Topotactic, Vapor-Phase, In Situ Monitored Formation of Ultrathin, Phase-Pure 2D-on-3D Halide Perovskite Surfaces.

Two-dimensional (2D) halide perovskites, HaPs, can provide chemical stability to three-dimensional (3D) HaP surfaces, protecting them from exposure to ambient species and from reacting with contacting layers. Both actions occur with 2D HaPs, with the general stoichiometry R2PbI4 (R: long or bulky organic amine) covering the 3D ones. Adding such covering films can also boost power conversion efficiencies of photovoltaic cells by passivating surface/interface trap states. For maximum benefit, we need conformal ultrathin and phase-pure (n = 1) 2D layers to enable efficient tunneling of photogenerated charge carriers through the 2D film barrier. Conformal coverage of ultrathin (<10 nm) R2PbI4 layers on 3D perovskites is challenging with spin coating; even more so is its upscaling for larger-area devices. We report on vapor-phase cation exchange of the 3D surface with the R2PbI4 molecules and real-time in situ growth monitoring by photoluminescence (PL) to determine limits for forming ultrathin 2D layers. We characterize the 2D growth stages, following the changing PL intensity-time profiles, by combining structural, optical, morphological, and compositional characterizations. Moreover, from quantitative X-ray photoelectron spectroscopy (XPS) analysis on 2D/3D bilayer films, we estimate the smallest width of a 2D cover that we can grow to be <5 nm, roughly the limit for efficient tunneling through a (semi)conjugated organic barrier. We also find that, besides protecting the 3D against ambient humidity-induced degradation, the ultrathin 2D-on-3D film also aids self-repair following photodamage.

NiN-Passivated NiO Hole-Transport Layer Improves Halide Perovskite-Based Solar Cell.

The interfaces between inorganic selective contacts and halide perovskites (HaPs) are possibly the greatest challenge for making stable and reproducible solar cells with these materials. NiOx, an attractive hole-transport layer as it fits the electronic structure of HaPs, is highly stable and can be produced at a low cost. Furthermore, NiOx can be fabricated via scalable and controlled physical deposition methods such as RF sputtering to facilitate the quest for scalable, solvent-free, vacuum-deposited HaP-based solar cells (PSCs). However, the interface between NiOx and HaPs is still not well-controlled, which leads at times to a lack of stability and Voc losses. Here, we use RF sputtering to fabricate NiOx and then cover it with a NiyN layer without breaking vacuum. The NiyN layer protects NiOx doubly during PSC production. Firstly, the NiyN layer protects NiOx from Ni3+ species being reduced to Ni2+ by Ar plasma, thus maintaining NiOx conductivity. Secondly, it passivates the interface between NiOx and the HaPs, retaining PSC stability over time. This double effect improves PSC efficiency from an average of 16.5% with a 17.4% record cell to a 19% average with a 19.8% record cell and increases the device stability.

Prospect of making XPS a high-throughput analytical method illustrated for a Cu x Ni1-x O y combinatorial material library.

Combinatorial material science crucially depends on robust, high-throughput characterization methods. While X-ray photoelectron spectroscopy (XPS) may provide detailed information about chemical and electronic properties, it is a time-consuming technique and, therefore, is not viewed as a high-throughput method. Here we present preliminary XPS data of 169 measurement spots on a combinatorial 72 × 72 cm2 Cu x Ni1-x O y compositional library to explore how characterization and evaluation routines can be optimized to improve throughput in XPS for combinatorial studies. In particular, two quantification approaches are compared. We find that a simple integration (of XPS peak regions) approach is suited for fast evaluation of, in the example system, the [Cu]/([Cu] + [Ni]) ratio. Complementary to that, the time-consuming (XPS peak-) fit approach provides additional insights into chemical speciation and oxidation state changes, without a large deviation of the [Cu]/([Cu] + [Ni]) ratio. This insight suggests exploiting the fast integration approach for 'real time' analysis during XPS data collection, paving the way for an 'on-the-fly' selection of points of interest (i.e., areas on the sample where sudden composition changes have been identified) for detailed XPS characterization. Together with the envisioned improvements when going from laboratory to synchrotron-based excitation sources, this will shorten the analysis time sufficiently for XPS to become a realistic characterization option for combinatorial material science.

Carbon Nanotube Reinforced Structural Composite Supercapacitor.

Carbon nanotubes exhibit mechanical properties ideally suited for reinforced structural composites and surface area and conductivity attractive for electrochemical capacitors. Here we demonstrate the multifunctional synergy between these properties in a composite material exhibiting simultaneous mechanical and energy storage properties. This involves a reinforcing electrode developed using dense, aligned carbon nanotubes grown on stainless steel mesh that is layered in an ion conducting epoxy electrolyte matrix with Kevlar or fiberglass mats. The resulting energy storage composites exhibit elastic modulus over 5 GPa, mechanical strength greater than 85 MPa, and energy density up to 3 mWh/kg for the total combined system including electrodes, current collector, Kevlar or fiberglass, and electrolyte matrix. Furthermore, findings from in-situ mechano-electro-chemical tests indicate simultaneous mechanical and electrochemical functionality with invariant and stable supercapacitor performance maintained throughout the elastic regime.