All-inorganic cesium lead iodide (CsPbI3) perovskite has improved thermal stability over the organic–inorganic hybrid perovskites and a suitable bandgap for optoelectronic and photovoltaic applications, but it is thermodynamically unstable at room temperature and has multiple structural polymorphs. Here, we show that the use of long-chain ammonium additives during thin film deposition as surface capping ligands results in the stabilization of metastable bulk CsPbI3 perovskite phases without alloying mixed cations or anions into the perovskite lattice. Moreover, two different metastable CsPbI3 perovskite polymorphs in the cubic (α-CsPbI3) and the much less common orthorhombic (β-CsPbI3) structures can be directly synthesized in a one-step spin coating film deposition by using oleylammonium or phenylethyl­ammonium additives, respectively, and both phases are stable at room temperature for months. Time-resolved photoluminescence and photoluminescence quenching experiments show that the photoexcited species in the stabilized orthorhombic CsPbI3 thin film are mainly free carriers under solar illumination with a carrier lifetime of ∼50 ns and carrier diffusion length on the order of ∼100 nm, which implies efficient carrier transport within the film despite the presence of surface ligands. Our results provide a new chemical strategy to synthesize metastable all-inorganic CsPbI3 perovskites, which, together with the good photophysical properties, will open them up for applications in photovoltaic and other optoelectronic devices.

Hybrid photonic-plasmonic systems have tremendous potential as versatile platforms for the study and control of nanoscale light-matter interactions since their respective components have either high-quality factors or low mode volumes. Individual metallic nanoparticles deposited on optical microresonators provide an excellent example where ultrahigh-quality optical whispering-gallery modes can be combined with nanoscopic plasmonic mode volumes to maximize the system's photonic performance. Such optimization, however, is difficult in practice because of the inability to easily measure and tune critical system parameters. In this Letter, we present a general and practical method to determine the coupling strength and tailor the degree of hybridization in composite optical microresonator-plasmonic nanoparticle systems based on experimentally measured absorption spectra. Specifically, we use thermal annealing to control the detuning between a metal nanoparticle's localized surface plasmon resonance and the whispering-gallery modes of an optical microresonator cavity. We demonstrate the ability to sculpt Fano resonance lineshapes in the absorption spectrum and infer system parameters critical to elucidating the underlying photonic-plasmonic hybridization. We show that including decoherence processes is necessary to capture the evolution of the lineshapes. As a result, thermal annealing allows us to directly tune the degree of hybridization and various hybrid mode quantities such as the quality factor and mode volume and ultimately maximize the Purcell factor to be 10.

Optical microresonators confine light to a particular microscale trajectory, are exquisitely sensitive to their microenvironment, and offer convenient readout of their optical properties. Taken together, this is an immensely attractive combination that makes optical microresonators highly effective as sensors and transducers. Meanwhile, advances in material science, fabrication techniques, and photonic sensing strategies endow optical microresonators with new functionalities, unique transduction mechanisms, and in some cases, unparalleled sensitivities. In this progress report, the operating principles of these sensors are reviewed, and different methods of signal transduction are evaluated. Examples are shown of how choice of materials must be suited to the analyte, and how innovations in fabrication and sensing are coupled together in a mutually reinforcing cycle. A tremendously broad range of capabilities of microresonator sensors is described, from electric and magnetic field sensing to mechanical sensing, from single-molecule detection to imaging and spectroscopy, from operation at high vacuum to in live cells. Emerging sensing capabilities are highlighted and put into context in the field. Future directions are imagined, where the diverse capabilities laid out are combined and advances in scalability and integration are implemented, leading to the creation of a sensor unparalleled in sensitivity and information content.

Organic-inorganic lead iodide perovskites are efficient materials for photovoltaics and light-emitting diodes. We report carrier decay dynamics of nanorods of mixed cation formamidinium and methylammonium lead iodide perovskites [HC(NH)][CHNH]PbI (FAMAPbI) synthesized through a simple solution method. The structure and FA/MA composition ratio of the single-crystal FAMAPbI nanorods are fully characterized, which shows that the mixed cation FAMAPbI nanorods are stabilized in the perovskite structure. The photoluminescence (PL) emission from FAMAPbI nanorods continuously shifts from 821 to 782 nm as the MA ratio (x) increases from 0 to 1 and is shown to be inhomogeneously broadened. Time-resolved PL from individual FAMAPbI nanorods demonstrates that lifetimes of mixed cation FAMAPbI nanorods are longer than those of the pure FAPbI or MAPbI nanorods, and the FAMAPbI displays the longest average PL lifetime of about 2 μs. These results suggest that mixed cation FAMAPbI perovskites are promising for high-efficiency photovoltaics and other optoelectronic applications.

Hybrid organic–inorganic perovskites demonstrate desirable photophysical behaviors and promising applications from efficient photovoltaics to lasing, but the fundamental nature of excited state species is still under debate. We collected time-resolved photoluminescence of single-crystal nanoplates of methylammonium lead iodide perovskite (MAPbI3) with excitation over a range of fluences and repetition rates to provide a more complete photophysical picture. A fundamentally different way of simulating the photophysics is developed that relies on unnormalized decays, global analysis over a large array of conditions, and inclusion of steady-state behavior; these details are critical to capturing observed behaviors. These additional constraints require inclusion of spatially correlated pairs along with free carriers and traps, demonstrating the importance of our comprehensive analysis. Modeling geminate and nongeminate pathways shows that geminate processes are dominant at high carrier densities and early times and that geminate recombination is catalyzed by free holes. Our combination of data and simulation provides a detailed picture of perovskite photophysics across multiple excitation regimes that was not previously available.