Energy-filtered Transmission Electron Microscopy Images Research Articles

Resolution Models for Energy-Filtered TEM Imaging over Thick Liquid or Amorphous Layers

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Iterative Bayesian denoising based on variance stabilization using Contourlet Transform with Sharp Frequency Localization: application to EFTEM images

BackgroundDue to the presence of high noise level in tomographic series of energy filtered transmission electron microscopy (EFTEM) images, alignment and 3D reconstruction steps become so difficult. To improve the alignment process which will in turn allow a more accurate and better three dimensional tomography reconstructions, a preprocessing step should be applied to the EFTEM data series.ResultsExperiments with real EFTEM data series at low SNR, show the feasibility and the accuracy of the proposed denoising approach being competitive with the best existing methods for Poisson image denoising. The effectiveness of the proposed denoising approach is thanks to the use of a nonparametric Bayesian estimation in the Contourlet Transform with Sharp Frequency Localization Domain (CTSD) and variance stabilizing transformation (VST). Furthermore, the optimal inverse Anscome transformation to obtain the final estimate of the denoised images, has allowed an accurate tomography reconstruction.ConclusionThe proposed approach provides qualitative information on the 3D distribution of individual chemical elements on the considered sample.

Impact of Low Molecular Weight Poly(3-hexylthiophene)s as Additives in Organic Photovoltaic Devices.

Despite tremendous progress in using additives to enhance the power conversion efficiency of organic photovoltaic devices, significant challenges remain in controlling the microstructure of the active layer, such as at internal donor-acceptor interfaces. Here, we demonstrate that the addition of low molecular weight poly(3-hexylthiophene)s (low-MW P3HT) to the P3HT/fullerene active layer increases device performance up to 36% over an unmodified control device. Low MW P3HT chains ranging in size from 1.6 to 8.0 kg/mol are blended with 77.5 kg/mol P3HT chains and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) fullerenes while keeping P3HT/PCBM ratio constant. Optimal photovoltaic device performance increases are obtained for each additive when incorporated into the bulk heterojunction blend at loading levels that are dependent upon additive MW. Small-angle X-ray scattering and energy-filtered transmission electron microscopy imaging reveal that domain sizes are approximately invariant at low loading levels of the low-MW P3HT additive, and wide-angle X-ray scattering suggests that P3HT crystallinity is unaffected by these additives. These results suggest that oligomeric P3HTs compatibilize donor-acceptor interfaces at low loading levels but coarsen domain structures at higher loading levels and they are consistent with recent simulations results. Although results are specific to the P3HT/PCBM system, the notion that low molecular weight additives can enhance photovoltaic device performance generally provides a new opportunity for improving device performance and operating lifetimes.

Novel method for measurement of transistor gate length using energy-filtered transmission electron microscopy

As the feature size of devices continues to decrease, transmission electron microscopy (TEM) is becoming indispensable for measuring the critical dimension (CD) of structures. Semiconductors consist primarily of silicon-based materials such as silicon, silicon dioxide, and silicon nitride, and the electrons transmitted through a plan-view TEM sample provide diverse information about various overlapped silicon-based materials. This information is exceedingly complex, which makes it difficult to clarify the boundary to be measured. Therefore, we propose a simple measurement method using energy-filtered TEM (EF-TEM). A precise and effective measurement condition was obtained by determining the maximum value of the integrated area ratio of the electron energy loss spectrum at the boundary to be measured. This method employs an adjustable slit allowing only electrons with a certain energy range to pass. EF-TEM imaging showed a sharp transition at the boundary when the energy-filter’s passband centre was set at 90 eV, with a slit width of 40 eV. This was the optimum condition for the CD measurement of silicon-based materials involving silicon nitride. Electron energy loss spectroscopy (EELS) and EF-TEM images were used to verify this method, which makes it possible to measure the transistor gate length in a dynamic random access memory manufactured using 35 nm process technology. This method can be adapted to measure the CD of other non-silicon-based materials using the EELS area ratio of the boundary materials.

Taking Advantage of Scattering Delocalization To Reduce Radiation Damage In Vibrational or Valence-Loss EELS and Energy-Filtered TEM Images

Taking Advantage of Scattering Delocalization To Reduce Radiation Damage In Vibrational or Valence-Loss EELS and Energy-Filtered TEM Images

Electron Energy-Loss Spectroscopy and Energy-Filtered TEM Imaging for the in situ Assessment of Reduction-Oxidation Reactions in Ni-Based Solid Oxide Fuel Cells

Electron Energy-Loss Spectroscopy and Energy-Filtered TEM Imaging for the in situ Assessment of Reduction-Oxidation Reactions in Ni-Based Solid Oxide Fuel Cells

Two-dimensional percolation threshold in confined Si nanoparticle networks

Non-percolating and percolating silicon quantum dot (QD) networks were investigated by plane-view energy filtered transmission electron microscopy (EF-TEM). The Si QD networks were prepared by plasma enhanced chemical vapor deposition on free standing 5 nm Si3N4 membranes, followed by high temperature annealing. The percolation threshold from non-percolating to percolating networks is found to be in between a SiOx stoichiometry of SiO0.5 up to SiO0.7. Using the EF-TEM images, key structural parameters of the Si QD ensemble were extracted and compared, i.e., their size distribution, nearest neighbor distance, and circularity. Increasing the silicon excess within the SiOx layer results in an ensemble of closer spaced, less size-controlled, and less circular Si QDs that give rise to coupling effects. Furthermore, the influence of the structural parameters on the optical and electrical Si QD ensemble properties is discussed.

A facile method to compare EFTEM maps obtained from materials changing composition over time.

Energy Filtered Transmission Electron Microscopy (EFTEM) is an analytical tool that has been successfully and widely employed in the last two decades for obtaining fast elemental maps in TEM mode. Several studies and efforts have been addressed to investigate limitations and advantages of such technique, as well as to improve the spatial resolution of compositional maps. Usually, EFTEM maps undergo post-acquisition treatments by changing brightness and contrast levels, either via dedicated software or via human elaboration, in order to maximize their signal-to-noise ratio and render them as visible as possible. However, elemental maps forming a single set of EFTEM images are usually subjected to independent map-by-map image treatment. This post-acquisition step becomes crucial when analyzing materials that change composition over time as a consequence of an external stimulus, because the map-by-map approach doesn't take into account how the chemical features of the imaged materials actually progress, in particular when the investigated elements exhibit very low signals. In this article, we present a facile procedure applicable to whole sets of EFTEM maps acquired on a sample that is evolving over time. The main aim is to find a common method to treat the images features, in order to make them as comparable as possible without affecting the information there contained.

Addressing preservation of elastic contrast in energy-filtered transmission electron microscopy

Energy-filtered transmission electron microscopy (EFTEM) images with resolutions of the order of an Ångström can be obtained using modern microscopes corrected for chromatic aberration. However, the delocalized nature of the transition potentials for atomic ionization often confounds direct interpretation of EFTEM images, leading to what is known as “preservation of elastic contrast”. In this paper we demonstrate how more interpretable images might be obtained by scanning with a focused coherent probe and incoherently averaging the energy-filtered images over probe position. We dub this new imaging technique energy-filtered imaging scanning transmission electron microscopy (EFISTEM). We develop a theoretical framework for EFISTEM and show that it is in fact equivalent to precession EFTEM, where the plane wave illumination is precessed through a range of tilts spanning the same range of angles as the probe forming aperture in EFISTEM. It is demonstrated that EFISTEM delivers similar results to scanning transmission electron microscopy with an electron energy-loss spectrometer but has the advantage that it is immune to coherent aberrations and spatial incoherence of the probe and is also more resilient to scan distortions.

Morphological Evolution and Its Impacts on Performance of Polymer Solar Cells

In this paper, the role of fullerene loading on the nanomorphology and photovoltaic performance of alternating copolymer poly{2-octyldodecyloxy-benzo[1,2-b;3,4-b] dithiophene-alt-5,6-bis(dodecyloxy)-4,7bis(thiophen-2-yl)-benzo[c] [1,2,5]-thiadiazole} (PBDT-ABT-1) blend films was investigated. The morphology of blend films with different Phenyl C-60-butyric acid methyl ester (PCBM) mixing ratios and solvent additives was studied using atomic force microscopy (AFM) and energy-filtered transmission electron microscopy (EFTEM). AFM and EFTEM images showed difference in the intermixing of polymer with fullerene between 1:1, 1:2, and 1:3 weight ratios. Polymer/PCBM intermixed domain size increases with higher PCBM weight ratios. X-ray diffraction measurements on the pristine polymer and blend films cast without additives did not show any peaks, suggesting an amorphous nature of PBDT-ABT-1. EFTEM images from the donor/acceptor composite showed intermixed polymer-PCBM domains separated by the polymer boundary. Furthermore, EFTEM images for di-iodooctane (DIO) additive cast film revealed purer polymer domain. Photo-charge extraction by linearly increasing voltage measurement exhibited that charge extraction is highest in the nanomorphology sample with a weight ratio of 1:2, corresponding to the lowest bimolecular recombination and the highest charge carrier mobility.

Elemental mapping of interfacial layers at the cathode of organic solar cells.

One of the limitations in understanding the performance of organic solar cells has been the unclear picture of morphology and interfacial layers developed at the active layer/cathode interface. Here, by utilizing the shadow-Focused Ion Beam technique to enable energy-filtered transmission electron microscopy imaging in conjunction with X-ray photoelectron spectroscopy (XPS) experiments, we examine the cross-section of polythiophene/fullerene solar cells to characterize interfacial layers near the semiconductor-cathode interface. Elemental mapping reveals that localization of fullerene to the anode interface leads to low fill factors and S-shaped current-voltage characteristics. Furthermore, the combination of elemental mapping and XPS depth profiles of devices demonstrate oxidation of the aluminum cathode at the active layer interface for devices without S-shaped characteristics and fill factors of 0.6. The presence of a thin dielectric at the semiconductor-cathode interface could minimize electronic barriers for charge extraction by preventing interfacial charge reorganization and band-bending.

Study of the nanoscale morphology of polythiophene fibrils and a fullerene derivative.

Nanoscale blending of electron-donor and electron-acceptor materials in solution-processed bulk heterojunction organic photovoltaic devices is crucial for achieving high power conversion efficiency. We used a classic blend of poly(3-hexylthiophene)/phenyl-C61-butyric acid methyl ester (P3HT/PCBM) as a model to observe the nanoscale morphology of the P3HT fibrils and PCBM nanoclusters in the mixture. Energy-filtered transmission electron microscopy (EFTEM) clearly revealed a nanoscopic phase separation. Randomly connected and/or nonconnected P3HT fibrous networks and PCBM domains, revealed by 2-dimensional micrographs, were observed by collecting electron energy loss spectra in the range of 19-30 eV. From EFTEM images, the average length and the diameter of P3HT fibrils were found to be approximately 70 ± 5 and 15 ± 2 nm, respectively. Combining the EFTEM, selected area electron diffraction, and X-ray diffraction results, the number and spacing of the ordered chains in P3HT fibrils were determined. There were 18 ± 3 repeating units of P3HT perpendicular to the fibril, ∼184 layers of π-π stacking along the fibril, and ∼9 layers of interchain stacking within the fibril. These conclusive observations provide insight into the number of molecules found in one instance of ordered-plane stacking. This information is useful for the calculation of charge transport in semicrystalline polymers. Using cross-section samples prepared with a focused ion beam technique, the vertical morphology of each phase was analyzed. By collecting 30 eV energy loss images, the phase separation in the P3HT/PCBM system was distinguishable. A higher P3HT concentration was observed at the top of the cell, near Al contact, which could possibly cause loss of carriers and recombination due to a mismatch in the P3HT and Al energy bands.

Linking Processing Parameters and Morphological Development in Organic Photovoltaics by Energy-Filtered TEM Imaging of Model Multilayer Structures

Linking Processing Parameters and Morphological Development in Organic Photovoltaics by Energy-Filtered TEM Imaging of Model Multilayer Structures

Elemental mapping in achromatic atomic-resolution energy-filtered transmission electron microscopy.

We present atomic-resolution energy-filtered transmission electron microscopy (EFTEM) images obtained with the chromatic-aberration-corrected FEI Titan PICO at the Ernst-Ruska Centre, Jülich, Germany. We find qualitative agreement between experiment and simulation for the background-subtracted EFTEM images of the Ti-L2,3 and O-K edges for a specimen of SrTiO3 oriented down the [110] zone axis. The simulations utilize the transition potential formulation for inelastic scattering, which permits a detailed investigation of contributions to the EFTEM image. We find that energy-filtered images of the Ti-L2,3 and O-K edges are lattice images and that the background-subtracted core-loss maps may not be directly interpretable as elemental maps. Simulations show that this is a result of preservation of elastic contrast, whereby the qualitative details of the image are determined primarily by elastic, coherent scattering. We show that this effect places a constraint on the range of specimen thicknesses which could theoretically yield directly useful elemental maps. In general, interpretation of EFTEM images is ideally accompanied by detailed simulations.

Silicon nanocrystals in SiNx/SiO2 hetero-superlattices: The loss of size control after thermal annealing

Superlattices containing 3 nm thick silicon rich silicon nitride sublayers and 3 nm and 10 nm thick SiO2 barriers were prepared by plasma enhanced chemical vapor deposition. Despite the as-prepared samples represented a well-kept multilayer structure with smooth interfaces, the high temperature annealing resulted in the total destruction of multilayer structure in the samples containing 3 nm SiO2 barriers. Energy-filtered transmission electron microscopy images of these samples indicated a silicon nanoclusters formation with sizes of 2.5–12.5 nm, which were randomly distributed within the structure. Although in the sample with 10 nm SiO2 barriers some fragments of the multilayer structure could be still observed after thermal annealing, nevertheless, the formation of large nanocrystals with diameters up to 10 nm was confirmed by dark field transmission electron microscopy. Thus, in contrast to the previously published results, the expected size control of silicon nanocrystals was lost. According to the FTIR results, the thermal annealing of SiNx/SiO2 superlattices led to the formation of silicon nanocrystals in mostly oxynitride matrix. Annealed samples demonstrated a photoluminescence peak at 885 nm related to the luminescence of silicon nanocrystals, as confirmed by time-resolved photoluminescence measurements. The loss of nanocrystals size control is discussed in terms of the migration of oxygen atoms from the SiO2 barriers into the silicon rich silicon nitride sublayers. A thermodynamic mechanism responsible for this process is proposed. According to this mechanism, the driving force for the oxygen migration is the gain in the configuration entropy related to the relative arrangements of oxygen and nitrogen atoms.

Nanostructure-Driven Ion Transport in PCBM-Based Polymer Electrolytes

Polyethylene oxide or PEO is an extensively-examined candidate for solid polymer electrolyte materials of lithium ion batteries, and its composite electrolytes has promising ion conductivities.1-3 Oxide nanoparticles with sizes of 5-10 nm are often introduced into these polymer-based composite electrolytes in order to suppress their room-temperature crystallite formation.1-9 The size, geometry and surface functionality of the added particles were known to largely affect the structure and performance of the blended electrolytes.5,10 In this study, we examined a functionalized-fullerene-based composite electrolytes, providing details in their self-assembled nanostructures, modulus, hardness, as well as temperature-dependent ion-conducting behaviors. To the best of our knowledge, no fullerene-based, lithium conducting, composite electrolyte has been reported previously.Herein we used a bench-mark fullerene derivative, phenyl-C61-butyric acid methyl ester (PCBM) as a model fullerene compound and performed impedance spectroscopy, equivalent circuit modeling, nanoscale elemental mapping (in transmission electron microscope), wide-angle X-ray diffraction, as well as nanoindentation to shed light on a 6-fold enhancement in low temperature (less than 50oC) ion conductivity of PEO - lithium bis(trifluoromethanesulfonyl) imide (LiTFSI)-PCBM electrolytes, along with the underlying changes in nanomorphology , mechanical properties, and crystal structures.Based on a previous density functional theory (DFT) calculation, 11 the interaction energies Ei among PEO polymers is estimated to be 2.58 kcal mol-1 per monomer, the Ei between PCBM and PEO is 3.50 kcal mol-1 per monomer (PCBM is taken as 1 repeat unit), and the Ei among PCBMs themselves is 6.01 kcal mol-1per monomer. This explains that at very low PCBM weight percentage, without sufficient PCBM-PCBM contacts, it is more energetically favorable for fullerenes to disperse into PEO matrix. However, with higher PCBM concentration, the fullerenes will efficiently pack with each other into domains with gradually increased dimensions. Quantification of PCBM domains is performed by line scan analysis of energy filtered TEM (EFTEM) images. Upon the addition of PCBM, the average domain sizes gradually increase from 3.4±1 nm ( 0% PCBM), to 4.6±1 nm (10% PCBM) and 4.9±2 nm (20% PCBM), and finally to 7.5±5 nm (40% PCBM ). (A precise determination of PCBM domain dimension is not possible when the domain size is less than 3 nm, due to the lack of EFTEM contrast in these samples). We attribute the observed ion conductivity improvement to those nanomorphological variation in PCBM-PEO-LiTFSi systems.(The plot below is obtained from line scan analysis of energy filtered TEM images of PCBM based composite blends as a function of PCBM weight percentage. For each blend, 56 domains in total are analyzed and their domain size distribution is plotted in the graph. )Reference:1. Croce, F.; Appetecchi, G. B.; Persi, L.; Scrosati, B., Nature 1998, 394(6692), 456-4582. Appetecchi, G. B.; Croce, F.; Hassoun, J.; Scrosati, B.; Salomon, M.; Cassel, F., Hot-pressed, dry, composite, Journal of Power Sources 2003, 114(1), 105-112;3. Xiong, H. M.; Zhao, X.; Chen, J. S., Journal of Physical Chemistry B 2001, 105(42), 10169-10174.4. Fullerton-Shirey, S. K.; Maranas, J. K., Journal of Physical Chemistry C 2010, 114(20), 9196-92065. Krawiec, W.; Scanlon, L. G.; Fellner, J. P.; Vaia, R. A.; Giannelis, E. P., Journal of Power Sources 1995, 54(2), 310-3156. Nan, C. W.; Fan, L. Z.; Lin, Y. H.; Cai, Q., Physical Review Letters 2003, 91(26)7. Liu, Y.; Lee, J. Y.; Hong, L., Journal of Applied Polymer Science 2003, 89(10), 2815-28228. Singh, T. J.; Bhat, S. V., Journal of Power Sources 2004, 129(2), 280-2879.Chen, H. W.; Chiu, C. Y.; Chang, F. C., Journal of Polymer Science Part B-Polymer Physics 2002, 40(13), 1342-1353.10. Dissanayake, M., Ionics 2004, 10(3-4), 221-225.11. Chen, J.; Yu, X.; Hong, K.; Messman, J. M.; Pickel, D. L.; Xiao, K.; Dadmun, M. D.; Mays, J. W.; Rondinone, A. J.; Sumpter, B. G.; Kilbey, S. M., II, Journal of Materials Chemistry 2012, 22(26), 13013-13022. Acknowledgements A portion of this research was conducted at the Center for Nanophase Materials Sciences, which is sponsored at Oak Ridge National Laboratory by the Division of Scientific User Facilities, Office of Basic Energy Sciences, U.S. Department of Energy.

Tailoring the surface density of silicon nanocrystals embedded in SiOx single layers

In this article, we explore the possibility of modifying the silicon nanocrystal areal density in SiOx single layers, while keeping constant their size. For this purpose, a set of SiOx monolayers with controlled thickness between two thick SiO2 layers has been fabricated, for four different compositions (x = 1, 1.25, 1.5, or 1.75). The structural properties of the SiOx single layers have been analyzed by transmission electron microscopy (TEM) in planar view geometry. Energy-filtered TEM images revealed an almost constant Si-cluster size and a slight increase in the cluster areal density as the silicon content increases in the layers, while high resolution TEM images show that the size of the Si crystalline precipitates largely decreases as the SiOx stoichiometry approaches that of SiO2. The crystalline fraction was evaluated by combining the results from both techniques, finding a crystallinity reduction from 75% to 40%, for x = 1 and 1.75, respectively. Complementary photoluminescence measurements corroborate the precipitation of Si-nanocrystals with excellent emission properties for layers with the largest amount of excess silicon. The integrated emission from the nanoaggregates perfectly scales with their crystalline state, with no detectable emission for crystalline fractions below 40%. The combination of the structural and luminescence observations suggests that small Si precipitates are submitted to a higher compressive local stress applied by the SiO2 matrix that could inhibit the phase separation and, in turn, promotes the creation of nonradiative paths.

Measurements of local chemistry and structure in Ni(O)–YSZ composites during reduction using energy-filtered environmental TEM

Energy-filtered transmission electron microscopy images are acquired during the reduction of a NiO-YSZ composite in H2 up to 600 °C. Temperature-resolved quantitative information about both chemistry and structure is extracted with nm spatial resolution from the data, paving the way for the development of detailed reduction models.

Sponge-like Si-SiO2nanocomposite—Morphology studies of spinodally decomposed silicon-rich oxide

Sponge-like Si nanostructures embedded in SiO2 were fabricated by spinodal decomposition of sputter-deposited silicon-rich oxide with a stoichiometry close to that of silicon monoxide. After thermal treatment a mean feature size of about 3 nm was found in the phase-separated structure. The structure of the Si-SiO2 nanocomposite was investigated by energy-filtered transmission electron microscopy (EFTEM), EFTEM tomography, and atom probe tomography, which revealed a percolated Si morphology. It was shown that the percolation of the Si network in 3D can also be proven on the basis of 2D EFTEM images by comparison with 3D kinetic Monte Carlo simulations.

Formation and coarsening of sponge-like Si-SiO2 nanocomposites

It has been recently found by energy filtered transmission electron microscopy (EFTEM) that metastable SiOx≈1 films decay into a Si nanowire network embedded in SiO2 by spinodal decomposition during thermal treatment. To have a guideline for nanocomposites fabrication, details of the morphology evolution have been studied by comparison of EFTEM images with kinetic Monte-Carlo (kMC) simulations. Pair correlation functions calculated by kMC have been adjusted to that extracted from EFTEM. This comparison leads to the conclusion about characteristic lengths of 3D morphologies. Combining kMC with EFTEM delivers the understanding for tailoring the properties like quantum confinement of the spongy Si.