Atomic-resolution Scanning Transmission Electron Research Articles

Controlling the half-metallicity of Heusler/Si(1 1 1) interfaces by a monolayer of Si–Co–Si

By using first-principles calculations we show that the spin-polarization reverses its sign at atomically abrupt interfaces between the half-metallic Co2(Fe,Mn)(Al,Si) and Si(1 1 1). This unfavourable spin-electronic configuration at the Fermi-level can be completely removed by introducing a Si–Co–Si monolayer at the interface. In addition, this interfacial monolayer shifts the Fermi-level from the valence band edge close to the conduction band edge of Si. We show that such a layer is energetically favourable to exist at the interface. This was further confirmed by direct observations of CoSi2 nano-islands at the interface, by employing atomic resolution scanning transmission electron microscopy.

Deformation twinning induced decomposition of lamellar LPSO structure and its re-precipitation in an Mg-Zn-Y alloy.

The high hardness or yield strength of an alloy is known to benefit from the presence of small-scale precipitation, whose hardening effect is extensively applied in various engineering materials. Stability of the precipitates is of critical importance in maintaining the high performance of a material under mechanical loading. The long period stacking ordered (LPSO) structures play an important role in tuning the mechanical properties of an Mg-alloy. Here, we report deformation twinning induces decomposition of lamellar LPSO structures and their re-precipitation in an Mg-Zn-Y alloy. Using atomic resolution scanning transmission electron microscopy (STEM), we directly illustrate that the misfit dislocations at the interface between the lamellar LPSO structure and the deformation twin is corresponding to the decomposition and re-precipitation of LPSO structure, owing to dislocation effects on redistribution of Zn/Y atoms. This finding demonstrates that deformation twinning could destabilize complex precipitates. An occurrence of decomposition and re-precipitation, leading to a variant spatial distribution of the precipitates under plastic loading, may significantly affect the precipitation strengthening.

The structure of a propagating MgAl2O4/MgO interface: linked atomic- and μm-scale mechanisms of interface motion

To understand how a new phase forms between two reactant layers, MgAl2O4 (spinel) has been grown between MgO (periclase) and Al2O3 (corundum) single crystals under defined temperature and load. Electron backscatter diffraction data show a topotaxial relationship between the MgO reactant and the MgAl2O4 reaction product. These MgAl2O4 grains are misoriented from perfect alignment with the MgO substrate by ~2–4°, with misorientation axes concentrated in the interface plane. Further study using atomic resolution scanning transmission electron microscopy shows that in 2D the MgAl2O4/MgO interface has a periodic configuration consisting of curved segments (convex towards MgO) joined by regularly spaced misfit dislocations occurring every ~4.5 nm (~23 atomic planes). This configuration is observed along the two equivalent [1 0 0] directions parallel to the MgAl2O4/MgO interface, indicating that the 3D geometry of the interface is a grid of convex protrusions of MgAl2O4 into MgO. At each minimum between the protrusions is a misfit dislocation. This geometry results from the coupling between long-range diffusion, which supplies Al3+ to and removes Mg2+ from the reaction interface, and interface reaction, in which climb of the misfit dislocations is the rate-limiting process. The extra oxygen atoms required for dislocation climb were likely derived from the reactant MgO, leaving behind oxygen vacancies that eventually form pores at the interface. The pores are dragged along by the propagating reaction interface, providing additional resistance to interface motion. The pinning effect of the pores leads to doming of the interface on the scale of individual grains.

Detection of picometer-order atomic displacements in drift-compensated HAADF-STEM images of gold nanorods.

Cs-corrected atomic resolution scanning transmission electron microscopy under a drift-compensated operation enabled us to acquire high-angle annular dark-field (HAADF) images of entire gold nanorods without distortion induced by specimen drift. The precision in locating the atomic columns was evaluated to be ±5 pm in the images thus obtained, which is comparable to the image pixel size. A high-precision HAADF image of a single-crystalline gold nanorod revealed that the tip portions at both ends tended to undergo outward displacements along the rod axis and inward contraction along the perpendicular direction. A single nanosecond pulse shot of laser light with a wavelength of 1064 nm and an average intensity of 7.3 kJ/m2 pulse deformed the nanorods into spherical shapes. Simultaneously, the particle interior was completely changed into a multiple twin structure. Substantial displacements of atomic columns on the order of several tens of picometers were confirmed to be localized in the corners of domains at multiple twin junctions. Both the magnitude and direction of displacements were linearly relaxed with increasing distance from a multiple junction.

Atomic-resolution analysis of degradation phenomena in SOFCS: A case study of SO2 poisoning in LSM cathodes

Solid oxide fuel cell (SOFC) degradation studies are often performed by scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM), and X-ray diffraction (XRD). However, it is difficult to use these techniques to observe processes occurring at the smallest scales. Here, we study sulfur poisoning of La0.8Sr0.2MnO3−δ (LSM) cathodes as a model case for atomic resolution scanning transmission electron microscopy (STEM) analysis with energy dispersive X-ray diffraction (EDX). Significant SrSO4 nanoparticle formation is observed after SO2 exposure, especially at grain boundaries in the LSM. In addition, La2O3 formation inside the grain was also confirmed. The formation of SrSO4 is identified with irreversible SOFC degradation, in addition to simple SO2 adsorption, which is reversible.

Highly strained AlAs-type interfaces in InAs/AlSb heterostructures

Spontaneously formed Al-As type interfaces of the InAs/AlSb system grown by molecular beam epitaxy for quantum cascade lasers were investigated by atomic resolution scanning transmission electron microscopy. Experimental strain profiles were compared to those coming from a model structure. High negative out-of-plane strains with the same order of magnitude as perfect Al-As interfaces were observed. The effects of the geometrical phase analysis used for strain determination were evidenced and discussed in the case of abrupt and huge variations of both atomic composition and bond length as observed in these interfaces. Intensity profiles performed on the same images confirmed that changes of chemical composition are the source of high strain fields at interfaces. The results show that spontaneously assembled interfaces are not perfect but extend over 2 or 3 monolayers.

Preparation and Loading Process of Single Crystalline Samples into a Gas Environmental Cell Holder for In Situ Atomic Resolution Scanning Transmission Electron Microscopic Observation.

A reproducible way to transfer a single crystalline sample into a gas environmental cell holder for in situ transmission electron microscopic (TEM) analysis is shown in this study. As in situ holders have only single-tilt capability, it is necessary to prepare the sample precisely along a specific zone axis. This can be achieved by a very accurate focused ion beam lift-out preparation. We show a step-by-step procedure to prepare the sample and transfer it into the gas environmental cell. The sample material is a GaP/Ga(NAsP)/GaP multi-quantum well structure on Si. Scanning TEM observations prove that it is possible to achieve atomic resolution at very high temperatures in a nitrogen environment of 100,000 Pa.

Phase Boundary Structure of LixFePO4 Cathode Material Revealed by Atomic-Resolution Scanning Transmission Electron Microscopy

A variety of cathode materials in lithium ion batteries exhibit phase separations during electrochemical reactions, where two phases with different Li compositions are in equilibrium across the phase interface. Because of the lattice mismatch between these phases, large structural distortions are introduced around the interface region. To characterize their potential effect upon the Li migration behavior, the phase interface structure should be determined accurately. In this study, we perform sophisticated structural analyses for phase interfaces in the well-known cathode material LixFePO4, using atomic resolution scanning transmission electron microscopy. The lattice deformation behavior and Li composition gradient are separately measured across the interface and superimposed after spatial calibrations. The combined result reveals that their relationship significantly deviates from simple models, such as Vegard’s law or other higher order interpolations. Notably, the interface region has small lattice sizes comparable to the FePO4 phase, while having intermediate Li compositions. The origin of observed structure is discussed considering the local phase stability by estimating the pair distance variations of dominant attractive/repulsive ionic couples. Because of the nonlinear variations of each structural parameter, well-optimized experiments with high spatial resolutions and sufficient accuracies are required to correctly understand the phase interface structures.

In-situ observation and atomic resolution imaging of the ion irradiation induced amorphisation of graphene.

Ion irradiation has been observed to induce a macroscopic flattening and in-plane shrinkage of graphene sheets without a complete loss of crystallinity. Electron diffraction studies performed during simultaneous in-situ ion irradiation have allowed identification of the fluence at which the graphene sheet loses long-range order. This approach has facilitated complementary ex-situ investigations, allowing the first atomic resolution scanning transmission electron microscopy images of ion-irradiation induced graphene defect structures together with quantitative analysis of defect densities using Raman spectroscopy.

Double Columnar Structure with a Nanogradient Composite for Increased Oxygen Diffusivity and Reduction Activity

The cathodic performances that can be achieved in solid oxide fuel cells (SOFCs), particularly in terms of oxygen diffusion, need to be improved so that high power densities can be produced at intermediate temperatures. Here, to improve the cathodic performance, a double columnar functional interlayer (DCFL) consisting of Sm0.2Ce0.8O2−δ (SDC) and Sm0.5Sr0.5CoO3−δ (SSC) is fabricated between a La0.9Sr0.1Ga0.8Mg0.2O3−δ electrolyte film and a SSC cathode film with pulsed laser deposition. The DCFL has a rough surface morphology consisting of nanosized grains (with diameters less than 5 nm), and it is formed of small columns that grow at an angle of ca. 45° from the substrate. Inserting the DCFL causes the electrical conductivity of the cathode to increase significantly, and the power density obtained by using it in a metal‐supported SOFC is increased. Atomic resolution scanning transmission electron microscopy (TEM) images and density functional theory calculations confirm that the samarium atoms in the SDC columns and cobalt atoms in the SSC columns are located at the interfaces between SDC and SSC columns. Therefore, it is possible a SmCoO3−δ nanogradient is formed, which may cause lattice distortions. The 18O2 concentration is actually much higher in the DCFL than in either of SSC or SDC films.

A new metastable precipitate phase in Mg–Gd–Y–Zr alloy

Mg–RE alloys are among the strongest Mg-based alloys due to their unique precipitation structures. A previously unobserved metastable phase (βT) is found to coexist with reported β″ and β′ metastable phases under peak ageing conditions in a Mg–Gd–Y–Zr alloy. The position of the RE elements within the βT phase is identified using atomic-resolution high-angle annular dark field scanning transmission electron microscopy imaging, and the βT phase is shown to have an orthorhombic structure with a stoichiometry of Mg5RE. Based on these observations, a new precipitation sequence is proposed.

Nucleation kinetics of entrained eutectic Si in Al–5Si alloys

A series of high-purity Al–5 wt.% Si alloys with trace additions of Sr, Fe and P were prepared by using arc-melting and subsequent melt-spinning. The nucleation phenomenon incorporating the free growth criterion of eutectic Si was investigated by using the entrained droplet technique, atomic resolution scanning transmission electron microscopy and differential scanning calorimetry. It was found that Sr addition exerts no positive effect on the nucleation process; instead, an increased undercooling was observed. A combined addition of Sr and Fe further increased the undercooling, as compared with the addition of Sr only. Only trace P addition has a profound effect on the nucleation of Si by a proposed formation of AlP patches on primary Al. The estimated AlP patch size was found to be sufficient for the free growth of Si to occur inside the eutectic droplet. Nucleation kinetics was discussed on the basis of classical nucleation theory and the free growth model. For the first time, realistic and physically meaningful nucleation site values were obtained. The interactions between Sr and P were also highlighted. This investigation demonstrates strong experimental supports for the free growth nucleation kinetics and the well-accepted impurity-induced twinning growth mechanism, as well as the poisoning of the twin plane re-entrant edge growth mechanism.

Atomic structure and microstructures of supertetragonal multiferroicBiFeO3thin films

We revisit the atomic structure and microstructure of the so-called supertetragonal phases of highly strained epitaxial ${\text{BiFeO}}_{3}$ thin films. Quantitative atomic resolution scanning transmission electron microscopy is used to directly image the atomic positions. A crystallographic phase suggested by electron diffraction and predicted by ab initio calculations is evidenced. Microtwins are reported in thickest films. Electron energy loss spectroscopy is further employed to reveal subtle electronic structure features, which, interpreted in a framework of antiferrodistortive distortions coupling with the substrate, point towards a phase closer to the $P$4mm purely tetragonal phase.

Strain analysis of compositionally tailored interfaces in InAs/GaSb superlattices

The effect of interface composition control on interfacial strain distribution in InAs/GaSb superlattices on (100)-GaSb substrates is investigated by atomic resolution scanning transmission electron microscopy. The interface composition was controlled by either depositing InSb at each interface or soaking the GaSb-on-InAs interface under Sb2 atmosphere. The strain profiles reveal a distinct difference in the extent to which the superlattice strain is balanced using the two methods. In particular, they indicate that the degree of strain balance achievable with soaking is inherently limited by the arsenic surface coverage during GaSb-on-InAs interface formation, emphasizing the influence of V/III flux ratio at this interface. The results also explain observed X-ray diffraction profiles.

Enhanced light element imaging in atomic resolution scanning transmission electron microscopy

We show that an imaging mode based on taking the difference between signals recorded from the bright field (forward scattering region) in atomic resolution scanning transmission electron microscopy provides an enhancement of the detectability of light elements over existing techniques. In some instances this is an enhancement of the visibility of the light element columns relative to heavy element columns. In all cases explored it is an enhancement in the signal-to-noise ratio of the image at the light column site. The image formation mechanisms are explained and the technique is compared with earlier approaches. Experimental data, supported by simulation, are presented for imaging the oxygen columns in LaAlO₃. Case studies looking at imaging hydrogen columns in YH₂ and lithium columns in Al₃Li are also explored through simulation, particularly with respect to the dependence on defocus, probe-forming aperture angle and detector collection aperture angles.

Nanoscale Probing of Voltage Activated Oxygen Reduction/Evolution Reactions in Nanopatterned (LaxSr1‐x)CoO3‐δ Cathodes

AbstractBias‐dependent mechanisms of reversible and irreversible electrochemical processes on a (La0.5Sr0.5)2CoO4±δ modified (LaxSr1‐x)CoO3‐ surface are studied using dynamic electrochemical strain microscopy (D‐ESM). The reversible oxygen reduction/evolution process is activated at voltages as low as 3–4 V and the degree of transformation increases linearly with applied bias. The irreversible processes associated with static surface deformation become apparent above 10–12 V. Post‐mortem focused‐ion milling combined with atomic resolution scanning transmission electron microscopy and electron energy loss spectroscopy is used to establish the mechanisms of irreversible transformations and attribute it to amorphization of the top layer of material. These studies both establish the framework for probing irreversible electrochemical processes in solids and illustrate rich spectrum of electrochemical transformations underpinning electrocatalytic activity in cobaltites.

Controlled polarity of sputter-deposited aluminum nitride on metals observed by aberration corrected scanning transmission electron microscopy

The polarity determination process of sputter-deposited aluminum nitride (AlN) on metals has been analyzed using aberration corrected atomic resolution scanning transmission electron microscope. Direct growth of c-axis orientated AlN on face centered cubic metals (fcc) (111) with the local epitaxy has been observed, and the polarity was determined at the AlN/metal interface. We found that the AlN polarity can be controlled by the base metal layer: N-polarity AlN grows on Pt(111) while Al-polarity AlN forms on Al(111). Based on these results, the growth mechanism of AlN on metals is discussed.

Atomistic observation of electron irradiation-induced defects in CeO2

ABSTRACTWe have investigated the atomistic structure of radiation-induced defects in CeO2 formed under 200 keV electron irradiation. Dislocation loops on {111} habit planes are observed, and they grow accompanying strong strain-field. Atomic resolution scanning transmission electron microscopy (STEM) observations with high angle annular dark-field (HAADF) and annular bright-field (ABF) imaging techniques showed that no additional Ce layers are inserted at the position of the dislocation loop, and that strong distortion and expansion is induced around the dislocation loops. These results are discussed that dislocation loops formed under electron irradiation are non-stoichiometric defects consist of oxygen interstitials.

Strain relaxation defects in perovskite oxide superlattices

Abstract

Fourier images in coherent convergent beam electron diffraction and atomic resolution scanning transmission electron microscopy

Fourier images in coherent convergent beam electron diffraction and atomic resolution scanning transmission electron microscopy