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The concept of electronic orbitals has enabled the understanding of a wide range of physical and chemical properties of solids through the definition of, for example, chemical bonding between atoms. In the transmission electron microscope, which is one of the most used and powerful analytical tools for high‐spatial‐resolution analysis of solids, the accessible quantity is the local distribution of electronic states. However, the interpretation of electronic state maps at atomic resolution in terms of electronic orbitals is far from obvious, not always possible, and often remains a major hurdle preventing a better understanding of the properties of the system of interest. In this review, the current state of the art of the experimental aspects for electronic state mapping and its interpretation as electronic orbitals is presented, considering approaches that rely on elastic and inelastic scattering, in real and reciprocal spaces. This work goes beyond resolving spectral variations between adjacent atomic columns, as it aims at providing deeper information about, for example, the spatial or momentum distributions of the states involved. The advantages and disadvantages of existing experimental approaches are discussed, while the challenges to overcome and future perspectives are explored in an effort to establish the current state of knowledge in this field. The aims of this review are also to foster the interest of the scientific community and to trigger a global effort to further enhance the current analytical capabilities of transmission electron microscopy for chemical bonding and electronic structure analysis. [ABSTRACT FROM AUTHOR]

Bournonite (CuPbSbS3) and enargite (Cu3AsS4) have recently been used as absorber layers in thin-film photovoltaic devices due to their ideal bandgap and ferroelectric properties. An understanding of the ferroelectric domain structure in these materials is required so that the benefits of the internal depolarizing electric fields can be fully exploited. Here, the atomic structure and electronic properties of domain walls (DWs) are elucidated through a combined aberration-corrected scanning transmission electron microscopy and density functional theory study. ∼90° and 180° DWs are observed in bournonite. As the 180° DW is charge neutral, it cannot contribute to the anomalous photovoltaic effect that leads to high open circuit voltages. The ∼90° DW shows a slight offset across the boundary, but the contributions of this to the anomalous photovoltaic effect are negligible. The DWs are also electrically passive, i.e., they do not result in significant recombination and do not block charge carrier transport. A high density of stacking faults (SF) was, however, observed in enargite. The SFs have a large number of defect states within the bandgap, which would lower the device efficiency through Shockley–Read–Hall recombination. [ABSTRACT FROM AUTHOR]

The microstructural evolution of Cu(In,Ga)Se2 absorber layers during a three-stage-type coevaporation process was studied to elucidate the effect of a Cu-rich stage on the formation of extended structural defects. Defect densities for two Cu-poor samples, one interrupted before and one after this crucial Cu-rich composition stage, were investigated by scanning transmission electron microscopy (STEM) imaging. The structure and chemical nature of individual defects were investigated by aberration-corrected high-resolution STEM in combination with electron energy-loss spectroscopy on the atomic-scale. In spite of the different defect densities between the two samples, most of the individual defects exhibited similar chemistry. In particular, the elemental distributions of atomic columns at {112} twin planes, which are very frequent in Cu(In,Ga)Se2 thin films, were found to be the same as in the defect-free grain interiors. In contrast, within grain boundaries, dislocation cores, and other structurally more complex defects, elemental redistributions of Cu and In were observed. [ABSTRACT FROM AUTHOR]

Trilayer heterostructures consisting of a ferroelectric bismuth ferrite (BFO) film sandwiched between ferromagnetic lanthanum strontium manganese oxide (LSMO) films were fabricated using pulsed laser deposition. Both BFO thicknesses (20 nm, 5 nm) and cooling rates were varied to investigate the role of processing parameters on the chemistry of the interfaces. The interfaces were investigated using a dedicated aberration corrected scanning transmission electron microscope (STEM) operated at 100 kV via STEM-high angle annular dark field (STEM-HAADF) and STEM-electron energy loss spectroscopy (STEM-EELS) modes. Combined analysis through STEM-HAADF and STEM-EELS revealed the formation of lattice distortion in certain regions of the BFO layer for the ∼5 nm film. Piezoresponse force microscopy (PFM) studies of the ∼5 nm BFO sample revealed weak ferroelectric domain switching. Stacking fault defects with mixed valence manganese (Mn-B site cation) were formed in the top LSMO layer when the heterostructure was cooled at a slower rate irrespective of BFO thickness, thereby demonstrating the effect of processing kinetics on the physical integrity of the heterostructure. [ABSTRACT FROM AUTHOR]

We investigate the interfacial structure of PbZr0.20Ti0.80O3 (PZT)/La0.67Sr0.33MnO3 (LSMO)/SrTiO3 heterostructures by combining low-magnification transmission electron microscopy imaging and spectroscopy techniques with high-resolution spherical-aberration corrected scanning transmission electron microscopy imaging, geometrical phase analysis, and spectroscopy results. For certain thickness regimes, the interface between PZT and LSMO is found to have a significant density of planar defects at the interface. Both A-site cation (Pb) diffusivity and highly inhomogeneous local strains are observed at the boundaries of the defect areas. It is proposed that Pb is incorporated as PbO Ruddlesden-Popper planar fault within the LSMO. These results underline the importance of chemical fluctuations caused by long-range strain fields associated with defect cores. [ABSTRACT FROM AUTHOR]

We report a study on multiferroic bismuth ferrite (BiFeO3, BFO)-ferromagnetic lanthanum strontium manganese oxide (La0.7Sr0.3MnO3, LSMO) epitaxial interfaces by scanning transmission electron microscopy-energy dispersive spectroscopy (STEM-EDS) and energy-filtered transmission electron microscopy (EFTEM). Epitaxial (001) oriented LSMO/BFO heterostructures were fabricated on a (001) strontium titanate (SrTiO3, STO) substrate using pulsed laser deposition (PLD). Different cooling conditions to room temperature (rapid or slow) were used to investigate the effect of fabrication conditions on the structural quality of the interfaces. The combined analysis of bright field transmission electron microscopy imaging, STEM-EDS and EFTEM data reveals that the LSMO-BFO heterostructure interface is free from any defects but the phases are chemically interdiffused over a length scale of ∼4 nm. [ABSTRACT FROM AUTHOR]

We investigate the structure of the (0001) basal twin boundary in Bi2Te3. Electron diffraction measurements show that this interface corresponds to a 180° rotation of the crystal about the [0001] axis, an alignment that reverses the stacking of the basal planes. The basal planes in the perfect Bi2Te3 structure are arranged in a repeating sequence of five-layer wide Te(1)–Bi–Te(2)–Bi–Te(1) packets. Thus, it is possible for the twin interface to be located at one of three distinct locations: at the Te(2) layer, the Bi layer, or the Te(1) layer. Using aberration-corrected high-angle annular dark field scanning transmission electron microscopy, we show that the twin boundary is terminated at the Te(1) layer, where the stacking forms a double-layer of Te. Our observations are consistent with ab initio calculations, which predict this twin termination to have the lowest interfacial energy of the three configurations we considered. Our calculations and observations also find a small expansion in the interplanar spacing at the interface. [ABSTRACT FROM AUTHOR]

We investigate the structure of the (0001) basal twin boundary in Bi2Te3. Electron diffraction measurements show that this interface corresponds to a 180° rotation of the crystal about the [0001] axis, an alignment that reverses the stacking of the basal planes. The basal planes in the perfect Bi2Te3 structure are arranged in a repeating sequence of five-layer wide Te(1)–Bi–Te(2)–Bi–Te(1) packets. Thus, it is possible for the twin interface to be located at one of three distinct locations: at the Te(2) layer, the Bi layer, or the Te(1) layer. Using aberration-corrected high-angle annular dark field scanning transmission electron microscopy, we show that the twin boundary is terminated at the Te(1) layer, where the stacking forms a double-layer of Te. Our observations are consistent with ab initio calculations, which predict this twin termination to have the lowest interfacial energy of the three configurations we considered. Our calculations and observations also find a small expansion in the interplanar spacing at the interface. [ABSTRACT FROM AUTHOR]