Dark-field Transmission Electron Microscopy Research Articles

On the formation of hierarchically structured L2 1 -Ni2TiAl type precipitates in a ferritic alloy

This study demonstrates a processing sequence used to generate coherent, two-phase L21-Ni2TiAl/B2-NiAl precipitates in a ferritic matrix, and documents their microstructural evolution. Dark-field and energy-filtered transmission electron microscopy in combination with energy-dispersive X-ray analysis are used to determine the structure and composition of the different phases in the course of the processing and aging treatment. Through rapid solidification, coherent L21-Ni2TiAl type precipitates with an internal network of curved, isotropic \( 1 / 2\langle 100\rangle \) antiphase boundaries form within the bcc-Fe matrix. The average width of the precipitates in the as-quenched state is 15 nm. During the subsequent aging heat treatment thin, anisotropic B2-NiAl zones are established, resulting in a three-tiered hierarchical microstructure. The L21-Ni2TiAl precipitates are coherent with the bcc-Fe matrix, while the fine B2-NiAl zones are coherently embedded in the Ni2TiAl precipitates and aligned along the \( \langle 100\rangle \) directions. The L21-Ni2TiAl parent precipitates have a width of 40 nm in the heat-treated stage and the B2-NiAl zones are 3–7 nm wide. Hence, the addition of Ti to Fe-rich Fe–Ni–Al alloys leads to the formation of coherent L21-Ni2TiAl precipitates in the bcc-Fe matrix with an internal network of fine, anisotropic B2-NiAl zones arranged in a hierarchical manner. These microstructures are of potential interest for designing and optimizing the mechanical properties of precipitation-strengthened ferritic alloys.

Polycrystallinity and Stacking in CVD Graphene

Graphene, a truly two-dimensional hexagonal lattice of carbon atoms, possesses remarkable properties not seen in any other material, including ultrahigh electron mobility, high tensile strength, and uniform broadband optical absorption. While scientists initially studied its intrinsic properties with small, mechanically exfoliated graphene crystals found randomly, applying this knowledge would require growing large-area films with uniform structural and physical properties. The science of graphene has recently experienced revolutionary change, mainly due to the development of several large-scale growth methods. In particular, graphene synthesis by chemical vapor deposition (CVD) on copper is a reliable method to obtain films with mostly monolayer coverage. These films are also polycrystalline, consisting of multiple graphene crystals joined by grain boundaries. In addition, portions of these graphene films contain more than one layer, and each layer can possess a different crystal orientation and stacking order. In this Account, we review the structural and physical properties that originate from polycrystallinity and stacking in CVD graphene. To begin, we introduce dark-field transmission electron microscopy (DF-TEM), a technique which allows rapid and accurate imaging of key structural properties, including the orientation of individual domains and relative stacking configurations. Using DF-TEM, one can easily identify "lateral junctions," or grain boundaries between adjacent domains, as well as "vertical junctions" from the stacking of graphene multilayers. With this technique, we can distinguish between oriented (Bernal or rhombohedral) and misoriented (twisted) configurations. The structure of lateral junctions in CVD graphene is sensitive to growth conditions and is reflected in the material's electrical and mechanical properties. In particular, grain boundaries in graphene grown under faster reactant flow conditions have no gaps or overlaps, unlike more slowly grown films. These structural differences can affect the material's electrical properties: for example, better-connected grain boundaries are more electrically conductive. However, grain boundaries in general are mechanically weaker than pristine graphene, which is an order of magnitude stronger than CVD graphene based on indentation measurements performed with an atomic force microscope. Vertical junctions in multilayer CVD graphene have two key structural features. First, bilayer graphene (BLG) with Bernal stacking exists in two mirrored configurations (AB or AC) that also form isolated domains. Similarly, oriented trilayer graphene also has alternating ABA and ABC stacked layers. Second, in twisted multilayer graphene, stacked layers lack long-range atomic registry and can move freely relative to each other, which generates unique optical properties. In particular, an interlayer optical excitation produces strong Raman and absorption peaks, dependent on the twist angle. A better understanding of the structural and physical properties of grain boundaries and multilayers in CVD graphene is central to realizing the full potential of graphene in large-scale applications. In addition, these studies provide a model for characterizing other layered materials, such as hexagonal boron nitride and MoS2, where similar polycrystallinity and stacking are expected when grown in large areas.

Microstructure of adiabatic shear bands in Ti6Al4V

Abstract Microstructural deformation mechanisms in adiabatic shear bands in Ti6Al4V are studied using traditional TEM and selected area diffraction, and more advanced microstructural characterisation techniques such as energy dispersive X-ray spectroscopy, high angle annular dark field STEM and conical dark field TEM. The shear bands under investigation are induced in Ti6Al4V samples by high strain rate compression of cylindrical and hat-shaped specimens in a split Hopkinson pressure bar setup. Samples from experiments interrupted at different levels of deformation are used to study the evolution of the microstructure in and nearby the shear bands. From the early stages of adiabatic shear band formation, TEM revealed strongly elongated equiaxed grains in the shear band. These band-like grains become narrower towards the centre of the band and start to fraction even further along their elongated direction to finally result in a nano-crystalline region in the core. In fully developed shear bands, twins and a needle-like martensite morphology are observed near the shear band.

Ostwald ripening in Al–Li alloys: A test of theory

AbstractExperimental characterization of microstructure evolution in three binary Al–Li alloys provides a quantitative test of diffusion screening theory. Particle size distributions, growth kinetics, and maximum particle sizes are obtained through quantitative, centered dark-field transmission electron microscopy. The dependences on δ′ precipitate volume fraction of the coarsening rate constant and maximum particle size are revealed, both of which have eluded determination for a half century. These experiments show that the diffusion screening theory for late-stage phase coarsening yields accurate predictions of maximum size of particle and relative coarsening constant.

Core/Shell Colloidal Semiconductor Nanoplatelets

We have recently synthesized atomically flat semiconductor colloidal nanoplatelets with quasi 2D geometry. Here, we show that core/shell nanoplatelets can be obtained with a 2D geometry that is conserved. The epitaxial growth of the shell semiconductor is performed at room temperature. We report the detailed synthesis of CdSe/CdS and CdSe/CdZnS structures with different shell thicknesses. The shell growth is characterized both spectroscopically and structurally. In particular, the core/shell structure appears very clearly on high-resolution, high-angle annular dark-field transmission electron microscope images, thanks to the difference of atomic density between the core and the shell. When the nanoplatelets stand on their edge, we can precisely count the number of atomic planes forming the core and the shell. This provides a direct measurement, with atomic precision, of the core nanoplatelets thickness. The constraints exerted by the shell growth on the core is analyzed using global phase analysis. The core/shell nanoplatelets we obtained have narrow emission spectra with full-width at half-maximum close to 20 nm, and quantum yield that can reach 60%.

Residual disorder and diffusion in thin Heusler alloy films

Co2FeSi/GaAs(110) and Co2FeSi/GaAs(111)B hybrid structures were grown by molecular-beam epitaxy and characterized by transmission electron microscopy (TEM) and X-ray diffraction. The films contained inhomogeneous distributions of ordered L2_1 and B2 phases. The average stoichiometry was controlled by lattice parameter measurements, however diffusion processes lead to inhomogeneities of the atomic concentrations and the degradation of the interface, influencing long-range order. An average long-range order of 30-60% was measured by grazing-incidence X-ray diffraction, i.e. the as-grown Co2FeSi films were highly but not fully ordered. Lateral inhomogeneities of the spatial distribution of long-range order in Co2FeSi were found using dark-field TEM images taken with superlattice reflections.

Experimental, computational and theoretical studies of δ′ phase coarsening in Al–Li alloys

Experimental characterization of microstructure evolution in three binary Al–Li alloys provides critical tests of both diffusion screening theory and multiparticle diffusion simulations, which predict late-stage phase-coarsening kinetics. Particle size distributions, growth kinetics and maximum particle sizes obtained using quantitative, centered dark-field transmission electron microscopy are compared quantitatively with theoretical and computational predictions. We also demonstrate the dependence on δ′ precipitate volume fraction of the rate constant for coarsening and the microstructure’s maximum particle size, both of which remained undetermined for this alloy system for nearly a half century. Our experiments show quantitatively that the diffusion-screening theoretical description of phase coarsening yields reasonable kinetic predictions, and that useful simulations of microstructure evolution are obtained via multiparticle diffusion. The tested theory and simulation method will provide useful tools for future design of two-phase alloys for elevated temperature applications.

Layer Number and Stacking Sequence Imaging of Few-Layer Graphene by Transmission Electron Microscopy

A method based on dark field transmission electron microscopy is developed to quantitively investigate the layer number and stacking order of multilayer graphene, demonstrated here on multilayer crystalline graphene synthesized by chemical vapor deposition. Our results show that the relative intensities of first- and second-order diffraction spots and contrast in corresponding dark field images are sufficient to identify the layer number and stacking order of graphene with layer number up to seven (7) or more with few-nanometer spatial resolution.

Structural characterization of GaAs self-assembled quantum dots grown by Droplet Epitaxy on Ge virtual substrates on Si

The structure of self-assembled quantum dots (QDs) grown by Droplet Epitaxy on Ge virtual substrates has been investigated by TEM. The QDs have a pyramidal shape with base and height of 50nm. By (002) dark field TEM it was seen that the pyramid top is Ga poor and Al rich most likely because of the higher mobility of Ga along the pyramid sides down to the base. The investigated QDs contain defects identified as As precipitates by Moirè fringes. The smallest ones (3–5nm) are coherent with the GaAs lattice suggesting that they could be a cubic phase of As precipitation. It seems to be a metastable phase since the hexagonal phase is recovered as the precipitate size increases above ∼5nm.

Structural characterization of He ion microscope platinum deposition and sub-surface silicon damage

In this paper we studied helium ion beam induced deposition (HIBID) of Pt on a silicon wafer using the recently commercialized helium ion microscope (HIM) at 25 kV and low beam currents. The motivation of this work was to understand the impact of light, inert helium ions on deposition rate and structure purity, with some implications on the usefulness of HIM nano-machining for circuit modification. Two Pt-rich deposits with sub-micron dimensions were grown with HIBID at different ion beam currents. The pillar and substrate structure were studied using bright and dark field TEM images. The authors analyzed metal purity profile of the HIBID deposit on height using energy dispersive x-ray spectroscopy. The maximum Pt content measured reached 41%, which is the highest measured metal content of a HIBID-grown structure. TEM studies of the sub-surface damage to the Si shows more damage below the deposit grown at a higher beam current. The differences in amorphization layer thickness between the two different beam currents are discussed. A comparison to Pt deposition by Ga FIB and electron beam induced deposition is provided, along with conclusions regarding the usage of HIBID technology for circuit modification.

Tilted Dark Field TEM of Twinning and Twisting in Tri- and Bi-layer Graphene

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

Angle-Resolved Raman Imaging of Interlayer Rotations and Interactions in Twisted Bilayer Graphene

Few-layer graphene is a prototypical layered material, whose properties are determined by the relative orientations and interactions between layers. Exciting electrical and optical phenomena have been observed for the special case of Bernal-stacked few-layer graphene, but structure-property correlations in graphene which deviates from this structure are not well understood. Here, we combine two direct imaging techniques, dark-field transmission electron microscopy (DF-TEM) and widefield Raman imaging, to establish a robust, one-to-one correlation between twist angle and Raman intensity in twisted bilayer graphene (tBLG). The Raman G band intensity is strongly enhanced due to a previously unreported singularity in the joint density of states of tBLG, whose energy is exclusively a function of twist angle and whose optical transition strength is governed by interlayer interactions, enabling direct optical imaging of these parameters. Furthermore, our findings suggest future potential for novel optical and optoelectronic tBLG devices with angle-dependent, tunable characteristics.

Structure of a new ternary compound with high magnesium content, so-called Gd13Ni9Mg78

The magnesium-rich composition Gd13Ni9Mg78 was synthesized from its constituent elements in sealed tantalum tubes in an induction furnace. X-ray diffraction, electron probe microanalysis and dark-field transmission electron microscopy (TEM) images revealed a new compound with a composition ranging from Gd10–15Ni8–12Mg72–78 and low crystallinity. In order to increase the crystallinity, different experimental conditions were investigated for numerous compounds with the initial composition Gd13Ni9Mg78. In addition, several heat treatments (from 573 to 823K) and cooling rates (from room temperature quenched down to 2Kh−1) have been tested. The best crystallinity was obtained for the slower cooling rates ranging from 2 to 6Kh−1. From the more crystallized compounds, the structure was partially deduced using TEM and an average cubic structure with lattice parameter a=4.55Å could be assumed. A modulation along both a∗ and b∗ axis with vectors of modulation q1=0.42a∗ and q2=0.42b∗ was observed. This compound, so-called Gd13Ni9Mg78, absorbs around 3wt.% of hydrogen at 603K, 30bars and a reasonable degree of reversibility is possible, because after the first hydrogenation, irreversible decomposition into MgH2, GdH2 and NiMg2H4 has been shown. The pathway of the reaction is described herein. The powder mixture after decomposition shows an interesting kinetics for magnesium without ball milling.

Dislocation-Driven CdS and CdSe Nanowire Growth

We report the synthesis of CdS and CdSe nanowires (NWs) and nanoribbons (NRs) with gold catalysts by H(2)-assisted chemical vapor deposition. Nanopods and nanocones were obtained without catalysts at higher system pressure. Transmission electron microscopy (TEM) studies, including two-beam TEM and displaced-aperture dark-field TEM characterization, were used to investigate the NW growth mechanism. Dislocation contrast and twist contours have been routinely observed within the synthesized one-dimensional (1D) CdS and CdSe NWs, suggesting the operation of the dislocation-driven NW growth mechanism under our experimental conditions. The Burgers vectors of dislocations and the associated Eshelby twists were measured and quantified. We hypothesize that gold nanoparticles provide nucleation sites to initiate the growth of CdS/CdSe NWs and lead to the formation of dislocations that continue to drive and sustain 1D growth at a low supersaturation level. Our study suggests that the dislocation-driven mechanism may also contribute to the growth of other 1D nanomaterials that are commonly considered to grow via the vapor-liquid-solid mechanism.

Methanol electrooxidation on carbon supported Aucore–Ptshell nanoparticles synthesized by an epitaxial growth method

Aucore–Ptshell (Au@Pt) nanoparticles supported on activated carbon (Au@Pt/C) are synthesized by an epitaxial growth method using HCOONa as a reducing agent. Through the characterization of the transmission electron microscope (TEM), high resolution TEM (HRTEM), high angle annular dark-field scanning TEM (HAADF-STEM) and X-ray powder diffraction (XRD), the Pt atoms grow epitaxially on the surface of the Au nanoparticles to form Pt shells with Au fcc structure. According to the results of the X-ray photoelectron spectroscopy (XPS), electrons transfer from Pt to Au. Cyclic voltammetry is employed to investigate the catalytic activities of the Au@Pt/C catalysts for the methanol electrooxidation (MEO) and the CO stripping. The results of the electrochemical measurements indicate that, the Au fcc structure of the Pt shell and the decrease in the electronic effect are propitious to the increases in the catalytic activity for the MEO and the CO tolerance of the Au@Pt/C catalysts.

Investigation of grain boundaries in BaSi2 epitaxial films on Si(1 1 1) substrates using transmission electron microscopy and electron-beam-induced current technique

a-Axis-oriented undoped n-BaSi2 epitaxial films were grown on Si(111) substrates by molecular beam epitaxy, and the crystalline quality and grain boundaries were investigated by means of reflection high-energy electron diffraction, X-ray diffraction, and transmission electron microscopy (TEM). The grain size of the BaSi2 films was estimated to be approximately 0.1–0.3μm, and straight grain boundaries (GBs) were observed in the plan-view TEM images. Dark-field TEM images under a two-beam diffraction condition showed that these GBs consist mostly of BaSi2 {011} planes. The diffusion length of minority carriers in n-BaSi2 was found to be approximately 10μm by an electron-beam-induced current technique.

Formation of nanoscale Th-coffinite

U-thorite, (Th,U)SiO4, from Ambohijatrova Masindray, Madagascar, was investigated to understand the behavior of Th and U during recrystallization of amorphous radiation-damaged, (Th,U)- orthosilicates. Optical microscopy and electron microprobe analyses reveal two types of U-thorite: (i) large (about 1 cm), orange, amorphous grains with composition: (Th0.88±0.02U0.09-0.01Pb0.029±0.002 REE0.01±0.001)1.00±0.01Si1.00±0.01; and (ii) green, microcrystalline U-thorite with composition: (Th0.76±0.05U0.08±0.01Ca0.07±0.01Pb0.014±0.005REE0.009±0.001)0.92±0.07Si1.12±0.06. Ca-free U-thorite-(i) is enriched in Th, U, and Pb (7.1, 1.2, and 1 wt%, respectively), and depleted in Si (3.0 wt%) compared to U-thorite-(ii). Recrystallization of U-thorite-(i) resulted in fracturing that facilitated migration of mobilized Th and U over a distance of about 300 μm, as evidenced by precipitation of U-thorite-(ii) in the fractures in associated apatite and garnet. Transmission electron microscopy observations and selected-area electron diffraction (SAED) patterns confirm that U-thorite-(i) is amorphous. U-thorite-(ii) forms: (1) single crystals (>1 μm in size) with variable amounts of amorphous material; or (2) randomly oriented, nanocrystalline aggregates (5-10 nm in size). TEM-EDX analyses show that the Th/U ratio in U-thorite-(i) and U-thorite-(ii) is ~6. High-angle annular dark-field scanning TEM (HAADF-STEM) and high-resolution TEM reveal that nanocrystalline Th-coffinite (20-40 nm in size) with Th/U ratio = 0.6, formed during recrystallization of U-thorite-(i). The calculated chemical Th-U-Pb ages of Uthorite-( i) range from 2.1-1.9 Ga and from 1.8-1.6 Ga, whereas U-thorite-(ii) ages range from 1.6-0.5 Ga. The calculated cumulative radiation dose for U-thorite-(i) varies from 1.6-1.8 × 1018 α-decay events/mg, which is equivalent to 136-152 displacements per atom (dpa), and for U-thorite-(ii) from 3-4.4 × 1017 (α-decay events/mg) (=27-37 dpa). The cumulative dose for Th-coffinite is 9.8 × 1017 α-decay events/mg (84 dpa).

Medium range order of bulk metallic glasses determined by variable resolution fluctuation electron microscopy

Variable resolution fluctuation electron microscopy (FEM) experiments are implemented with hollow-cone dark-field transmission electron microscopy. Medium range order lengths of zirconium and iron based bulk metallic glasses and amorphous silicon nitride are determined from the FEM results. It shows that maximum normalized intensity variances of FEM images occur when their nominal resolution approaches the correlation length Λ of the amorphous materials. Additionally, differences in the length and magnitude of medium range order are compared between metallic and covalent bond amorphous materials.

Single-Crystalline, Stoichiometric Bi2Te3 Nanowires for Transport in the Basal Plane

Bi2Te3 nanowires were grown in a nanostructured Al2O3 matrix by potential-pulsed electrochemical deposition. The wires had diameters of 50 nm to 80 nm and length of about 56 μm. Cross-sections prepared for scanning electron microscopy revealed uniform growth with deviations in length of less than 10%. The wires were deposited with reduction potentials between −150 mV and −250 mV. A reduction potential of −200 mV yielded an average Te content of 63.2 at.% as determined by calibrated, high-accuracy energy-dispersive x-ray spectrometry in transmission electron microscopy (TEM). The chemical composition was uniform along the length of the nanowires but depended on their diameter. The Te content increased by about 1 at.% when the diameter of the nanowires decreased from 80 nm to 50 nm. Selected-area electron diffraction combined with dark-field TEM imaging revealed single-crystalline wires; no grain boundaries were detected. The nanowires grew along the [110] and [210] directions; the c axis was perpendicular to the wire axis, allowing basal plane transport unaffected by grain boundaries.

Twinning and Twisting of Tri- and Bilayer Graphene

The electronic, optical, and mechanical properties of bilayer and trilayer graphene vary with their structure, including the stacking order and relative twist, providing novel ways to realize useful characteristics not available to single layer graphene. However, developing controlled growth of bilayer and trilayer graphene requires efficient large-scale characterization of multilayer graphene structures. Here, we use dark-field transmission electron microscopy for rapid and accurate determination of key structural parameters (twist angle, stacking order, and interlayer spacing) of few-layer CVD graphene. We image the long-range atomic registry for oriented bilayer and trilayer graphene, find that it conforms exclusively to either Bernal or rhombohedral stacking, and determine their relative abundances. In contrast, our data on twisted multilayers suggest the absence of such long-range atomic registry. The atomic registry and its absence are consistent with the two different strain-induced deformations we observe; by tilting the samples to break mirror symmetry, we find a high density of twinned domains in oriented multilayer graphene, where multiple domains of two different stacking configurations coexist, connected by discrete twin boundaries. In contrast, individual layers in twisted regions continuously stretch and shear independently, forming elaborate Moiré patterns. These results, and the twist angle distribution in our CVD graphene, can be understood in terms of an angle-dependent interlayer potential model.