A TEM phase plate loading system with loading monitoring and nano-positioning functions

We present a phase plate loading system developed for a commercial transmission electron microscope (TEM). Our system can be installed without modifying the optical design of the TEM. This system is equipped with a loading monitoring set that allows users to easily and safely locate the phase plate between the pole pieces, and also comes with an airlock that permits quick loading of a phase plate without the need to re-vent the TEM column. The system uses a home-made three-axis nano-positioner to precisely position the phase plate hole at the desired location. Our system has a precision of ∼10 nm, an improvement of one order of magnitude compared with the precision of a phase plate holder modified from an objective aperture. We demonstrate the successful installation and the use of the loading system to place a phase plate at the desired position. Our phase plate loading system can be used to accommodate various types of phase plates and thus provides a good way to greatly speed up the development of TEM phase plates.     

Optimizing the phase shift and the cut-on periodicity of phase plates for TEM

Images acquired with a phase plate often exhibit fringing and/or contrast reversal artifacts. The two basic parameters controlling the performance of the phase plate are phase shift and cut-on periodicity. We investigate theoretically and numerically the effect of these parameters on the image quality. The analysis covers not just the typical negative phase shift phase plates but also positive phase shift ones. The theoretical study derives formulas for calculating the optimal phase plate phase shift and for the maximum achievable contrast with a given specimen. Two figures of merit - fidelity and contrast - were defined and used to quantify the numerical results. Larger cut-on periodicities provide better performance with higher contrast and less artifacts in the images. Both, the theoretical results and the simulations indicate that positive phase shift phase plates generate higher contrast with better linearity and are free from contrast reversal artifacts. However, with such phase plates the amplitude and the phase contrast components are opposed to each other and the simulations show stronger fringing outside of objects. Based on these results it is difficult to predict if and to what extent the positive phase shift phase plates will be advantageous in practice. Two methods for reduction of fringing artifacts were compared—tapered phase plate and low-frequency amplification software filter. Overall the software solution produced better results and is much easier to implement than modifying the hardware of the phase plate to realize the taper.     

Characterization of Si nanocrystals by different TEM-based techniques

Silicon nanocrystals (Si-nc) embedded in SiO₂ matrix and obtained by ion implantation (50 keV, 1.0×10¹⁷ Si/cm²) were characterized by means of three different transmission electron microscopy (TEM) techniques: Dark Field (DF), Scanning TEM Annular Dark Field (STEM-ADF) and Z contrast. The strengths and weaknesses of each technique for the characterization of the Si-nc were evaluated and discussed. DF imaging, which has the best contrast, was chosen to give the average Si-nc size evaluated to 5.6 nm. On the other hand, STEM-ADF, which is only sensitive to the crystalline phase, provided an evaluation of the Si-nc density of 3.27×10¹⁷ nc/cm³. Finally, comparison between the STEM-ADF and Z contrast imaging permitted to evaluate the amorphous phase remaining after the annealing to around 12%.     

Passive control of circular cylinder wake in shallow flow

The control of vortex shedding of a circular cylinder in shallow water using a splitter plate located in the downstream of the circular cylinder was studied by employing particle image velocimetry (PIV) technique. Experiments were carried out in a water channel having a test section of 8000 mm × 1000 mm × 750 mm dimensions at a Reynolds number of 6250. The length of the splitter plate (L) was varied within the range of 0.5 ? L/D ? 2 with an increment of 0.5. The plate was submerged into water at different height ratios (h_p/h_w) such as 0.25, 0.5, 0.75 and 1.0. Mean velocity vector field, corresponding vorticity contours, streamline topologies and turbulent quantities were calculated using 300 instantaneous velocity vector field measured by PIV. As the ratio of h_p/h_w increases, the effect of the splitter plate on the suppression of the vortex shedding increases. Flow characteristics and examination of spectra indicate that Karman vortex shedding is attenuated pronouncedly for the cases of L/D ? 1 and h_p/h_w ? 0.75. The transverse Reynolds normal stress is more effective on the attenuation of turbulent kinetic energy than the streamwise Reynolds normal stress. The value of peak transverse Reynolds normal stress is reduced to 90% of that of the bare cylinder at most.     

Transmission electron microscopy at 20 kV for imaging and spectroscopy

The electron optical performance of a transmission electron microscope (TEM) is characterized for direct spatial imaging and spectroscopy using electrons with energies as low as 20 keV. The highly stable instrument is equipped with an electrostatic monochromator and a C_S-corrector. At 20 kV it shows high image contrast even for single-layer graphene with a lattice transfer of 213 pm (tilted illumination). For 4 nm thick Si, the 200 reflections (271.5 pm) were directly transferred (axial illumination). We show at 20 kV that radiation-sensitive fullerenes (C₆₀) within a carbon nanotube container withstand an about two orders of magnitude higher electron dose than at 80 kV. In spectroscopy mode, the monochromated low-energy electron beam enables the acquisition of EELS spectra up to very high energy losses with exceptionally low background noise. Using Si and Ge, we show that 20 kV TEM allows the determination of dielectric properties and narrow band gaps, which were not accessible by TEM so far. These very first results demonstrate that low kV TEM is an exciting new tool for determination of structural and electronic properties of different types of nano-materials.     

Structural imaging of β-Si3N4 by spherical aberration-corrected high-resolution transmission electron microscopy

Modern transmission electron microscopes (TEM) allow utilizing the spherical aberration coefficient as an additional free parameter for optimizing resolution and contrast. By tuning the spherical aberration coefficient of the objective lens, isolated nitrogen atom columns as well as the Si–N dumbbells within the six-membered ring were imaged in β-Si₃N₄ along [0 0 0 1] and [0 0 0 1¯] projections with a dumbbell spacing of 0.94 Å in white atom contrast. This has been obtained with negative or positive spherical aberration coefficient. We clarify contrast details in β-Si₃N₄ by means of extended image calculations. A simple procedure has been shown for pure phase imaging, which is restricted to linear imaging conditions.     

Grain boundary enrichment in the FePt polymorphic A1 to L10 phase transformation

A series of Fe_54±1Pt_46±1 thin films have been sputter-deposited and annealed at various times and temperatures to facilitate the A1 to L1₀ polymorphic phase transformation. The annealing times span one minute to tens of minutes over temperatures of 300–800 °C. The films were characterized by X-ray and electron diffraction and atom probe tomography. This time–temperature regime provides ‘snap-shots’ into the compositional segregation evolution at the grain boundaries during the polymorphic phase transformation. The as-deposited A1 phase showed a preferential segregation of Pt to the grain boundaries. The reduction of Pt enrichment at the boundaries was observed for all L1₀ ordered films.     

Imaging of soft and hard materials using a Boersch phase plate in a transmission electron microscope

Using two levels of electron beam lithography, vapor phase deposition techniques, and FIB etching, we have fabricated an electrostatic Boersch phase plate for contrast enhancement of weak phase objects in a transmission electron microscope. The phase plate has suitable dimensions for the imaging of small biological samples without compromising the high-resolution capabilities of the microscope. A micro-structured electrode allows for phase tuning of the unscattered electron beam, which enables the recording of contrast enhanced in-focus images and in-line holograms. We have demonstrated experimentally that our phase plate improves the contrast of carbon nanotubes while maintaining high-resolution imaging performance, which is demonstrated for the case of an AlGaAs heterostructure. The development opens a new way to study interfaces between soft and hard materials.     

Pawley and Rietveld refinements using electron diffraction from L1₂-type intermetallic Au₃Fe₁-x nanocrystals during their in-situ order-disorder transition

During the in-situ order-disorder transition of intermetallic L1₂-type Au₃Fe_1−x nanocrystals, structural information has been retrieved from their electron diffraction patterns based on the Pawley refinement that is unrelated to the electron kinematical or dynamical scattering nature as well as the Rietveld refinement using a kinematical approximation. At room temperature, it was found that the nanocrystals contain approximately x=40% vacancies at the Fe site. Based on in-situ heating this phase displayed an irreversible order-disorder transition, with the transition temperature between 553 and 593 K. A sudden increase in lattice parameter was detected during the first heating from the ordered phase, while the second heating of the disordered phase showed only a linear relationship with temperature. From the lattice parameter measurement of the disordered phase, the coefficient of thermal expansion was estimated as 1.462×10⁻⁵ K⁻¹. The long-range order parameter S was determined by the refined site occupancies, as well as the integrated intensities of the superlattice (1 0 0) and fundamental (2 2 0) reflections using the Pawley and Rietveld refinements during the order-disorder transition. Considering the dynamical scattering effect, Blackman two-beam approximation theory was applied to corrected S, which slightly attenuated after the correction. A comparison of the electron diffraction with X-ray diffraction data was made. It was demonstrated that elemental and structural information could be retrieved through quantitative electron diffraction studies of the nanomaterials. Since the Pawley refinement algorithm does not include the electron scattering event, it is especially useful to refine the electron diffraction data regardless of the sample thickness.     

Construction of an organic crystal structural model based on combined electron and powder X-ray diffraction data and the charge flipping algorithm

The structure of an organic dye 1,5-diaminoanthraquinone (DAAQ) nanowire was studied by both electron diffraction and X-ray powder diffraction. The unit cell of the crystal was determined from a series of tilted selected area electron diffraction patterns (monoclinic: a=3.78 Å, b=9.73 Å, c=15.01 Å and β=82.4°). By using precession electron diffraction, the following extinction conditions were determined, 0k0: k=2n and 00l: l=2n, which give the space group as P2₁/C (no. 14). The powder charge flipping algorithm was applied to resolve the phase problem and the structural model of the DAAQ crystal was built.     

Three dimensional atom probe imaging of GaAsSb quantum rings

Unambiguous evidence of ring-shaped self-assembled GaSb nanostructures grown by molecular beam epitaxy is presented on the basis of atom-probe tomography reconstructions and dark field transmission electron microscopy imaging. The GaAs capping process causes a strong segregation of Sb out of the center of GaSb quantum dots, leading to the self-assembled GaAs_xSb_1−x quantum rings of 20-30 nm in diameter with x∼0.33.     

Fabrication and characterization of ZnO thin film for hydrogen gas sensing prepared by RF-magnetron sputtering

A ZnO thin film-based gas sensor was fabricated using a SiO₂/Si substrate with an integrated platinum comb-like electrode and heating element. The structural characteristics, morphology, and surface roughness of the as-grown ZnO nanostructure were investigated. The optical properties were examined by UV–vis spectrophotometry. The film revealed the presence of a c-axis oriented (0 0 2) phase of 20.8 nm grain size. The sensor response was tested for hydrogen concentrations of 50, 70, 100, 200, 400, and 500 ppm at operating temperatures ranging from 250 °C to 400 °C. The sensitivity toward 50 and 200 ppm of hydrogen at the optimum operating temperature of 350 °C were about 78% and 98%, respectively. The response was linear within the range of 50–200 ppm of hydrogen concentration. Our results demonstrated the potential application of ZnO nanostructure for fabricating cost-effective and high-performance gas sensors.     

A new aberration-corrected,energy-filtered LEEM/PEEM instrument. I. Principles and design

We describe a new design for an aberration-corrected low energy electron microscope (LEEM) and photo electron emission microscope (PEEM), equipped with an in-line electron energy filter. The chromatic and spherical aberrations of the objective lens are corrected with an electrostatic electron mirror that provides independent control over the chromatic and spherical aberration coefficients C_c and C₃, as well as the mirror focal length, to match and correct the aberrations of the objective lens. For LEEM (PEEM) the theoretical resolution is calculated to be ∼1.5 nm (∼4 nm). Unlike previous designs, this instrument makes use of two magnetic prism arrays to guide the electron beam from the sample to the electron mirror, removing chromatic dispersion in front of the mirror by symmetry. The aberration correction optics was retrofitted to an uncorrected instrument with a base resolution of 4.1 nm in LEEM. Initial results in LEEM show an improvement in resolution to ∼2 nm.     

Field evaporation behavior in [0 0 1] FePt thin films

Though the atom probe has provided unprecedented atomic identification and spatial imaging capability, the basic reconstruction assumption of a smooth hemispherical tip shape creates significant challenges in yielding high fidelity chemical information for atomic species with extreme differences in fields required for field evaporation. In the present study, the evaporation behavior and accompanying artifacts are examined for the super-cell lattice structure of L1₀ FePt, where alternating Fe and Pt planes exist in the [0 0 1] orientation. Elemental Fe and Pt have significant differences in field strengths providing a candidate system to quantify these issues. Though alloys can result in changes in the elemental field strength, the intrinsic nature of elemental planes in [0 0 1] L1₀ provides a system to determine to what extent basic assumptions of elemental field strengths can break down in understanding reconstruction artifacts in this intermetallic alloy. The reconstruction of field evaporation experiments has shown depletion of Fe at the (0 0 2) pole and zone axes. Compositional profiles revealed an increase in Fe and atom count moving outward from the pole. The depletion at the low indexed pole and zone axes was determined to be the result of local magnification and electrostatic effects. The experimental results are compared to an electrostatic simulation model.     

Medium-range order in molecular materials: Fluctuation electron microscopy for detecting fullerenes in disordered carbons

During a fluctuation electron microscopy (FEM) study of disordered carbons, we found that samples containing C₆₀ exhibit a normalized variance peak at 7.1 nm⁻¹ that appears to be a unique indicator of tight curvature in layered materials. This peak is associated with the characteristic in-plane carbon–carbon bond distance of ∼0.14 nm in graphene. Diffraction from this spacing is normally forbidden in planar graphene (and graphite), but becomes allowed when the layer structure is interrupted. Such interruptions arise at the edges of graphite fragments and also when 5-rings are incorporated into a layer. We show that the curvature induced by a high density of 5-rings, such as that in C₆₀, can dominate the variance peak at 7.1 nm⁻¹. FEM simulations reveal that the variance peak at ∼7.1 nm⁻¹, which we label F₁, is one of several fullerene-signature peaks, with others occurring at Q values of 10.6 nm⁻¹ (F₂) and 12.4 nm⁻¹ (F₃). We conclude that FEM is a sensitive method for detecting dilute quantities of highly curved pentagon-rich fullerenes, such as C₆₀, when dispersed within disordered graphitic carbon.     

Energy resolution of an Omega-type monochromator and imaging properties of the MANDOLINE filter

We report on the energy resolution properties of an Omega-type monochromator. In a TEM/STEM setup with a MANDOLINE filter and extreme stability of the high voltage and the filter current, an energy resolution of 43 meV for 0.1 s exposure time and 87 meV for 100 s exposure time was measured at 200 kV with 40 meV monochromator slit width. The monochromized zero-loss peaks are additionally characterized by their edge steepness. Moreover a drop in the monochromized zero-loss peak by 10³ after 260 meV can be obtained even without deconvolution. For small fields of view, the energy resolution mostly does not depend on the MANDOLINE filter. With the Corrected OMEGA filter an energy resolution of 41 meV was measured for 0.03 s exposure time at 200 kV with 30 meV monochromator slit width and 77 meV for 50 s exposure time at 80 kV with 40 meV monochromator slit width. Furthermore, the MANDOLINE filter’s setup and imaging properties are presented such as isochromaticity (<5 meV) and transmissivity (T_(1 eV)=17,400 nm²), which set a new standard for imaging energy filters and allow EFTEM spectrum imaging with energy windows ≤200 meV and reasonable fields of view.     

Investigation of some dielectric properties of phosphate glasses doped with iron oxides,by a microwave technique

The effects of iron ions on dielectric properties of lithium sodium phosphate glasses were studied by non-usual, fast and non-destructive microwave techniques. The dielectric constant (ε′), insertion loss (L) and microwave absorption spectra (microwave response) of the selected glass system xFe₂O₃·(1 − x)(50P₂O₅·25Li₂O·25Na₂O), being x = 0, 3, 6, … , 15 expressed in mol.%, were investigated. The dielectric constant of the samples was investigated at 9.00 GHz using the shorted-line method (SLM) giving the minimum value of ε′ = 2.10 ± 0.02 at room temperature, and increasing further with x, following a given law. It was observed a gradual increasing slope of ε′ in the temperature range of 25 ? t ? 330 °C, at the frequency of 9.00 GHz. Insertion loss (measured at 9.00 GHz) and measurements of microwave energy attenuation, at frequencies ranging from 8.00 to 12.00 GHz were also studied as a function of iron content in the glass samples.     

Effect of molybdenum tri-oxide molar ratio on the optical and some physical properties of tellurite-vanadate-molybdate glasses

Glasses with composition (60 − x)V₂O₅-40TeO₂ − x MoO₃ with 20 ? x ? 60 (in mol%) have been prepared using the usual melt quenching method. The optical absorption spectra of the glasses have been recorded in the wavelength range 300-800 nm. The position of the absorption edge and therefore the optical band gap values were found to be depend on the glass composition. For these glasses, the optical band gap was found to be in the range 2.03-2.86 eV with increasing of MoO₃ concentration. The absorption spectrum fitting method was employed to obtain the energy gap. In this method, only the measurement of the absorbance spectrum of the glass is needed. For each sample, the width of the band tail was determined. Also, the density and glass transition temperature values indicate that the rigidity and packing of the samples increase with increase in MoO₃ concentration as a network former.     

Optimum HRTEM image contrast at 20 kV and 80 kV--exemplified by graphene

The dependence of high-resolution transmission electron microscopy (HRTEM) image contrast of graphene on the adjustable parameters of an aberration-corrected microscope operated at 80 and 20 kV has been calculated and, for 80 kV, compared with measurements. We used density functional theory to determine the projected atom potential and obtained the image intensity by averaging over the energy distribution of the imaging electrons, as derived from the electron energy loss spectroscopy measurements. Optimum image contrast has been determined as a function of energy spread of the imaging electrons and chromatic aberration coefficient, showing that significant improvement of contrast can be achieved at 80 kV with the help of a monochromator, however at 20 kV only with chromatic aberration correction and bright atom contrast conditions.     

Thermal sensors based on p-Pb0.925Yb0.075Te:Te and n-Pb0.925Yb0.075Se0.2Te0.8 thin films grown using thermal evaporation method

We utilize p-Pb_0.925Yb_0.075Te:Te and n-Pb_0.925Yb_0.075Se_0.2Te_0.8 ingots in a standard solid-state microwave synthesis route to fabricate thermally evaporated thin films. The nanostructure and composition of the films were studied through X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and energy dispersive X-ray spectroscopy (EDX). The Seebeck coefficient and electrical conductivity were measured at a temperature range of 298–523 K. The micro-thermoelectric devices were composed of 20 pairs and 10 pairs of p-Pb_0.925Yb_0.075Te:Te and n-Pb_0.925Yb_0.075Se_0.2Te_0.8 thin films on glass substrates, respectively. The dimensions of the thin films thermoelectric generators which comprised of 10-pair were 12 mm × 10 mm, whereas, 20-pair were 23 mm × 20 mm, respectively of legs connected through aluminum electrodes. The serial 20-pair p–n thermocouples generated a maximum output open-circuit voltage of 275.3 mV and a maximum output power of 54.37 nW at a temperature difference of ΔT = 162 K; the values are 109.4 mV and 16.68 nW at ΔT = 162 K for the 10-pair thermocouples, respectively.