Christoph Gammer

In Situ Study of Lithiation and Delithiation of MoS2 Nanosheets Using Electrochemical Liquid Cell Transmission Electron Microscopy.

We report the observation of lithiation/delithiation of MoS2 nanosheets in a LiPF6/EC/DEC commercial electrolyte for the application of lithium-ion batteries using electrochemical liquid cell transmission electron microscopy (TEM). Upon discharge in a voltage range of 1.8-1.2 V, MoS2 on the Ti electrode underwent irreversible decomposition resulting in fragmentation of the MoS2 nanosheets into 5-10 nm MoS2 nanoparticles. Repeated experiments also show that some MoS2 nanosheets do not decompose upon lithiation. Instead, lithiation induced structural expansion and deformation has been observed. A solid-electrolyte interface (SEI) was formed on the anode side of the Ti electrode in contact with Li metal. The SEI layer is composed of LiF nanocrystals distributed within the entire layer with the constituent elements C, O, and F. However, no passivation film was observed on the cathode side of the Ti electrode with MoS2 nanosheets on it. Such an in situ electrochemical liquid cell TEM study sheds light on battery degradation mechanisms.

Strain mapping at nanometer resolution using advanced nano-beam electron diffraction

We report on the development of a nanometer scale strain mapping technique by means of scanning nano-beam electron diffraction. Only recently possible due to fast acquisition with a direct electron detector, this technique allows for strain mapping with a high precision of 0.1% at a lateral resolution of 1u2009nm for a large field of view reaching up to 1u2009μm. We demonstrate its application to a technologically relevant strain-engineered GaAs/GaAsP hetero-structure and show that the method can even be applied to highly defected regions with substantial changes in local crystal orientation. Strain maps derived from atomically resolved scanning transmission electron microscopy images were used to validate the accuracy, precision and resolution of this versatile technique.

Diffraction contrast imaging using virtual apertures

Two methods on how to obtain the full diffraction information from a sample region and the associated reconstruction of images or diffraction patterns using virtual apertures are demonstrated. In a STEM-based approach, diffraction patterns are recorded for each beam position using a small probe convergence angle. Similarly, a tilt series of TEM dark-field images is acquired. The resulting datasets allow the reconstruction of either electron diffraction patterns, or bright-, dark- or annular dark-field images using virtual apertures. The experimental procedures of both methods are presented in the paper and are applied to a precipitation strengthened and creep deformed ferritic alloy with a complex microstructure. The reconstructed virtual images are compared with conventional TEM images. The major advantage is that arbitrarily shaped virtual apertures generated with image processing software can be designed without facing any physical limitations. In addition, any virtual detector that is specifically designed according to the underlying crystal structure can be created to optimize image contrast.

Highly mobile ferroelastic domain walls in compositionally graded ferroelectric thin films

Domains and domain walls are critical in determining the response of ferroelectrics, and the ability to controllably create, annihilate, or move domains is essential to enable a range of next-generation devices. Whereas electric-field control has been demonstrated for ferroelectric 180° domain walls, similar control of ferroelastic domains has not been achieved. Here, using controlled composition and strain gradients, we demonstrate deterministic control of ferroelastic domains that are rendered highly mobile in a controlled and reversible manner. Through a combination of thin-film growth, transmission-electron-microscopy-based nanobeam diffraction and nanoscale band-excitation switching spectroscopy, we show that strain gradients in compositionally graded PbZr1-xTixO3 heterostructures stabilize needle-like ferroelastic domains that terminate inside the film. These needle-like domains are highly labile in the out-of-plane direction under applied electric fields, producing a locally enhanced piezoresponse. This work demonstrates the efficacy of novel modes of epitaxy in providing new modalities of domain engineering and potential for as-yet-unrealized nanoscale functional devices.

Optimizing disk registration algorithms for nanobeam electron diffraction strain mapping

Scanning nanobeam electron diffraction strain mapping is a technique by which the positions of diffracted disks sampled at the nanoscale over a crystalline sample can be used to reconstruct a strain map over a large area. However, it is important that the disk positions are measured accurately, as their positions relative to a reference are directly used to calculate strain. In this study, we compare several correlation methods using both simulated and experimental data in order to directly probe susceptibility to measurement error due to non-uniform diffracted disk illumination structure. We found that prefiltering the diffraction patterns with a Sobel filter before performing cross correlation or performing a square-root magnitude weighted phase correlation returned the best results when inner disk structure was present. We have tested these methods both on simulated datasets, and experimental data from unstrained silicon as well as a twin grain boundary in 304 stainless steel.

Local and transient nanoscale strain mapping during in situ deformation

The mobility of defects such as dislocations controls the mechanical properties of metals. This mobility is determined both by the characteristics of the defect and the material, as well as the local stress and strain applied to the defect. Therefore, the knowledge of the stress and strain during deformation at the scale of defects is important for understanding fundamental deformation mechanisms. Here, we demonstrate a method of measuring local stresses and strains during continuous in situ deformation with a resolution of a few nanometers using nanodiffraction strain mapping. Our results demonstrate how large multidimensional data sets captured with high speed electron detectors can be analyzed in multiple ways after an in situ TEM experiment, opening the door for true multimodal analysis from a single electron scattering experiment.

Influence of the Ag concentration on the medium-range order in a CuZrAlAg bulk metallic glass

Fluctuation electron microscopy of bulk metallic glasses of CuZrAl(Ag) demonstrates that medium-range order is sensitive to minor compositional changes. By analyzing nanodiffraction patterns medium-range order is detected with crystal-like motifs based on the B2 CuZr structure and its distorted structures resembling the martensitic ones. This result demonstrates some structural homology between the metallic glass and its high temperature crystalline phase. The amount of medium-range order seems slightly affected with increasing Ag concentration (0, 2, 5 at.%) but the structural motifs of the medium-range ordered clusters become more diverse at the highest Ag concentration. The decrease of dominant clusters is consistent with the destabilization of the B2 structure measured by calorimetry and accounts for the increased glass-forming ability.

Effect of composition on the structure of lithium- and manganese-rich transition metal oxides

The choice of chemical composition of lithium- and manganese-rich transition metal oxides used as cathode materials in lithium-ion batteries can significantly impact their long-term viability as storage solutions for clean energy automotive applications. Their structure has been widely debated: conflicting conclusions drawn from individual studies often considering different compositions have made it challenging to reach a consensus and inform future research. Here, complementary electron microscopy techniques over a wide range of length scales reveal the effect of lithium-to-transition metal-ratio on the surface and bulk structure of these materials. We found that decreasing the lithium-to-transition metal-ratio resulted in a significant change in terms of order and atomic-level local composition in the bulk of these cathode materials. However, throughout the composition range studied, the materials consisted solely of a monoclinic phase, with lower lithium content materials showing more chemical ordering defects. In contrast, the spinel-structured surface present on specific crystallographic facets exhibited no noticeable structural change when varying the ratio of lithium to transition metal. The structural observations from this study warrant a reexamination of commonly assumed models linking poor electrochemical performance with bulk and surface structure.

Nano-scale Strain Mapping Using Advanced STEM with a Direct Electron Detector

Elastic strain is an important materials property in semiconductor heterostructures, both controlling the crystal growth as well as directly affecting the electronic properties. Imaging and quantifying defect strain fields at the nanometer scale is therefore of great importance in these materials. Although HRTEM coupled with image processing algorithms such as GPA [1] has proven to be a very accurate method to measure strain, it still requires high quality specimens that are necessarily thin, which enhances strain relaxation. Recent advances in probe forming optics and detection systems allow STEM to be used for strain mapping both in imaging and diffraction mode.

Correlation between Electrical Transport and NanoscaleStrain in InAs/In 0.6 Ga 0.4 As Core–ShellNanowires

Free-standing semiconductor nanowires constitute an ideal material system for the direct manipulation of electrical and optical properties by strain engineering. In this study, we present a direct quantitative correlation between electrical conductivity and nanoscale lattice strain of individual InAs nanowires passivated with a thin epitaxial In0.6Ga0.4As shell. With an in situ electron microscopy electromechanical testing technique, we show that the piezoresistive response of the nanowires is greatly enhanced compared to bulk InAs, and that uniaxial elastic strain leads to increased conductivity, which can be explained by a strain-induced reduction in the band gap. In addition, we observe inhomogeneity in strain distribution, which could have a reverse effect on the conductivity by increasing the scattering of charge carriers. These results provide a direct correlation of nanoscale mechanical strain and electrical transport properties in free-standing nanostructures.