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.

Microcavity Enhanced Raman Spectroscopy of Fullerene C60 Bucky Balls.

Raman spectroscopy is a widely used characterization technique in material science. It is a non-destructive tool with relatively simple instrumentation, and provides intrinsic qualitative information of analytes by probing their vibrational modes. In many cases, Raman enhancement is essential for detecting low-intensity signals in high-noise environments, spectrally unresolved features, and hidden modes. Here we present optical and Raman spectroscopic characterization of fullerene C 60 in a gold microcavity. The fabrication of single-layered gold mirrors is facile, low cost and direct but was proven to give considerably significant enhancement. The findings of this work demonstrate the cavity resonance as a powerful tool in obtaining tunability over individual peak for selective enhancement in the tuned spectral range. The PL of the material within the cavity has demonstrated a red shift assumed to be caused by the low-energy transitions. These transitions are induced by virtual low-energy states generated by the cavity. We further observe that adopting this principle enables resolution of active Raman modes that until now were unobserved. Finally, we assigned the new experimentally observed modes to the corresponding motions calculated by DFT.