Search

The detailed examination of electron scattering in solids is of crucial importance for the theory of solid-state physics, as well as for the development and diagnostics of novel materials, particularly those for micro- and nanoelectronics. Among others, an important parameter of electron scattering is the inelastic mean free path (IMFP) of electrons both in bulk materials and in thin films, including 2D crystals. The amount of IMFP data available is still not sufficient, especially for very slow electrons and for 2D crystals. This situation motivated the present study, which summarizes pilot experiments for graphene on a new device intended to acquire electron energy-loss spectra (EELS) for low landing energies. Thanks to its unique properties, such as electrical conductivity and transparency, graphene is an ideal candidate for study at very low energies in the transmission mode of an electron microscope. The EELS are acquired by means of the very low-energy electron microspectroscopy of 2D crystals, using a dedicated ultra-high vacuum scanning low-energy electron microscope equipped with a time-of-flight (ToF) velocity analyzer. In order to verify our pilot results, we also simulate the EELS by means of density functional theory (DFT) and the many-body perturbation theory. Additional DFT calculations, providing both the total density of states and the band structure, illustrate the graphene loss features. We utilize the experimental EELS data to derive IMFP values using the so-called log-ratio method.

Two-dimensional materials, such as graphene, are usually prepared by chemical vapor deposition (CVD) on selected substrates, and their transfer is completed with a supporting layer, mostly polymethyl methacrylate (PMMA). Indeed, the PMMA has to be removed precisely to obtain the predicted superior properties of graphene after the transfer process. We demonstrate a new and effective technique to achieve a polymer-free CVD graphene — by utilizing low-energy electron irradiation in a scanning low-energy electron microscope (SLEEM). The influence of electron-landing energy on cleaning efficiency and graphene quality was observed by SLEEM, Raman spectroscopy (the presence of disorder D peak) and XPS (the deconvolution of the C 1s peak). After removing the absorbed molecules and polymer residues from the graphene surface with slow electrons, the individual graphene layers can also be distinguished outside ultra-high vacuum conditions in both the reflected and transmitted modes of a scanning low-energy (transmission) electron microscope.

Electron-beam-induced deposition of various materials from suitable precursors has represented an established branch of nanotechnology for more than a decade. A specific alternative is carbon deposition on the basis of hydrocarbons as precursors that has been applied to grow various nanostructures including masks for subsequent technological steps. Our area of study was unintentional electron-beam-induced carbon deposition from spontaneously adsorbed hydrocarbon molecules. This process traditionally constitutes a challenge for scanning electron microscopy practice preventing one from performing any true surface studies outside an ultrahigh vacuum and without in-situ cleaning of samples, and also jeopardising other electron-optical devices such as electron beam lithographs. Here we show that when reducing the energy of irradiating electrons sufficiently, the e-beam-induced deposition can be converted to e-beam-induced release causing desorption of hydrocarbons and ultimate cleaning of surfaces in both an ultrahigh and a standard high vacuum. Using series of experiments with graphene samples, we demonstrate fundamental features of e-beam-induced desorption and present results of checks for possible radiation damage using Raman spectroscopy that led to optimisation of the electron energy for damage-free cleaning. The method of preventing carbon contamination described here paves the way for greatly enhanced surface sensitivity of imaging and substantially reduced demands on vacuum systems for nanotechnological applications.

Low voltage electron microscopes working in transmission mode, like LVEM5 (Delong Instruments, Czech Republic) working at accelerating voltage 5 kV or scanning electron microscope working in transmission mode with accelerating voltage below 1 kV, require ultrathin sections with the thickness below 20 nm. Decreasing of the primary electron energy leads to enhancement of image contrast, which is especially useful in the case of biological samples composed of elements with low atomic numbers. As a result treatments with heavy metals, like post-fixation with osmium tetroxide or ultrathin section staining, can by omitted. The disadvantage is reduced penetration ability of incident electrons influencing the usable thickness of the specimen resulting in the need of ultrathin sections of under 20 nm thickness. In this study we want to answer basic questions concerning the cutting of extremely ultrathin sections: Is it possible routinely and reproducibly to cut extremely thin sections of biological specimens embedded in commonly used resins with contemporary ultramicrotome techniques and under what conditions? Microsc. Res. Tech. 79:512-517, 2016. © 2016 Wiley Periodicals, Inc.

Summary Commercially available graphene samples are examined by Raman spectroscopy and very low energy scanning transmission electron microscopy. Limited lateral resolution of Raman spectroscopy may produce a Raman spectrum corresponding to a single graphene layer even for flakes that can be identified by very low energy electron microscopy as an aggregate of smaller flakes of various thicknesses. In addition to diagnostics of graphene samples at larger dimensions, their electron transmittance can also be measured at very low energies.

An overview of recent developments in very low energy scanning electron microscopy is presented. Electron optical aspects are briefly summarized including the low energy beam formation in a cathode lens equipped column, comparison of the sequential and overlapped electric and magnetic fields in the objective lens, and detection issues including extension to the transmitted electron mode as well as to the multichannel detection of signal sorted according to the polar angle of emission. In addition to the acquisition of contrasts specific for the very low energy range, advantages of detection of electrons backscattered to large angles from the surface normal are demonstrated on selected application examples.

Study of the grain structure in the equal channel angular pressing processed copper by means of the cathode lens equipped ultrahigh vacuum scanning low energy electron microscope is reported. The grain contrast was found achieving its maximum at electron energies below about 30 eV where it alternated its sign and exhibited dependence on electron energy specific for the grain orientation. The energy dependence of the electron reflectance seemed to be capable of serving as a fingerprint enabling determination of the crystalline orientation. In the cathode lens mode at hundreds of eV fine details of the microstructure are also observable including twins and low angle grain boundaries. This is explained by acquisition of high-angle backscattered slow electrons, normally not acquired in standard scanning electron microscopes. The very low energy electron reflectance is promising as an alternative to the EBSD method owing to its high resolution and fast data acquisition.

By introducing a cathode lens below or inside the objective lens of a scanning electron microscope, many experiments similar to those typical of the LEEM method can be performed. The conditions for the diffraction of slow electrons are modified by the convergence of the primary beam, and challenges include the necessity of managing the signal species propagating along the optical axis in a direction opposite to that of the primary beam. However, even a simple implementation, providing the integral dark-field signal only, has not only delivered plenty of results in the very low energy range below 50 eV, but the performance in the range of hundreds of eV and units of keV has also been substantially improved. The scanning LEEM method is illustrated using experimental results acquired by additionally employing multichannel detection and detection of transmitted electrons.

A method for scanning electron microscopy imaging of nonconductive specimens, based on measurement and utilisation of a critical energy, is described in detail together with examples of its application. The critical energy, at which the total electron yield curve crosses the unit level, is estimated on the basis of measurement of the image signal development from the beginning of irradiation. This approach, concentrated onto the detected signal as the only quantity crucial for the given purpose of acquiring a noncharged micrograph, evades consequences of any changes in an irradiated specimen that influence the total electron yield curve and possibly also the critical energy value. Implementation of the automated method, realised using a cathode lens-equipped scanning electron microsope (SEM), enables one to establish a mean rate of charging over the field of view and its dependence on the electron landing energy. This dependence enables one to determine the energy of a minimum damage of the image of the given field of view. Factors influencing reliability and applicability of the method are discussed and examples of noncharged micrographs of specimens from both life and material science fields are presented.

Studies concerning assessment of the image quality in scanning electron microscopes and studies evaluating the detective efficiency of the secondary electrical (SE) detectors in these microscopes must be based on statistics of SE emission. The vast majority of previous studies have applied Poisson statistics, although their prerequisites have not been satisfied in must cases. This paper is concerned with the limits to the applicability of Poisson statistics to SE emission. Adequate definition of a non-Poisson factor in the variance of the number of SEs emitted is discussed. and a simple formula for this factor is derived for the low yield case in which both the primary and the backscattered electron are assumed not to release more than one SE. These conditions are met with conductive specimens composed of light elements at primary electron (PE) energies of tens of keV. For the lightest specimens, such as carbon, the non-Poisson factor can even be neglected for PEs >10 keV.

Significant differences in backscattered electron (BSE) yields exist between the surfaces cleaned by methods used in electron microscopy and spectroscopy. These differences have been observed for Au, Cu and Al specimens, and are interpreted on the basis of simulated BSE yields. Composition and thickness of the surface contamination layers, responsible for the differences, are estimated. The results (7 nm of carbon on Au or 3 nm of oxide on Al) remain within expectation and indicate that the BSE yield measurements and BSE images should be interpreted cautiously. Peculiar results are obtained for Cu, perhaps due to a different cleaning procedure. A new concept of an information depth for the BSE signal is introduced as a depth within which the total BSE yield can be modelled as composed of the yields of layers proportional to their thickness weighted by the escape depths. This concept proved satisfactory for thin surface layers and brought the information depth values 2 to 4 times smaller than first estimated, i.e. half the penetration depth.

The real point resolution of an SEM image is treated in a two-dimensional model where the decisive quantity is the root-mean-square distance of the emitted electron from the pixel centre. This quantity is computed taking into account the direct illumination of the specimen surface by the primary spot the dimensions of which are given by the electron optical column and the indirect illumination from a virtual source of the backscattered electrons in the specimen depth the properties of which depend on the specimen. Because the second order movement of the full distribution is considered here instead of some measure of the central narrow peak of secondaries, the backscattered electron influence significantly deteriorates the resulting resolution. Reasonable approximations regarding both contributions, particularly the Monte-Carlo modelling of the backscattering process by algorithms providing acceptable results down to 1 keV and the approximate relations describing the secondary and backscattered electron emission again down to 1 keV, enabled us to bring the considerations up to numerical results for some typical instruments, namely a "cheap" SEM, a "top" SEM and a low-energy SEM (LESEM) adapted from the cheap SEM by using the cathode lens. The optimum landing energy providing the best point resolution, computed for the individual chemical elements, falls into the range 1 to 5 keV for the cheap SEM and it remains around 1 keV (with some uncertainty caused by the approximations mentioned) for both the top SEM and LESEM. Similarly, the real resolution for the elements ranges between 16 and 45 nm when the cheap SEM with a 3.4 nm nominal spotsize at 30 keV is used, between 3.5 and 9 nm for the 0.7 nm top SEM and between 5.5 and 7 nm for the cheap SEM adapted to LESEM.

Low energy microscopy is treated as the low energy limit of electron microscopy as a whole in all its basic branches, i.e. the emission, transmission and scanning microscopies. The instrumental and methodological aspects are briefly discussed. These include the interaction of electrons with a solid, the contrast formation mechanisms, the instrumentation problems and actual progress achieved in all three microscopies, from the point of view of lowering the energy of electrons, impacting or leaving the specimen, down to the low energy range below 5 keV and the very low energy range below 50 eV.

High resolution can be obtained in the scanning electron microscope (SEM) for a very low landing energy of electrons, even for that below 50 eV, when a cathode lens is used with the specimen as a cathode held at a high negative potential but the detection of signal electrons is totally different compared with classical SEM. Primary electrons with an energy of the order of tens of keV are decelerated in the field of the cathode lens to a very low landing energy and signal electrons originating in the specimen are accelerated and collimated by the same field to a narrow beam with an electron energy nearly the same as that of the primary beam. To detect these signal electrons we must deflect them from the optical axis without deteriorating the properties of the primary beam. The design of a novel type of separator of the primary and signal electrons consisting of two stages, each of them formed by the electric and magnetic crossed fields, is presented, together with calculated trajectories for both primary and signal electrons.

We demonstrate the possibility to examine the free-standing foils of thicknesses in units of nm in the scanning low energy electron microscope, using both reflected and transmitted electrons. Very high contrast has been obtained in dependence on the thickness and structure of the foil. A contribution of secondary electrons to the forward scattered electron signal is discussed and a way of suppressing it is presented. Examples of reflected, total transmitted and dark field transmitted electron signal for two graphene-like samples are shown. Dependence of the transmitted signal on the electron energy is observed.

Minimum necessary adaptations are described that are sufficient for obtaining very low energy electron micrographs (VLEEMs) from commercially available routine scanning electron micrographs (SEMs) with the electrons accelerated to an energy of the order of tens of keV. A cathode lens inserted into the specimen chamber enables one to decelerate electrons in front of the specimen surface to a desired low landing energy, which can be freely varied even down to zero. When a potential slightly more negative than the accelerating voltage is applied, a scanning mirror electron microscopy mode can be effected. The achievable point resolution at very low energies proves to be not too dependent on the objective lens parameters, so that the physical limit of aberrations of the homogeneous field of the cathode lens is nearly attainable. The detection efficiency for the standard Everhart-Thornley secondary electron detector is discussed, and results for the routine Tesla BS 340 SEM are presented.

We have developed a Scanning Low Energy Electron Microscope (SLEEM) based on the Cathode Lens (CL) principle [1]. A resolution of 4.5 nm at 20 eV, 0.8 nm at 200 eV and 0.5 nm at 15 keV primary beam energy can nowadays be obtained in a commercially available instrument [2]. One of the main advantages of operation at low energies is the decrease in the interaction volume from approximately 1 μιη at 10 keV to 10 nm at 100 eV. The material contrast can be optimised and the charging effect suppressed at a tailored electron energy. Wave-optical contrasts are also available beneath 50 eV. The specimen may be immersed in a strong magnetic field in addition to an electrostatic field in order to obtain a small spot size across the whole energy range. The same fields influence the signal trajectories, so we can choose which part of the angular and energy distributions of emitted electrons are to be collected. Certain arrangements provide strong crystallographic contrast. Imaging conditions have been tailored to various material types. Experiments have been performed in an experimental ultrahigh vacuum (UHV) SLEEM and in an XHR SEM Magellan 400L.

One of the well-proven and efficient methods of obtaining a very low-energy impact of primary electrons in the scanning electron microscope is to introduce a retarding field element below the pole piece of the objective lens (OL). It is advantageous to use the specimen alone as the negatively biased electrode (i.e., cathode of the cathode lens). The optical power of the cathode lens modifies some of the standard parameters of the image formation such as relation of working distance to OL excitation or magnification to the scanning coils current, the impact angle of primary electrons, and so forth. In computer-controlled electron microscopes these parameters, particularly with regard to focusing and magnification, can be corrected automatically. Derivation of algorithms for such corrections and their experimental verifications are presented in this paper. Furthermore, a more accurate analytical expression for the focal length of an aperture lens is derived.

Extended abstract of a paper presented at Microscopy and Microanalysis 2012 in Phoenix, Arizona, USA, July 29 – August 2, 2012.

A novel principle of an in-lens detector of very slow electrons is described and the detector efficiency discussed. The detector was built into a coaxial column for a Cylindrical Mirror Analyser for Auger electron microanalysis. In order to obtain a very low energy scanned imaging, a cathode lens was formed between the final electrode of the column and a negatively biased specimen. The signal electrons accelerated within the cathode lens field enter the column and after being mirrored back impact a micro-channel-plate based detector fitted around the optical axis. The acceptance of the detector, expressed as a ratio of the number of electrons impacting the detector to the full emission of a cosine source, was calculated to be 0.86 for 1 eV and 0.985 for 10 eV electrons. Then, the efficiency of conversion into output pulses is 0.35 and 0.31, respectively; these parameters are superior to those of conventional SEM detectors for secondary electrons. Micrographs taken at low energies ranging down to units of eV are presented.

The backscattering contrast was studied using silicon-metal-film sandwiches in which the incomplete metal layer consists of a regular array of strips. For various combinations of metals and thin film materials, data concerning contrasts of the strips in Auger emission are presented. For different configurations the Auger image contrast varies in the magnitude and even contrast reversal is observed in the dependence on the primary energy. It even varies for the different constituents of the surface films.

This paper concerns the problem of testing the image resolution in scanned electron micrographs, namely from the point of view of the image contrast for the standard gold/carbon test specimen within the full energy scale, down to eV units. Microscopes equipped with a cathode lens are considered and experimental results are presented for three devices differing in vacuum conditions and fields surrounding the specimen. At very low energies, the contrast is shown to either invert or disappear and this ambiguity is discussed and confronted with data simulated on the basis of measured electron yields from gold and carbon. It is concluded that the observations can be explained in terms of the surface cleanliness and strength of the surrounding fields.