Vibrational spectroscopy in the electron microscope.

Vibrational spectroscopies using infrared radiation, Raman scattering, neutrons, low-energy electrons and inelastic electron tunnelling are powerful techniques that can analyse bonding arrangements, identify chemical compounds and probe many other important properties of materials. The spatial resolution of these spectroscopies is typically one micrometre or more, although it can reach a few tens of nanometres or even a few ångströms when enhanced by the presence of a sharp metallic tip. If vibrational spectroscopy could be combined with the spatial resolution and flexibility of the transmission electron microscope, it would open up the study of vibrational modes in many different types of nanostructures. Unfortunately, the energy resolution of electron energy loss spectroscopy performed in the electron microscope has until now been too poor to allow such a combination. Recent developments that have improved the attainable energy resolution of electron energy loss spectroscopy in a scanning transmission electron microscope to around ten millielectronvolts now allow vibrational spectroscopy to be carried out in the electron microscope. Here we describe the innovations responsible for the progress, and present examples of applications in inorganic and organic materials, including the detection of hydrogen. We also demonstrate that the vibrational signal has both high- and low-spatial-resolution components, that the first component can be used to map vibrational features at nanometre-level resolution, and that the second component can be used for analysis carried out with the beam positioned just outside the sample--that is, for 'aloof' spectroscopy that largely avoids radiation damage.

Properties of Dipole-Mode Vibrational Energy Losses Recorded From a TEM Specimen.

The authors discuss the dipole vibrational modes that predominate in the energy-loss spectra of ionic materials below 1 eV, concentrating on thin-film specimens of typical transmission electron microscopy (TEM) thickness. The thickness dependence of the intensity is shown to be a useful guide to the bulk or surface character of vibrational peaks. The lateral and depth resolution of the energy-loss signal is investigated with the aid of finite-element calculations.

Secondary-electron imaging of bulk crystalline specimens in an aberration corrected STEM.

Atomic-scale electron microscopy traditionally probes thin specimens, with thickness below 100 nm, and its feasibility for bulk samples has not been documented. In this study, we explore the practicality of scanning transmission electron microscope (STEM) imaging with secondary electrons (SE), using a silicon-wedge specimen having a maximum thickness of 18 µm. We find that the atomic structure is present in the entire thickness range of the SE images although the background intensity increases moderately with thickness. The consistent intensity of secondary electron (SE) images at atomic positions and the modest increase in background intensity observed in silicon suggest a limited contribution from SEs generated by backscattered electrons, a conclusion supported by our multislice calculations. We conclude that achieving atomic resolution in SE imaging for bulk specimens is indeed attainable using aberration-corrected STEM and an aberration-corrected scanning electron microscope (SEM) may have the capacity for atomic-level resolution, holding great promise for future strides in materials research.

NanoMi: An open source electron microscope hardware and software platform.

We outline a public license (open source) electron microscopy platform, referred to as NanoMi. NanoMi offers a modular, flexible electron microscope platform that can be utilized for a variety of applications, such as microscopy education and development of proof-of-principle experiments, and can be used to complement an existing experimental apparatus. All components are ultra-high vacuum compatible and the electron optics elements are independent from the vacuum envelope. The individual optical components are mounted on a 127 mm (5-inch) diameter half-pipe, allowing customizing of electron optics for a variety of purposes. The target capabilities include SEM, TEM, scanning TEM (STEM), and electron diffraction (ED) at up to 50 keV incident electron energy. The intended image resolution in SEM, TEM and STEM modes is ≈ 10 nm. We describe the existing components and the interfaces among components that ensure their compatibility and interchangeability. The paper provides a resource for those who consider building or utilizing their own NanoMi.

Phase plates in the transmission electron microscope: operating principles and applications.

In this paper, we review the current state of phase plate imaging in a transmission electron microscope. We focus especially on the hole-free phase plate design, also referred to as the Volta phase plate. We discuss the implementation, operating principles and applications of phase plate imaging. We provide an imaging theory that accounts for inelastic scattering in both the sample and in the hole-free phase plate.

Water-soluble J-type rosette nanotubes with giant molar ellipticity.

A new self-assembling tricyclic module (×K1) featuring the Watson-Crick H-bonding arrays of guanine and cytosine fused to an internal pyridine ring was synthesized. When dissolved in water at room temperature, this module rapidly self-assembles into hexameric rosettes, which then stack to form J-type rosette nanotubes (RNTs) with increased inner/outer diameters and the largest molar ellipticity ever reported (4 × 10(6) deg·M(-1)·m(-1)). Using a combination of imaging and spectroscopic techniques we established the structure of ×K1-RNT and have shown that the extended π system of the self-assembling module resulted in a new family of J-type RNTs with enhanced intermodular electronic communication.

Imaging of radiation-sensitive samples in transmission electron microscopes equipped with Zernike phase plates.

We have optimized a bright-field transmission electron microscope for imaging of high-resolution radiation-sensitive materials by calculating the imaging dose n(0) needed to obtain a signal-to-noise ratio (SNR)=5. Installing a Zernike phase plate (ZP) decreases the dose needed to detect single atoms by as much as a factor of two at 300 kV. For imaging larger objects, such as Gaussian objects with full-width at half-maximum larger than 0.15 nm, ZP appears more efficient in reducing the imaging dose than correcting for spherical aberration. The imaging dose n(0) does not decrease with extending of chromatic resolution limit by reducing chromatic aberration, using high accelerating potential (U(0)=300 kV), because the image contrast increases slower than the reciprocal of detection radius. However, reducing chromatic aberration would allow accelerating potential to be reduced leading to imaging doses below 10 e(-)/A(2) for a single iodine atom when a CS-corrector and a ZP are used together. Our simulations indicate that, in addition to microscope hardware, optimization is heavily dependent on the nature of the specimen under investigation.

Low-dose performance of parallel-beam nanodiffraction.

We evaluate the low-dose performance of parallel nano-beam diffraction (NBD) in the transmission electron microscope as a method for characterizing radiation sensitive materials at low electron irradiation dose. A criterion, analogous to Rose's, is established for detecting a diffraction spot with desired signal-to-noise ratio. Our experimental data show that a dose substantially lower than in high-resolution bright-field imaging is sufficient to determine structure and orientation of individual nanoscale objects embedded in amorphous matrix. In an instrument equipped with a cold field-emission gun it is possible to form a probe with sub-3 nm diameter and sub-0.3 mrad convergence angle with sufficient beam current to record a diffraction pattern with less than 0.2 s acquisition time. The interpretation of NBD patterns is identical to that of selected area diffraction patterns. We illustrate the physical principles underlying good low-dose performance of NBD by means of a phase grating. The electron irradiation dose needed to detect a diffraction peak in NBD is found proportional to 1/N2, where N is the number of lattice planes contributing to the peak.

Thermal expansion coefficient measurement from electron diffraction of amorphous films in a TEM.

We measured the linear thermal expansion coefficients of amorphous 5-30 nm thick SiN and 17 nm thick Formvar/Carbon (F/C) films using electron diffraction in a transmission electron microscope. Positive thermal expansion coefficient (TEC) was observed in SiN but negative coefficients in the F/C films. In case of amorphous carbon (aC) films, we could not measure TEC because the diffraction radii required several hours to stabilize at a fixed temperature.

Bright-field TEM imaging of single molecules: dream or near future?

We examine the suitability of spherical aberration (C(S))-corrected (CS) and uncorrected (UC) transmission electron microscopes (TEM) for conventional bright-field imaging of radiation-sensitive materials. We have chosen an individual molecule suspended in vacuum as a hypothetical example of a well-defined radiation-sensitive sample. We find that for this particular sample, CS instruments provide about 30% improvement over an UC instrument in terms of signal/noise ratio per unit electron dose at 300kV. The lowest imaging doses can be achieved in CS instruments equipped with high-brightness electron source operated at low incident electron energies. Our calculations suggest that it may be possible to image individual, iodine- or bromine-substituted organic molecules in bright-field mode, at doses lower than the accepted values for radiation damage of aromatic molecules.

Alternative methods of identifying the oxidation of metallic nanoparticles embedded in a matrix.

We compare methods for valence-state analysis based on energy-loss near-edge structure (ELNES), including the white-line ratio (WLR), pre-edge peak (prepeak) and post-edge peak (postpeak) techniques. Starting from multiple-scattering calculations, we correlate the appearance of a prepeak in the O-K edge and postpeak in the L-edge with oxidation of a transition metal (TM). The ability to use more than one technique is especially advantageous for a nanocomposite of metallic nanoparticles embedded in a matrix, as we show for the case of iron nanoparticles in a silica matrix.

Valence state map of iron oxide thin film obtained from electron spectroscopy imaging series.

This paper demonstrates the applicability of electron-spectroscopic imaging (ESI) for valence-state mapping of the iron oxide system. We have previously developed a set of signal-processing methods for an ESI series, to allow mapping of sp(2)/sp(3) ratio, dielectric function and energy bandgap. In this study, these methods are applied to generate a valence-state map of an iron oxide thin film (Fe/alpha-Fe(2)O(3)). Two problems, data undersampling and a convolution effect associated with extraction of the image-spectrum from the core loss image series, were overcome by using cubic-polynomial interpolation and maximum-entropy deconvolution. As a result, the reconstructed image-spectrum obtained from the ESI series images has a quality as good as that of conventional electron energy-loss spectra. The L(3)/L(2) ratio of the reconstructed ESI spectrum is determined to be 3.30+/-0.30 and 5.0+/-0.30 for Fe and alpha-Fe(2)O(3), respectively. Our L(3)/L(2) ratio mapping shows an accurate correspondence across the Cu/Fe/alpha-Fe(2)O(3) region. The effect of delocalization and chromatic aberration on the ESI resolution is discussed and estimated to be about 2 nm for the case of L(3)/L(2) ratio mapping.

Interpretation of the postpeak in iron fluorides and oxides.

A broad post-edge peak (postpeak) in the core-loss spectrum of a relatively thick TEM specimen is readily accounted for by plural scattering of the transmitted electrons, involving a core-loss and a bulk plasmon. However, we observe a prominent postpeak, about 40 eV above iron L3 edge, even in very thin films of iron fluoride. The peak gradually disappears as fluorine is removed by electron irradiation, as indicated by decay of the fluorine K-edge and change in white-line ratio, but appears when an iron film is oxidized, therefore it appears to be characteristic of iron in an oxidized state. To study its origin, we performed real-space multiple-scattering (RSMS) calculations of the near-edge fine structure of the Fe L-edge, allowing us to discuss the origin of the postpeak within the framework of electron-scattering theory. In the belief that oxygen and fluorine anions in transition-metal compounds are strong backscatters, we propose that the postpeak is a common feature of transition metals in an oxidized state and can be used as an additional verification of such oxidization in an unknown sample.

Energy-loss near-edge fine structures of iron nanoparticles.

Body centered cubic (bcc) Fe nanoparticles were fabricated by in situ decomposition of iron fluoride films in a transmission electron microscope. Electron energy-loss near edge structure (ELNES) was used to characterize this exposure process. In particular, the L(3)/L(2) white-line intensity ratio (WLR) was used to monitor the iron valence state during exposure, and as an indicator of other properties of the iron nanoparticles. Iron nanoparticles with sizes between 2 and 20nm exhibit a constant WLR, whose value is same as that for a continuous bcc iron film, suggesting little or no dependence of the local magnetic moment or structure on the particle size. A broad but prominent peak which occurs 40eV after the L(3)-ionization threshold in the iron fluoride, is absent for a metallic iron film but reappears when the iron is converted to an oxide. Long-range ferromagnetic coupling was observed in samples densely populated with iron nanoparticles. Because there is little interaction between particles and the supporting carbon substrate, these samples provide an ideal model system for studying the influence of particle size and interparticle distance on magnetic properties.

Bring your paper into the 'Fast Lane' of the editorial process and increase your changes for final acceptance in Micron, The International Research and Review Journal for Microscopy.

In the past few years Micron has revised the scope of the journal, bringing it back to its original core values when it was founded in 1969. Micron's aim is to be the leading international microscopy and microanalysis journal, covering the latest advances in the fields of biological and physical science. In order to achieve this, the editorial team carefully revised the guidelines to authors in 2011. As a team we now find it timely to report on the outcomes of this policy change.

Accurate measurement of relative tilt and azimuth angles in electron tomography: a comparison of fiducial marker method with electron diffraction.

Electron tomography is a method whereby a three-dimensional reconstruction of a nanoscale object is obtained from a series of projected images measured in a transmission electron microscope. We developed an electron-diffraction method to measure the tilt and azimuth angles, with Kikuchi lines used to align a series of diffraction patterns obtained with each image of the tilt series. Since it is based on electron diffraction, the method is not affected by sample drift and is not sensitive to sample thickness, whereas tilt angle measurement and alignment using fiducial-marker methods are affected by both sample drift and thickness. The accuracy of the diffraction method benefits reconstructions with a large number of voxels, where both high spatial resolution and a large field of view are desired. The diffraction method allows both the tilt and azimuth angle to be measured, while fiducial marker methods typically treat the tilt and azimuth angle as an unknown parameter. The diffraction method can be also used to estimate the accuracy of the fiducial marker method, and the sample-stage accuracy. A nano-dot fiducial marker measurement differs from a diffraction measurement by no more than ±1°.

Local thickness measurement through scattering contrast and electron energy-loss spectroscopy.

Scattering contrast measurements were performed on thin films of amorphous carbon and polycrystalline Au, as well as single-crystal MgO nanocubes. Based on the exponential absorption law, mass-thickness can be obtained within 10% accuracy by measuring the incident and transmitted intensities in the same image. For mass-thickness measurement of a thin amorphous specimen, a small collection semiangle improves the measurement sensitivity, whereas for the measurement of polycrystalline or single-crystal specimens, a large collection semiangle should be used to reduce diffraction-contrast effects. EELS thickness measurements on MgO nanocubes suggest that the Kramers-Kronig sum-rule method (with correction for plural and surface scattering) gives 10% accuracy at medium collection semiangles but overestimates the thickness at small collection semiangles, due to underestimation of the surface-mode scattering. The log-ratio method, with a formula for inelastic mean free path proposed by Malis et al. (1988), provides 10% accuracy at small collection semiangle, while that proposed by Iakoubovskii et al. (2008a) is preferable for medium and large collection semiangles. As a result of this work, we provide recommendations of preferred methods and conditions for local-thickness measurement in the TEM.