Atomic-resolution Annular Dark-field Imaging Research Articles

Low-Temperature Solution Synthesis of Transition Metal Dichalcogenide Alloys with Tunable Optical Properties.

Nanostructures of layered transition metal dichalcogenide (TMD) alloys with tunable compositions are promising candidates for a broad scope of applications in electronics, optoelectronics, topological devices, and catalysis. Most TMD alloy nanostructures are synthesized as films on substrates using gas-phase methods at high temperatures. However, lower temperature solution routes present an attractive alternative with the potential for larger-scale, higher-yield syntheses of freestanding, higher surface area materials. Here, we report the direct solution synthesis of colloidal few-layer TMD alloys, MoxW1-xSe2 and WS2ySe2(1-y), exhibiting fully tunable metal and chalcogen compositions that span the MoSe2-WSe2 and WS2-WSe2 solid solutions, respectively. Chemical guidelines for achieving the targeted compounds are presented, along with comprehensive structural characterizations (X-ray diffraction, electron microscopy, Raman, and UV-visible spectroscopies). High-resolution microscopic imaging confirms the formation of TMD alloys and identifies a random distribution of the alloyed elements. Analysis of the tilt-angle dependency of the intensities associated with atomic-resolution annular dark field imaging line scans reveals the types of point vacancies present in the samples, thus providing atomic-level insights into the structures of colloidal TMD alloy nanostructures that were previously only accessible for substrate-confined films. The A excitonic transition of the TMD alloy nanostructures can be readily adjusted between 1.51 and 1.93 eV through metal and chalcogen alloying, correlating the compositional modulation to the realization of tunable optical properties.

Influence of surface relaxation of strained layers on atomic resolution ADF imaging

Surface relaxation of thin transmission electron microscopy (TEM) specimens of strained layers results in a severe bending of lattice planes. This bending significantly displaces atoms from their ideal channeling positions which has a strong impact on the measured annular dark field (ADF) intensity.With the example of GaAs quantum wells (QW) embedded in a GaP barrier, we model the resulting displacements by elastic theory using the finite element (FE) formalism. Relaxed and unrelaxed super cells served as input for state of the art frozen phonon simulation of atomic resolution ADF images.We systematically investigate the dependencies on the sample´s geometric parameters, i.e. QW width and TEM sample thickness, by evaluating the simulated intensities at the atomic column´s positions as well as at the background positions in between. Depending on the geometry the ADF intensity can be affected in a range several nm from the actual interface.Moreover, we investigate the influence of the surface relaxation on the angular distribution of the scattered intensity. At high scattering angles we observe an intensity reduction at the interface as well as in the GaP barrier due to de-channeling. The amount of intensity reduction at an atomic column is directly proportional to its mean square displacement. On the contrary we find a clearly increased intensity at low angles caused by additional diffuse scattering. We discuss the implications for quantitative evaluations as well as strategies to compensate for the reduced intensities.

Quantitative annular dark-field imaging of single-layer graphene-II: atomic-resolution image contrast.

We have investigated how accurately atomic-resolution annular dark-field (ADF) images match between experiments and simulations to conduct more reliable crystal structure analyses. Quantitative ADF imaging, in which the ADF intensity at each pixel represents the fraction of the incident probe current, allows us to perform direct comparisons with simulations without the use of fitting parameters. Although the conventional comparison suffers from experimental uncertainties such as an amorphous surface layer and specimen thickness, in this study we eliminated such uncertainties by using a single-layer graphene as a specimen. Furthermore, to reduce image distortion and shot noises in experimental images, multiple acquisitions with drift correction were performed, and the atomic ADF contrast was quantitatively acquired. To reproduce the experimental ADF contrast, we used three distribution functions as the effective source distribution in simulations. The optimum distribution function and its full-width at half-maximum were evaluated by measuring the residuals between the experimental and simulated images. It was found that the experimental images could be explained well by a linear combination of a Gaussian function and a Lorentzian function with a longer tail than the Gaussian function.

Atomic scale characterization of vacancy ordering in oxygen conducting membranes.

This article presents a comprehensive investigation of (La, Sr)FeO3 by correlated atomic resolution annular dark field imaging and electron energy loss spectroscopy. Here, the ability of these techniques to characterize point defect formation and phase transitions under reducing conditions in situ in the scanning transmission electron microscope is evaluated and the influence of oxygen vacancies on the structure-property relationships is discussed. In particular, the evolution of the Ruddlesden-Popper, Brownmillerite, and Aurivillius phases can be associated directly with the ionic and electronic conductivity of the bulk material under different thermodynamic conditions. These results lead naturally to an atomistic defect chemistry model to explain the high temperature ionic and electronic conductivity in this and other perovskite materials.