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The effect of an electric field on local domain structure near a 24° tilt grain boundary in a 200 nm-thick Pb(Zr_0.2Ti_0.8)O₃bi-crystal ferroelectric film was probed using synchrotron nanodiffraction. The bi-crystal film was grown epitaxially on SrRuO₃-coated (001) SrTiO₃24° tilt bi-crystal substrates. From the nanodiffraction data, real-space maps of the ferroelectric domain structure around the grain boundary prior to and during application of a 200 kV cm⁻¹electric field were reconstructed. In the vicinity of the tilt grain boundary, the distributions of densities ofc-type tetragonal domains with thecaxis aligned with the film normal were calculated on the basis of diffracted intensity ratios ofc- anda-type domains and reference powder diffraction data. Diffracted intensity was averaged along the grain boundary, and it was shown that the density ofc-type tetragonal domains dropped to ∼50% of that of the bulk of the film over a range ±150 nm from the grain boundary. This work complements previous results acquired by band excitation piezoresponse force microscopy, suggesting that reduced nonlinear piezoelectric response around grain boundaries may be related to the change in domain structure, as well as to the possibility of increased pinning of domain wall motion. The implications of the results and analysis in terms of understanding the role of grain boundaries in affecting the nonlinear piezoelectric and dielectric responses of ferroelectric materials are discussed. 

Nanostructuring photocatalytic and catalytic materials substantially increases the surface‐to‐volume ratio, thereby exposing a greater number of active sites essential for enhanced catalytic efficiency. However, optimizing these efficiencies requires the non‐destructive,operandointerrogation of individual nanocrystals under realistic catalytic conditions—a capability that has long remained elusive. Here, this challenge is addressed by reporting three‐dimensional imaging of defects, crystal morphology, and strain dynamics in individual Bi₂WO₆(BWO) nanoflakes using Bragg coherent diffractive imaging (BCDI) underoperandotemperature, gas, and light‐driven conditions. It is demonstrated that maintaining a constant temperature of 40°C thermally activates charge carriers, likely enhancing their mobility and reducing recombination rates. Furthermore, an Argon (Ar) gas flow stabilizes the reaction environment, while a mixed Hydrogen–Nitrogen (H₂+ N₂) flow induces a hydrogen‐triggered semiconducting‐to‐metallic (SM) electronic phase transition accompanied by a structural transformation, as supported by density functional theory (DFT) calculations. Both DFT and BCDI analyses reveal that during the SM phase transition, a new structural phase nucleates near defects and propagates inhomogeneously. Notably, the onset of nanoscale cracking is observed, driven by localized strain accumulation and environmental cycling, which increases surface area and potentially introduces new reactive sites. These findings illustrate that combining advanced nanostructuring withoperandoimaging techniques can provide critical insights into the local structural features that govern photocatalytic performance, paving the way for the rational design of next‐generation photocatalytic materials. 

Abstract Hydrogen fuel cells and electrolyzers operating below 600 °C, ideally below 400 °C, are essential components in the clean energy transition. Yttrium‐doped barium zirconate BaZr_0.8Y_0.2O_3‐d(BZY) has attracted a lot of attention as a proton‐conducting solid oxide for electrochemical devices due to its high chemical stability and proton conductivity in the desired temperature range. Grain interfaces and topological defects modulate bulk proton conductivity and hydration, especially at low temperatures. Therefore, understanding the nanoscale crystal structure dynamics in situ is crucial to achieving high proton transport, material stability, and extending the operating range of proton‐conducting solid oxides. Here, Bragg coherent X‐ray diffractive imaging is applied to investigate in situ and in 3D nanoscale dynamics in BZY during hydration over 40 h at 200 °C, in the low‐temperature range. An unexpected activity of topological defects and subsequent cracking is found on a nanoscale covered by the macroscale stability. The rearrangements in structure correlate with emergent regions of different lattice constants, suggesting heterogeneous hydration. The results highlight the extent and impact of nanoscale processes in proton‐conducting solid oxides, informing future development of low‐temperature protonic ceramic electrochemical cells. 

Abstract Non‐equilibrium defects often dictate the macroscopic properties of materials. They largely define the reversibility and kinetics of processes in intercalation hosts in rechargeable batteries. Recently, imaging methods have demonstrated that transient dislocations briefly appear in intercalation hosts during ion diffusion. Despite new discoveries, the understanding of impact, formation and self‐healing mechanisms of transient defects, including and beyond dislocations, is lacking. Here, operando X‐ray Bragg Coherent Diffractive Imaging (BCDI) and diffraction peak analysis capture the stages of formation of a unique metastable domain boundary, defect self‐healing, and resolve the local impact of defects on ionic diffusion in Na_xNi_1−yMn_yO₂intercalation hosts in a charging sodium‐ion battery. Results, applicable to a wide range of layered intercalation materials due to the shared nature of framework layers, elucidate new dynamics of transient defects and their connection to macroscopic properties, and suggest how to control the nanostructure dynamics. 

Abstract Structural and ion‐ordering phase transitions limit the viability of sodium‐ion intercalation materials in grid scale battery storage by reducing their lifetime. However, the combination of phenomena in nanoparticulate electrodes creates complex behavior that is difficult to investigate, especially on the single‐nanoparticle scale under operating conditions. In this work, operando single‐particle X‐ray diffraction (oSP‐XRD) is used to observe single‐particle rotation, interlayer spacing, and layer misorientation in a functional sodium‐ion battery. oSP‐XRD is applied to Na_2/3[Ni_1/3Mn_2/3]O₂, an archetypal P2‐type sodium‐ion‐positive electrode material with the notorious P2‐O2 phase transition induced by sodium (de)intercalation. It is found that during sodium extraction, the misorientation of crystalline layers inside individual particles increases before the layers suddenly align just prior to the P2‐O2 transition. The increase in the long‐range order coincides with an additional voltage plateau signifying a phase transition prior to the P2‐O2 transition. To explain the layer alignment, a model for the phase evolution is proposed that includes a transition from localized to correlated Jahn–Teller distortions. The model is anticipated to guide further characterization and engineering of sodium‐ion intercalation materials with P2‐O2 type transitions. oSP‐XRD, therefore, opens a powerful avenue for revealing complex phase behavior in heterogeneous nanoparticulate systems.