Evidence of the Monopolar-Dipolar Crossover Regime: A Multiscale Study of Ferroelastic Domains by In Situ Microscopy Techniques.

The elastic interaction between kinks (and antikinks) within domain walls plays a pivotal role in shaping the domain structure, and their dynamics. In bulk materials, kinks interact as elastic monopoles, dependent on the distance between walls (d-1) and typically characterized by a rigid and straight domain configuration. In this work the evolution of the domain structure is investigated, as the sample size decreases, by the means of in situ heating microscopy techniques on free-standing samples. As the sample size decreases, a significant transformation is observed: domain walls exhibit pronounced curvature, accompanied by an increase in both domain wall and junction density. This transformation is attributed to the pronounced influence of kinks, inducing sample warping, where "dipole-dipole" interactions are dominant (d-2). Moreover, a critical thickness range that delineates a crossover between the monopolar and dipolar regimens is experimentally identified and corroborated by atomic simulations. These findings are relevant for in situ TEM studies and for the development of novel devices based on free-standing ferroic thin films and nanomaterials.

The Effect of Chemical Environment and Temperature on the Domain Structure of Free-Standing BaTiO3 via In Situ STEM.

Ferroelectrics, due to their polar nature and reversible switching, can be used to dynamically control surface chemistry for catalysis, chemical switching, and other applications such as water splitting. However, this is a complex phenomenon where ferroelectric domain orientation and switching are intimately linked to surface charges. In this work, the temperature-induced domain behavior of ferroelectric-ferroelastic domains in free-standing BaTiO3 films under different gas environments, including vacuum and oxygen-rich, is studied by in situ scanning transmission electron microscopy (STEM). An automated pathway to statistically disentangle and detect domain structure transformations using deep autoencoders, providing a pathway towards real-time analysis is also established. These results show a clear difference in the temperature at which phase transition occurs and the domain behavior between various environments, with a peculiar domain reconfiguration at low temperatures, from a-c to a-a at ≈60 °C. The vacuum environment exhibits a rich domain structure, while under the oxidizing environment, the domain structure is largely suppressed. The direct visualization provided by in situ gas and heating STEM allows to investigate the influence of external variables such as gas, pressure, and temperature, on oxide surfaces in a dynamic manner, providing invaluable insights into the intricate surface-screening mechanisms in ferroelectrics.

Dislocation and strain mapping in metamorphic parabolic-graded InGaAs buffers on GaAs.

We investigate different architectures for parabolic-graded InGaAs metamorphic buffers grown on GaAs using transmission electron microscopy techniques. The different architectures include InGaP and AlInGaAs/InGaP superlattices with different GaAs substrate misorientations and the inclusion of a strain balancing layer. Our results correlate: (i) the density and distribution of dislocations in the metamorphic buffer and (ii) the strain in the next layer preceding the metamorphic buffer, which varies for each type of architecture. Our findings indicate that the dislocation density in the lower region of the metamorphic layer ranges between 108 and 1010 cm-2, with AlInGaAs/InGaP superlattice samples exhibiting higher values compared to samples with InGaP films. We have identified two waves of dislocations, with threading dislocations typically located lower in the metamorphic buffer (~ 200-300 nm) in comparison to misfit dislocations. The measured localised strain values are in good agreement with theoretical predications. Overall, our results provide a systematic insight into the strain relaxation across different architectures, highlighting the various approaches that can be used to tailor strain in the active region of a metamorphic laser. Supplementary Information: The online version contains supplementary material available at 10.1007/s10853-023-08597-y.

Effects of Multiple Local Environments on Electron Energy Loss Spectra of Epitaxial Perovskite Interfaces.

The role of local chemical environments in the electron energy loss spectra of complex multiferroic oxides was studied using computational and experimental techniques. The evolution of the O K-edge across an interface between bismuth ferrite (BFO) and lanthanum strontium manganate (LSMO) was considered through spectral averaging over crystallographically equivalent positions to capture the periodicity of the local O environments. Computational techniques were used to investigate the contribution of individual atomic environments to the overall spectrum, and the role of doping and strain was considered. Chemical variation, even at the low level, was found to have a major impact on the spectral features, whereas strain only induced a small chemical shift to the edge onset energy. Through a combination of these methods, it was possible to explain experimentally observed effects such as spectral flattening near the interface as the combination of spectral responses from multiple local atomic environments.

Avalanche criticality in LaAlO[Formula: see text] and the effect of aspect ratio.

Ferroic domain dynamics, as a function of external stimuli, can be collectively described as scale-invariant avalanches characterised by a critical exponent that are sensitive to the complexity of the domain microstructure. The understanding and manipulation of these avalanches lies at the heart of developing novel applications such as neuromorphic computing. Here we combine in situ heating optical observations and mean-field analysis to investigate the collective domain behaviour in pure-ferroelastic lanthanum aluminate (LaAlO[Formula: see text]) as a function of aspect ratio, the ratio of sample length to width, where the movement of the domains is predominantly driven by thermal stresses via thermal expansion/contraction during heat cycling. Our observations demonstrate that the aspect ratio induces (1) distinctive domain microstructures at room temperature, (2) a deviation of dynamical behaviour at high temperatures and (3) critical exponent mixing in the higher aspect ratio samples that accompanies this behaviour. While the critical exponents of each aspect ratio fall within mean-field predicted values, we highlight the effect that the aspect ratio has in inducing exponent mixing. Hence, furthering our understanding towards tuning and controlling avalanches which is crucial for fundamental and applied research.

Towards 3D characterisation of site-controlled InGaAs pyramidal QDs at the nanoscale.

In this work, we report an extensive investigation via transmission electron microscopy (TEM) techniques of InGaAs/GaAs pyramidal quantum dots (PQDs), a unique site-controlled family of quantum emitters that have proven to be excellent sources of single and entangled photons. The most striking features of this system, originating from their peculiar fabrication process, include their inherently 3-dimensional nature and their interconnection to a series of nanostructures that are formed alongside them, such as quantum wells and quantum wires. We present structural and chemical data from cross-sectional and plan view samples of both single and stacked PQDs structures. Our findings identify (i) the shape of the dot, being hexagonal and not triangular as previously assumed, (ii) the chemical distribution at the facets and QD area, displaying clear Indium diffusion, and (iii) a near absence of Aluminium (from the AlAs marker) at the bottom of the growth profile. Our results shed light on previously unreported structural and chemical features of PQDs, which is of extreme relevance for further development of this family of quantum emitters. Supplementary Information: The online version contains supplementary material available at 10.1007/s10853-022-07654-2.

ZnO nucleation into trititanate nanotubes by ALD equipment techniques, a new way to functionalize layered metal oxides.

In this contribution, we explore the potential of atomic layer deposition (ALD) techniques for developing new semiconductor metal oxide composites. Specifically, we investigate the functionalization of multi-wall trititanate nanotubes, H2Ti3O7 NTs (sample T1) with zinc oxide employing two different ALD approaches: vapor phase metalation (VPM) using diethylzinc (Zn(C2H5)2, DEZ) as a unique ALD precursor, and multiple pulsed vapor phase infiltration (MPI) using DEZ and water as precursors. We obtained two different types of tubular H2Ti3O7 species containing ZnO in their structures. Multi-wall trititanate nanotubes with ZnO intercalated inside the tube wall sheets were the main products from the VPM infiltration (sample T2). On the other hand, MPI (sample T3) principally leads to single-wall nanotubes with a ZnO hierarchical bi-modal functionalization, thin film coating, and surface decorated with ZnO particles. The products were mainly characterized by electron microscopy, energy dispersive X-ray, powder X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. An initial evaluation of the optical characteristics of the products demonstrated that they behaved as semiconductors. The IR study revealed the role of water, endogenous and/or exogenous, in determining the structure and properties of the products. The results confirm that ALD is a versatile tool, promising for developing tailor-made semiconductor materials.

Elastic distortion determining conduction in BiFeO3 phase boundaries.

It is now well-established that boundaries separating tetragonal-like (T) and rhombohedral-like (R) phases in BiFeO3 thin films can show enhanced electrical conductivity. However, the origin of this conductivity remains elusive. Here, we study mixed-phase BiFeO3 thin films, where local populations of T and R can be readily altered using stress and electric fields. We observe that phase boundary electrical conductivity in regions which have undergone stress-writing is significantly greater than in the virgin microstructure. We use high-end electron microscopy techniques to identify key differences between the R-T boundaries present in stress-written and as-grown microstructures, to gain a better understanding of the mechanism responsible for electrical conduction. We find that point defects (and associated mixed valence states) are present in both electrically conducting and non-conducting regions; crucially, in both cases, the spatial distribution of defects is relatively homogeneous: there is no evidence of phase boundary defect aggregation. Atomic resolution imaging reveals that the only significant difference between non-conducting and conducting boundaries is the elastic distortion evident - detailed analysis of localised crystallography shows that the strain accommodation across the R-T boundaries is much more extensive in stress-written than in as-grown microstructures; this has a substantial effect on the straightening of local bonds within regions seen to electrically conduct. This work therefore offers distinct evidence that the elastic distortion is more important than point defect accumulation in determining the phase boundary conduction properties in mixed-phase BiFeO3.

Correction: Giant resistive switching in mixed phase BiFeO3via phase population control.

Correction for 'Giant resistive switching in mixed phase BiFeO3via phase population control' by David Edwards et al., Nanoscale, 2018, 10, 17629-17637.

Giant resistive switching in mixed phase BiFeO3via phase population control.

Highly-strained coherent interfaces, between rhombohedral-like (R) and tetragonal-like (T) phases in BiFeO3 thin films, often show enhanced electrical conductivity in comparison to non-interfacial regions. In principle, changing the population and distribution of these interfaces should therefore allow different resistance states to be created. However, doing this controllably has been challenging to date. Here, we show that local thin film phase microstructures (and hence R-T interface densities) can be changed in a thermodynamically predictable way (predictions made using atomistic simulations) by applying different combinations of mechanical stress and electric field. We use both pressure and electric field to reversibly generate metastable changes in microstructure that result in very large changes of resistance of up to 108%, comparable to those seen in Tunnelling Electro-Resistance (TER) devices.

Synthesis of epitaxial metal oxide nanocrystals via a phase separation approach.

Perovskite phase instability of BiMnO3 has been exploited to synthesize epitaxial metal oxide magnetic nanocrystals. Thin film processing conditions are tuned to promote the breakdown of the perovskite precursor into Bi2O3 matrix and magnetic manganese oxide islands. Subsequent cooling in vacuum ensures complete volatization of the Bi2O3, thus leaving behind an array of self-assembled magnetic Mn3O4 nanostructures. Both shape and size can be systematically controlled by the ambient oxygen environments and deposition time. As such, this approach can be extended to any other Bi-based complex ternary oxide system as it primarily hinges on the breakdown of parent Bi-based precursor and subsequent Bi2O3 volatization.

A template and catalyst-free metal-etching-oxidation method to synthesize aligned oxide nanowire arrays: NiO as an example.

Although NiO is one of the canonical functional binary oxides, there has been no report so far on the effective fabrication of aligned single crystalline NiO nanowire arrays. Here we report a novel vapor-based metal-etching-oxidation method to synthesize high-quality NiO nanowire arrays with good vertical alignment and morphology control. In this method, Ni foils are used as both the substrates and the nickel source; NiCl(2) powder serves as the additional Ni source and provides Cl(2) to initiate mild etching. No template is deliberately employed; instead a nanograined NiO scale formed on the NiO foil guides the vapor infiltration and assists the self-assembled growth of NiO nanowires via a novel process comprising simultaneous Cl(2) etching and gentle oxidation. Furthermore, using CoO nanowires and Co-doped NiO as examples, we show that this general method can be employed to produce nanowires of other oxides as well as the doped counterparts.

Chemistry of the Fe2O3/BiFeO3 Interface in BiFeO3 Thin Film Heterostructures.

We investigate the interfacial chemistry of secondary Fe2O3 phases formed in a BiFeO3 (BFO) layer in BFO/ La0.67Sr0.33MnO3 (LSMO)/SrTiO3 (STO) heterostructures. A combination of high-resolution spherical aberration corrected scanning TEM and spectroscopy results, reveals that specific chemical and crystallographic similarities between Fe2O3 and BFO, enable the BFO layer to form a facile host for Fe2O3.