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Deviations of local structure and chemistry from the average crystalline unit cell are increasingly recognized to have a significant influence on the properties of many technologically important materials. Here, we present the vector pair correlation function (vPCF) as a new real-space crystallographic analysis method, which can be applied to atomic-resolution scanning transmission electron microscopy (STEM) images to quantify and analyze structural order/disorder correlations. Our STEM-based vPCFs have several advantages over radial PCFs and/or 3D pair distribution functions from x-ray total scattering: vPCFs explicitly retain crystallographic orientation information, are spatially resolved, can be applied directly on a sublattice basis, and are suitable for any material that can be imaged with STEM. To show the utility of our approach, we measure partial vPCFs in Ba5SmSn3Nb7O30 (BSSN), a tetragonal tungsten bronze (TTB) structured complex oxide. Many TTBs are known to be classical or relaxor ferroelectrics, and these properties have been correlated with the presence of superlattice ordering. BSSN, specifically, exhibits relaxor behavior and an incommensurate structural modulation. From the vPCF data, we observe that, of the cation sites, only the Ba (A2) sublattice is structurally modulated. We then infer the local modulation vector and reveal a marked anisotropy in its correlation length. Finally, short-range correlated polar displacements on the B2 cation sites are observed. This work introduces the vPCF as a powerful real-space crystallography technique, which enables direct, robust quantification of short-to-long range order on a sublattice-specific basis and is applicable to a wide range of complex material types.

The solid‐state synthesis of perovskite BiFeO3 has been a topic of interest for decades. Many studies have reported challenges in the synthesis of BiFeO3 from starting oxides of Bi2O3 and Fe2O3, mainly associated with the development of persistent secondary phases such as Bi25FeO39 (sillenite) and Bi2Fe4O9 (mullite). These secondary phases are thought to be a consequence of unreacted Fe‐rich and Bi‐rich regions, that is, incomplete interdiffusion. In the present work, in situ high‐temperature X‐ray diffraction is used to demonstrate that Bi2O3 first reacts with Fe2O3 to form sillenite Bi25FeO39, which then reacts with the remaining Fe2O3 to form BiFeO3. Therefore, the synthesis of perovskite BiFeO3 is shown to occur via a two‐step reaction sequence with Bi25FeO39 as an intermediate compound. Because Bi25FeO39 and the γ‐Bi2O3 phase are isostructural, it is difficult to discriminate them solely from X‐ray diffraction. Evidence is presented for the existence of the intermediate sillenite Bi25FeO39 using quenching experiments, comparisons between Bi2O3 behavior by itself and in the presence of Fe2O3, and crystal structure examination. With this new information, a proposed reaction pathway from the starting oxides to the product is presented. [ABSTRACT FROM AUTHOR]

The discovery of ferroelectricity in polar wurtzite-based ternary materials, such as Al1−xBxN, has attracted attention due to their compatibility with complementary metal–oxide–semiconductor processes and potential use in integrated non-volatile memory devices. However, the origin of ferroelectricity and the fundamental control of the polarization switching in these materials are still under intensive investigation but appear to be related to local disorder induced from the alloying. In this work, we report the effect of boron alloying on the local structure of Al1−xBxN films deposited by magnetron sputtering. Our results reveal a diminished crystalline order as a function of boron concentration, accompanied by a reduction in the spontaneous polarization. The film disorder is primarily associated with the dissimilar bond lengths between Al–N and B–N and the formation of threading dislocations induced by B incorporation in the structure. [ABSTRACT FROM AUTHOR]

Time-dependent increases in electrical conductivity in dielectrics exposed to a direct-current voltage bias can be detrimental to device reliability and lifetime, while the same phenomenon may be exploited for resistive switching functionality. The applied electric field induces the electromigration of charged point defects, resulting in spatially inhomogeneous stoichiometry and modifications in the electrode electrostatics. Herein, we monitor the time-dependent changes in leakage current in rutile TiO 2 with platinum electrodes. Current–voltage measurements before and after the extended electrical biasing demonstrate that changes in the electrostatics of the cathode Schottky barrier are responsible for the time-dependent increases in leakage current. We also find that electromigration is accelerated along the ⟨ 001 ⟩ relative to the ⟨ 010 ⟩ crystallographic direction in contrast to what would be predicted by high-temperature diffusion kinetics. We find the observed anisotropic behavior to be consistent with a change in the defect charge state of the titanium interstitials and dominant transport path at lower temperatures. A comparison of optical color front migration kinetics to the temporal evolution of leakage current further supports the interpretation that ionic electromigration near the cathode interface is responsible for the increased leakage current in the electrically degraded state. [ABSTRACT FROM AUTHOR]

Plan view scanning transmission electron microscopy was used to investigate the microstructural connections to device resistance in inline phase change switch devices. It was revealed that massive structural changes occur in GeTe during switching, most notably the formation of an assembly of voids along the device centerline and large GeTe grains on either side of an "active region." Restructuring of this variety was tied to changes in ON-state resistance with increasing pulse number, where initially porous and fine-grained (10-20 nm) GeTe was converted to large crystalline domains comprising the majority of the RF gap (400-700 nm). A phenomenological model for this microstructure is presented in which the OFF pulse melts a given width of GeTe, and upon cooling crystalline material outside the melt region acts as a template for an inward-propagating crystalline growth front. The voids observed along the device centerline were correlated to increasing OFF state resistance and a relatively stable ON state with increasing pulse number via a series resistance model. As a result of this analysis, OFF state resistance was suggested as an early indicator of device reliability. An improved GeTe deposition process was implemented to limit void formation, which is shown to have a more stable OFF-state resistance with increasing pulse number. [ABSTRACT FROM AUTHOR]