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The interaction of high-energy electrons and X-ray photons with soft semiconductors such as halide perovskites is essential for the characterisation and understanding of these optoelectronic materials. Using nano-probe diffraction techniques, which can investigate physical properties on the nanoscale, we perform studies of the interaction of electron and X-ray radiation with state-of-the-art (FA$_{0.79}$MA$_{0.16}$Cs$_{0.05}$)Pb(I$_{0.83}$Br$_{0.17}$)$_3$ hybrid halide perovskite films (FA, formamidinium; MA, methylammonium). We track the changes in the local crystal structure as a function of fluence using scanning electron diffraction and synchrotron nano X-ray diffraction techniques. We identify perovskite grains from which additional reflections, corresponding to PbBr$_2$, appear as a crystalline degradation phase after fluences of ~200 e$^-${\AA}$^{-2}$. These changes are concomitant with the formation of small PbI$_2$ crystallites at the adjacent high-angle grain boundaries, with the formation of pinholes, and with a phase transition from tetragonal to cubic. A similar degradation pathway is caused by photon irradiation in nano-X-ray diffraction, suggesting common underlying mechanisms. Our approach explores the radiation limits of these materials and provides a description of the degradation pathways on the nanoscale. Addressing high-angle grain boundaries will be critical for the further improvement of halide polycrystalline film stability, especially for applications vulnerable to high-energy radiation such as space photovoltaics., Comment: 25 pages, 5 figures

Halide perovskites excel in the pursuit of highly efficient thin film photovoltaics, with power conversion efficiencies reaching 25.5% in single junction and 29.5% in tandem halide perovskite/silicon solar cell configurations. Operational stability of perovskite solar cells remains a barrier to their commercialisation, yet a fundamental understanding of degradation processes, including the specific sites at which failure mechanisms occur, is lacking. Recently, we reported that performance-limiting deep sub-bandgap states appear in nanoscale clusters at particular grain boundaries in state-of-the-art $Cs_{0.05}FA_{0.78}MA_{0.17}Pb(I_{0.83}Br_{0.17})_{3}$ (MA=methylammonium, FA=formamidinium) perovskite films. Here, we combine multimodal microscopy to show that these very nanoscale defect clusters, which go otherwise undetected with bulk measurements, are sites at which degradation seeds. We use photoemission electron microscopy to visualise trap clusters and observe that these specific sites grow in defect density over time under illumination, leading to local reductions in performance parameters. Scanning electron diffraction measurements reveal concomitant structural changes at phase impurities associated with trap clusters, with rapid conversion to metallic lead through iodine depletion, eventually resulting in pinhole formation. By contrast, illumination in the presence of oxygen reduces defect densities and reverses performance degradation at these local clusters, where phase impurities instead convert to amorphous and electronically benign lead oxide. Our work shows that the trapping of charge carriers at sites associated with phase impurities, itself reducing performance, catalyses redox reactions that compromise device longevity. Importantly, we reveal that both performance losses and intrinsic degradation can be mitigated by eliminating these defective clusters., Comment: 23 pages, 3 figures, Stuart Macpherson and Tiarnan A. S. Doherty contributed equally

Strain engineering is used to obtain desirable materials properties in a range of modern technologies. Direct nanoscale measurement of the three-dimensional strain tensor field within these materials has however been limited by a lack of suitable experimental techniques and data analysis tools. Scanning electron diffraction has emerged as a powerful tool for obtaining two-dimensional maps of strain components perpendicular to the incident electron beam direction. Extension of this method to recover the full three-dimensional strain tensor field has been restricted though by the absence of a formal framework for tensor tomography using such data. Here, we show that it is possible to reconstruct the full non-symmetric strain tensor field as the solution to an ill-posed tensor tomography inverse problem. We then demonstrate the properties of this tomography problem both analytically and computationally, highlighting why incorporating precession to perform scanning precession electron diffraction may be important. We establish a general framework for non-symmetric tensor tomography and demonstrate computationally its applicability for achieving strain tomography with scanning precession electron diffraction data.

Crystal orientation mapping experiments typically measure orientations that are similar within grains and misorientations that are similar along grain boundaries. Such (mis)orientation data will cluster in (mis)orientation space and clusters are more pronounced if preferred orientations or special orientation relationships are present. Here, cluster analysis of (mis)orientation data is described and demonstrated using distance metrics incorporating crystal symmetry and the density-based clustering algorithm DBSCAN. Frequently measured (mis)orientations are identified as corresponding to grains, grain boundaries or orientation relationships, which are visualised both spatially and in three-dimensional (mis)orientation spaces. A new open-source python library, orix, is also reported.

The formation of exciton-polaritons allows the transport of energy over hundreds of nanometres at velocities up to 10^6 m s^-1 in organic semiconductors films in the absence of external cavity structures.

T-(Al20Cu2Mn3) phase dispersoids are important for limiting recovery and controlling grain growth in Al-Cu alloys. However, these dispersoids can also reduce precipitation hardening by acting as heterogeneous nucleation sites and may lead to increased susceptibility towards pitting corrosion when galvanically coupled with S-(Al2CuMg) phase precipitates. The interplay between T- and S-phases is therefore important for understanding their effect on the mechanical and electrochemical properties of Al-Cu-Mg alloys. Here, the crystallographic relationships between the T-phase, S-phase, and surrounding Al matrix were investigated in an Al-1.31Cu-1.14Mg-0.13Ag-0.10Fe-0.28Mn (at.%) alloy by combining scanning precession electron diffraction with misorientation analysis in 3-dimensional axis-angle space and correlated high-resolution transmission electron microscopy. Orientation relationships are identified between all three phases, revealing S-T orientation relationships for the first time. Differences in S-Al orientation relationships for precipitates formed at T-phase interfaces compared to their non-interfacial counterparts were also identified. These insights provide a comprehensive assessment of the crystallographic relationships in T-/S-phase aggregates, which may guide future alloy design., Comment: 10 pages, 9 figures

In this paper we propose a new joint model for the reconstruction of tomography data under limited angle sampling regimes. In many applications of Tomography, e.g. Electron Microscopy and Mammography, physical limitations on acquisition lead to regions of data which cannot be sampled. Depending on the severity of the restriction, reconstructions can contain severe, characteristic, artefacts. Our model aims to address these artefacts by inpainting the missing data simultaneously with the reconstruction. Numerically, this problem naturally evolves to require the minimisation of a non-convex and non-smooth functional so we review recent work in this topic and extend results to fit an alternating (block) descent framework. We illustrate the effectiveness of this approach with numerical experiments on two synthetic datasets and one Electron Microscopy dataset., Comment: Revised manuscript accepted for publication in Inverse Problems

Using nanometer spatial resolution electron-energy loss spectroscopy (EELS), energy dispersive X-ray spectroscopy (EDS), and cathodoluminescence (CL) mapping, we demonstrate that Au alloys containing a poor plasmonic metal (Pd) can nevertheless sustain multiple size-dependent localized surface plasmon resonances and observe strong field enhancement at Pd-rich tips, where the composition is in fact least favorable for plasmons. These Au/Pd stellated nanocrystals are also involved in substrate and interparticle coupling, as unraveled by EELS tilt series.

The performance of magnetic nanoparticles is intimately entwined with their structure, mean size and magnetic anisotropy. Besides, ensembles offer a unique way of engineering the magnetic response by modifying the strength of the dipolar interactions between particles. Here we report on an experimental and theoretical analysis of magnetic hyperthermia, a rapidly developing technique in medical research and oncology. Experimentally, we demonstrate that single-domain cubic iron oxide particles resembling bacterial magnetosomes have superior magnetic heating efficiency compared to spherical particles of similar sizes. Monte Carlo simulations at the atomic level corroborate the larger anisotropy of the cubic particles in comparison with the spherical ones, thus evidencing the beneficial role of surface anisotropy in the improved heating power. Moreover we establish a quantitative link between the particle assembling, the interactions and the heating properties. This knowledge opens new perspectives for improved hyperthermia, an alternative to conventional cancer therapies., Comment: Accepted for publication in Scientific Reports, 52 pages including supporting info, 7+12 figures

We present an electron energy loss study using energy filtered TEM of spatially resolved surface plasmon excitations on a silver nanorod of aspect ratio 14.2 resting on a 30 nm thick silicon nitride membrane. Our results show that the excitation is quantized as resonant modes whose intensity maxima vary along the nanorod's length and whose wavelength becomes compressed towards the ends of the nanorod. Theoretical calculations modelling the surface plasmon response of the silver nanorod-silicon nitride system show the importance of including retardation and substrate effects in order to describe accurately the energy dispersion of the resonant modes., Comment: 9 pages, 6 figures

The crystallographic structure of CdSe nanoparticles attached to carbon nanotubes has been elucidated by means of high resolution transmission electron microscopy and high angle annular dark field scanning transmission electron microscopy tomography. CdSe rod-like nanoparticles, grown in solution together with carbon nanotubes, undergo a morphological transformation and become attached to the carbon surface. Electron tomography reveals that the nanoparticles are hexagonal-based with the (001) planes epitaxially matched to the outer graphene layer., Comment: 7 pages, 8 figures

Temperature dependent impedance spectroscopy enables the many contributions to the dielectric and resistive properties of condensed matter to be deconvoluted and characterized separately. We have achieved this for multiferroic epitaxial thin films of BiFeO3 (BFO) and BiMnO3 (BMO), key examples of materials with strong magneto-electric coupling. We demonstrate that the true film capacitance of the epitaxial layers is similar to that of the electrode interface, making analysis of capacitance as a function of film thickness necessary to achieve deconvolution. We modeled non-Debye impedance response using Gaussian distributions of relaxation times and reveal that conventional resistivity measurements on multiferroic layers may be dominated by interface effects. Thermally activated charge transport models yielded activation energies of 0.60 eV +- 0.05 eV (BFO) and 0.25 eV +- 0.03 eV (BMO), which is consistent with conduction dominated by oxygen vacancies (BFO) and electron hopping (BMO). The intrinsic film dielectric constants were determined to be 320 +- 75 (BFO) and 450 +- 100 (BMO).

Mixed valent manganites are noted for their unusual magnetic,electronic and structural phase transitions. The La1-xCaxMnO3 phase diagram shows that below transition temperatures in the range 100-260 K, compounds with 0.2 < x < 0.5 are ferromagnetic and metallic whereas those with 0.5 < x < 0.9 are antiferromagnetic and charge ordered. In a narrow region around x = 0.5, these totally dissimilar states are thought to coexist. Uehara et al. have shown that charge order and charge disorder can coexist in the related compound La0.25Pr0.375Ca0.375MnO3. Here, we present electron microscopy data for La0.5Ca0.5MnO3 that sheds light on the distribution of coexisting phases and uncovers a novel and unexpected phase. Using electron holography and Fresnel imaging, we find micron sized ferromagnetic regions spanning several grains coexisting with similar sized regions with no local magnetisation. Holography shows that the ferromagnetic regions have a local magnetisation of 3.4 +- 0.2 mB/Mn (the spin aligned value is 3.5 mB/Mn). We use electron diffraction and dark field imaging to show that charge order exists in regions with no net magnetisation and, surprisingly, can also occur in ferromagnetic regions., Comment: 5 pages of pdf with 2 figures included