Operando Study Insights into Lithiation/Delithiation Processes in a Poly(ethylene oxide) Electrolyte of All-Solid-State Lithium Batteries by Grazing-Incidence X-ray Scattering.

Poly(ethylene oxide) (PEO)-based composite electrolytes (PCEs) are considered as promising candidates for next-generation lithium-metal batteries (LMBs) due to their high safety, easy fabrication, and good electrochemical stability. Here, we utilize operando grazing-incidence small-angle and wide-angle X-ray scattering to probe the correlation of electrochemically induced changes and the buried morphology and crystalline structure of the PCE. Results show that the two irreversible reactions, PEO-Li+ reduction and TFSI- decomposition, cause changes in the crystalline structure, array orientation, and morphology of the PCE. In addition, the reversible Li plating/stripping process alters the inner morphology, especially the PEO-LiTFSI domain radius and distance between PEO-LiTFSI domains, rather than causing crystalline structure and orientation changes. This work provides a new path to monitor a working battery in real time and to a detailed understanding of the Li+ diffusion mechanism, which is essential for developing highly transferable and interface-stable PCE-based LMBs.

Trace Water in Lead Iodide Affecting Perovskite Crystal Nucleation Limits the Performance of Perovskite Solar Cells.

The experimental replicability of highly efficient perovskite solar cells (PSCs) is a persistent challenge faced by laboratories worldwide. Although trace impurities in raw materials can impact the experimental reproducibility of high-performance PSCs, the in situ study of how trace impurities affect perovskite film growth is never investigated. Here, light is shed on the impact of inevitable water contamination in lead iodide (PbI2 ) on the replicability of device performance, mainly depending on the synthesis methods of PbI2 . Through synchrotron-based structure characterization, it is uncovered that even slight additions of water to PbI2 accelerate the crystallization process in the perovskite layer during annealing. However, this accelerated crystallization also results in an imbalance of charge-carrier mobilities, leading to a degradation in device performance and reduced longevity of the solar cells. It is also found that anhydrous PbI2 promotes a homogenous nucleation process and improves perovskite film growth. Finally, the PSCs achieve a remarkable certified power conversion efficiency of 24.3%. This breakthrough demonstrates the significance of understanding and precisely managing the water content in PbI2 to ensure the experimental replicability of high-efficiency PSCs.

High-Power Impulse Magnetron Sputter Deposition of Ag on Self-Assembled Au Nanoparticle Arrays at Low-Temperature Dewetting Conditions.

Plasmons have facilitated diverse analytical applications due to the boosting signal detectability by hot spots. In practical applications, it is crucial to fabricate straightforward, large-scale, and reproducible plasmonic substrates. Dewetting treatment, via applying direct thermal annealing of metal films, has been used as a straightforward method in the fabrication of such plasmonic nanostructures. However, tailoring the evolution of the dewetting process of metal films poses considerable experimental complexities, mainly due to nanoscale structure formation. Here, we use grazing-incidence small- and wide-angle X-ray scattering for the in situ investigation of the high-power impulse magnetron sputter deposition of Ag on self-assembled Au nanoparticle arrays at low-temperature dewetting conditions. This approach allows us to examine both the direct formation of binary Au/Ag nanostructure and the consequential impact of the dewetting process on the spatial arrangement of the bimetallic nanoparticles. It is observed that the dewetting at 100 °C is sufficient to favor the establishment of a homogenized structural configuration of bimetallic nanostructures, which is beneficial for localized surface plasmon resonances (LSPRs). The fabricated metal nanostructures show potential application for the surface-enhanced Raman scattering (SERS) detection of rhodamine 6G molecules. As SERS platform, bimetallic nanostructures formed with dewetting conditions turn out to be superior to those without dewetting conditions. The method in this work is envisioned as a facile strategy for the fabrication of plasmonic nanostructures.

Elucidating the Roles of Nafion/Solvent Formulations in Copper-Catalyzed CO2 Electrolysis.

Nafion ionomer, composed of hydrophobic perfluorocarbon backbones and hydrophilic sulfonic acid side chains, is the most widely used additive for preparing catalyst layers (CLs) for electrochemical CO2 reduction, but its impact on the performance of CO2 electrolysis remains poorly understood. Here, we systematically investigate the role of the catalyst ink formulation on CO2 electrolysis using commercial CuO nanoparticles as the model pre-catalyst. We find that the presence of Nafion is essential for achieving stable product distributions due to its ability to stabilize the catalyst morphology under reaction conditions. Moreover, the Nafion content and solvent composition (water/alcohol fraction) regulate the internal structure of Nafion coatings, as well as the catalyst morphology, thereby significantly impacting CO2 electrolysis performance, resulting in variations of C2+ product Faradaic efficiency (FE) by >3×, with C2+ FE ranging from 17 to 54% on carbon paper substrates. Using a combination of ellipsometry and in situ Raman spectroscopy during CO2 reduction, we find that such selectivity differences stem from changes to the local reaction microenvironment. In particular, the combination of high water/alcohol ratios and low Nafion fractions in the catalyst ink results in stable and favorable microenvironments, increasing the local CO2/H2O concentration ratio and promoting high CO surface coverage to facilitate C2+ production in long-term CO2 electrolysis. Therefore, this work provides insights into the critical role of Nafion binders and underlines the importance of optimizing Nafion/solvent formulations as a means of enhancing the performance of electrochemical CO2 reduction systems.

Revealing Surface and Interface Evolution of Molybdenum Nitride as Carrier-Selective Contacts for Crystalline Silicon Solar Cells.

Molybdenum nitride (MoNx) was perceived as carrier-selective contacts (CSCs) for crystalline silicon (c-Si) solar cells due to having proper work functions and excellent conductivities. However, the poor passivation and non-Ohmic contact at the c-Si/MoNx interface endow an inferior hole selectivity. Here, the surface, interface, and bulk structures of MoNx films are systematically investigated by X-ray scattering, surface spectroscopy, and electron microscope analysis to reveal the carrier-selective features. Surface layers with the composition of MoO2.51N0.21 form upon air exposure, which induces the overestimated work function and explains the origin of inferior hole selectivities. The c-Si/MoNx interface is confirmed to adopt long-term stability, providing guidance for designing stable CSCs. A detailed evolution of the scattering length density, domain sizes, and crystallinity in the bulk phase is presented to elucidate its superior conductivity. These multiscale structural investigations offer a clear structure-function correlation of MoNx films, providing key inspiration for developing excellent CSCs for c-Si solar cells.

Decoding the Self-Assembly Plasmonic Interface Structure in a PbS Colloidal Quantum Dot Solid for a Photodetector.

Hybrid plasmonic nanostructures have gained enormous attention in a variety of optoelectronic devices due to their surface plasmon resonance properties. Self-assembled hybrid metal/quantum dot (QD) architectures offer a means of coupling the properties of plasmonics and QDs to photodetectors, thereby modifying their functionality. The arrangement and localization of hybrid nanostructures have an impact on exciton trapping and light harvesting. Here, we present a hybrid structure consisting of self-assembled gold nanospheres (Au NSs) embedded in a solid matrix of PbS QDs for mapping the interface structures and the motion of charge carriers. Grazing-incidence small-angle X-ray scattering is utilized to analyze the localization and spacing of the Au NSs within the hybrid structure. Furthermore, by correlating the morphology of the Au NSs in the hybrid structure with the corresponding differences observed in the performance of photodetectors, we are able to determine the impact of interface charge carrier dynamics in the coupling structure. From the perspective of architecture, our study provides insights into the performance improvement of optoelectronic devices.