm2 and the same electron optical parameters as for PEM, the resolution is calculated to be 27 A for LEEM and 21 A for MEM.     

Sialolith characterization by scanning electron microscopy and X-ray photoelectron spectroscopy

The objective of this study has been to characterize sialolith, a calcium phosphate deposit that develops in the human oral cavity, by high-resolution field emission scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The morphological and chemical data obtained helped in the determination of their formation mechanism in salivary glands. Sialoliths in the submandibular salivary glands may arise secondary to sialodenitis, but not via a luminal organic nidus. We believe this is the first study that characterizes a sialolith by XPS.     

Dark field photoelectron emission microscopy of micron scale few layer graphene

We demonstrate dark field imaging in photoelectron emission microscopy (PEEM) of heterogeneous few layer graphene (FLG) furnace grown on SiC(000-1). Energy-filtered, threshold PEEM is used to locate distinct zones of FLG graphene. In each region, selected by a field aperture, the k-space information is imaged using appropriate transfer optics. By selecting the photoelectron intensity at a given wave vector and using the inverse transfer optics, dark field PEEM gives a spatial distribution of the angular photoelectron emission. In the results presented here, the wave vector coordinates of the Dirac cones characteristic of commensurate rotations of FLG on SiC(000-1) are selected providing a map of the commensurate rotations across the surface. This special type of contrast is therefore a method to map the spatial distribution of the local band structure and offers a new laboratory tool for the characterisation of technically relevant, microscopically structured matter.     

Contrast effects in photoelectron microscopy; UV dose-dependent quantum yields of biological surface components

The relative brightness of photoelectron microscopy images as a function of exposure to UV light has been determined from model systems representative of biological cell surface components. Quantitative data for amino acid homopolymers, L-α-dipalmitoylphosphatidylcholine, and the polysaccharide Ficoll are reported as the absolute photoelectron quantum yields. The photoelectron quantum yields increase substantially over the initial values. For example, the quantum yields of poly-L-tyrosine at 200 nm is initially about 5 × 10^?8 electrons/incident photon. The quantum yield increases with 254 nm irradiation, leveling off at about 5 × 10^?4 electrons/incident photon after a dose of 3 × 10²¹ quanta cm^?2. Pre-irradiation of poly-L-tyrosine in the presence of certain chemical agents, for example, the Lewis base diborane (B₂H₆), results in a substantial reduction of the dose-dependent increase in quantum yield. Exposure to the reducing agent stannane (SnH₄) essentially eliminates the effect. These chemical treatments provide methods of controlling the UV dose-dependent effects in the photoelectron images.     

Depth sectioning in scanning transmission electron microscopy based on core-loss spectroscopy

Recent and ongoing improvements in aberration correction have opened up the possibility of depth sectioning samples using the scanning transmission electron microscope in a fashion similar to the confocal scanning optical microscope. We explore questions of principle relating to image interpretability in the depth sectioning of samples using electron energy loss spectroscopy. We show that provided electron microscope probes are sufficiently fine and detector collection semi-angles are sufficiently large we can expect to locate dopant atoms inside a crystal. Furthermore, unlike high angle annular dark field imaging, electron energy loss spectroscopy can resolve dopants of smaller atomic mass than the supporting crystalline matrix.     

Photoelectron microscopy and photoelectron quantum yields of the fluorescent dyes flourescein and rhodamine

Photoelectric properties of the dyes fluorescein and rhodamine were determined with the aim of assessing the usefulness of these compounds as labels in photoelectron microscopy. The photoelectron quantum yields were measured over the wavelength range 180–230 nm. At 230 nm the quantum yields for fluorescein disodium salt, rhodamine B free base and rhodamine B HCl salt are approximately 10^-5 electrons per incident photon. At 180nm these values rise to approximately 10^-3 electrons per incident photon. All forms of fluorescein do not have the same quantum yield. The neutral form of fluorescein has a quantum yield an order of magnitude lower than the disodium salt. Beam current measurements were performed on labeled and unlabeled proteins to determine the effect of the high light intensity employed in the photoelectron microscope. The initial beam current measurements and the quantum yield curves are consistent and demonstrate that there is significant contrast between labeled and unlabeled proteins. However, after several minutes in the photoelectron microscope, the proteins become more photoemissive and the contrast diminishes. This change in contrast explains several puzzling observations in the literature.     

Linear versus non-linear structural information limit in high-resolution transmission electron microscopy

A widely used performance criterion in high-resolution transmission electron microscopy (HRTEM) is the information limit. It corresponds to the inverse of the maximum spatial object frequency that is linearly transmitted with sufficient intensity from the exit plane of the object to the image plane and is limited due to partial temporal coherence. In practice, the information limit is often measured from a diffractogram or from Young's fringes assuming a weak phase object scattering beyond the inverse of the information limit. However, for an aberration corrected electron microscope, with an information limit in the sub-angstrom range, weak phase objects are no longer applicable since they do not scatter sufficiently in this range. Therefore, one relies on more strongly scattering objects such as crystals of heavy atoms observed along a low index zone axis. In that case, dynamical scattering becomes important such that the non-linear and linear interaction may be equally important. The non-linear interaction may then set the experimental cut-off frequency observed in a diffractogram. The goal of this paper is to quantify both the linear and the non-linear information transfer in terms of closed form analytical expressions. Whereas the cut-off frequency set by the linear transfer can be directly related with the attainable resolution, information from the non-linear transfer can only be extracted using quantitative, model-based methods. In contrast to the historic definition of the information limit depending on microscope parameters only, the expressions derived in this paper explicitly incorporate their dependence on the structure parameters as well. In order to emphasize this dependence and to distinguish from the usual information limit, the expressions derived for the inverse cut-off frequencies will be referred to as the linear and non-linear structural information limit. The present findings confirm the well-known result that partial temporal coherence has different effects on the transfer of the linear and non-linear terms, such that the non-linear imaging contributions are damped less than the linear imaging contributions at high spatial frequencies. This will be important when coherent aberrations such as spherical aberration and defocus are reduced.     

Image division technique in pre-acquisition analysis of information content for automated microscopy

This article presents a method that allows for reliable automated image acquisition of specimens with high information content in light microscopy with emphasis on fluorescence microscopy applications. Automated microscopy typically relies on autofocusing used for the analysis of information content behaviour along the z-axis within each field of view. However, in the case of a field of view containing more objects that do not lie precisely in one z-plane, traditional autofocusing methods fail due to their principle of operation. We avoid this issue by reducing the original problem to a set of simple and performable tasks: we divide the field of view into a small number of tiles and process each of them individually. The obtained results enable discovering z-planes with rich information content that remain hidden during global analysis of the whole field of view. Our approach therefore outperforms other acquisition methods including the manual one. A large part of the contribution is oriented towards practical application.     

Digital filters to restore information from fast scanning tunnelling microscopy images

A transfer function—similar to that used in optical cases to correct blurring effects due to the circular aperture of the system—is presented here to restore scanning tunnelling microscopy (STM) images. Due to the conical geometry of the tip-sample system, we have established an analogy between the process of image formation in STM and in optical systems. The transfer function utilized, similar to that calculated by Stokseth, allows us to differentiate between the blurring effects introduced along the x and y axes. These effects are different due, mainly, to the different velocities achieved along the x and y directions. Furthermore we have measured the β parameter that characterizes the classical 1/fβ noise present in STM data, demonstrating its independence from experimental conditions. A Wiener filter is utilized to restore the images using the previous assumptions given for the transfer function and noise effects.     

The extension of scanning transmission electron microscopy by use of diffraction information.

The information contained in the intensity distribution of the convergent beam electron diffraction pattern, produced in the detector plane for each incident beam position in a scanning transmission electron microscope, may be used to enhance the resolution of the microscope or else to decrease the electron irradiation of the specimen involved in deducing information at any particular level of resolution. The structural information concerning the specimen may be obtained, for example by interpretation of the Patterson function using image-seeking methods. The statistical error involved due to the finite number of electrons available may be derived by considering the efficiency of use of the information contained in Patterson function peaks. The most efficient means for using the available information appears to be that based on information theory concepts, which employ the integral over the product of the observed diffraction pattern intensity and the intensity calculated for known or postulated groupings of atoms. The reduction in radiation damage possible by use of this method, relative to that involved in the separate imaging of individual atoms, may be by a factor of approximately n, where n is the number of atoms in the known or postulated group being sought.     

Comparison in spatial spreads of secondary electron information between scanning ion and scanning electron microscopy

Monte Carlo simulations have been carried out to compare the spatial spreads of secondary electron (SE) information in scanning ion microscopy (SIM) with scanning electron microscopy (SEM). Under Ga ion impacts, the SEs are excited by three kinds of collision-partners, that is, projectile ion, recoiled target atom, and target electron. The latter two partners dominantly contribute to the total SE yield gamma for the materials of low atomic number Z2. For the materials of high Z2, on the other hand, the projectile ions dominantly contribute to gamma. These Z2 dependencies generally cause the gamma yield to decrease with an increasing Z2, in contrast with the SE yield delta under electron impacts. Most of the SEs are produced in the surface layer of about 5lambda in depth (lambda: the mean free path of SEs), as they are independent of the incident probe. Under 30 keV Ga ion impacts, the spatial spread of SE information is roughly as small as 10 nm, decreasing with an increasing Z2. Under 10 keV electron impacts, the SEI excited by the primary electrons has a small spatial spread of about 5lambda, but the SEII excited by the backscattered electrons has a large one of several 10 to several 100 nanometers, decreasing with an increasing Z2. The main cause of a small spread of SE information at ion impact is the short ranges of the projectile ions returning to the surface to escape as backscattered ions, the recoiled target atoms, and the target electrons in collision cascade. The 30 keV Ga-SIM imaging is better than the 10 keV SEM imaging in spatial resolution for the structure/material measurements. Here, zero-size probes are assumed.     

Time-resolved photoelectron spectroscopy of liquids

We present a novel setup for the investigation of ultrafast dynamic processes in a liquid jet using time-resolved photoelectron spectroscopy. A magnetic-bottle type spectrometer with a high collection efficiency allows the very sensitive detection of photoelectrons emitted from a 10 μm thick liquid jet. This translates into good signal/noise ratio and rapid data acquisition making femtosecond time-resolved experiments feasible. We describe the experimental setup, a detailed spectrometer characterization based on the spectroscopy of nitric oxide in the gas phase, and results from femtosecond time-resolved experiments on sodium iodide solutions. The latter experiments reveal the formation and evolution of the solvated electron and we characterize two distinct spectral components corresponding to initially thermalized and unthermalized solvated electrons. The absence of dark states in photoionization, the direct measurement of electron binding energies, and the ability to resolve dynamic processes on the femtosecond time scale make time-resolved photoelectron spectroscopy from the liquid jet a very promising method for the characterization of photochemical processes in liquids.     

Development of a new photoelectron spectroscopy instrument combining an electrospray ion source and photoelectron imaging

A new apparatus has been constructed that combines electrospray ionization with a quadrupole mass filter, hexapole ion trap, and velocity-map imaging. The purpose is to record photoelectron images of isolated chromophore anions. To demonstrate the capability of our instrument we have recorded the photodetachment spectra of isolated deprotonated phenol and indole anions. To our knowledge, this is the first time that the photodetachment energy of the deprotonated indole anion has been recorded.     

Photoelectron imaging and photoelectron labeling

Photoelectron imaging involves the photoejection of low-energy electrons from a specimen surface exposed to UV light. The electrons are then accelerated and focused by an electron-optics system in much the same way fluorescent light is focused in an optical microscope. Thus, photoelectron imaging is the electron-optical analog of fluorescence microscopy. In combination with photoemissive labels it serves to extend the range of studies possible by fluorescence, for example in work on cell surfaces and internal structures of cells that have been exposed by detergent extraction of membranes.