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.
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.
Intrinsically disordered proteins, such as tau protein, adopt a variety of conformations in solution, complicating solution-phase structural studies. We employ an anti-Brownian electrokinetic (ABEL) trap to prolong measurements of single tau proteins in solution. Once trapped, we record the fluorescence anisotropy to investigate the diversity of conformations sampled by the single molecules. A distribution of anisotropy values obtained from trapped tau protein is conspicuously bimodal while those obtained by trapping a globular protein or individual fluorophores are not. Time-resolved fluorescence anisotropy measurements are used to provide an explanation of the bimodal distribution as originating from a shift in the compaction of the two different families of conformations.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.