Phonon-driven intra-exciton Rabi oscillations in CsPbBr3 halide perovskites.

Coupling electromagnetic radiation with matter, e.g., by resonant light fields in external optical cavities, is highly promising for tailoring the optoelectronic properties of functional materials on the nanoscale. Here, we demonstrate that even internal fields induced by coherent lattice motions can be used to control the transient excitonic optical response in CsPbBr3 halide perovskite crystals. Upon resonant photoexcitation, two-dimensional electronic spectroscopy reveals an excitonic peak structure oscillating persistently with a 100-fs period for up to ~2 ps which does not match the frequency of any phonon modes of the crystals. Only at later times, beyond 2 ps, two low-frequency phonons of the lead-bromide lattice dominate the dynamics. We rationalize these findings by an unusual exciton-phonon coupling inducing off-resonant 100-fs Rabi oscillations between 1s and 2p excitons driven by the low-frequency phonons. As such, prevailing models for the electron-phonon coupling in halide perovskites are insufficient to explain these results. We propose the coupling of characteristic low-frequency phonon fields to intra-excitonic transitions in halide perovskites as the key to control the anharmonic response of these materials in order to establish new routes for enhancing their optoelectronic properties.

Active Reaction Control of Cu Redox State Based on Real-Time Feedback from In Situ Synchrotron Measurements.

We achieve a target material state by using a recursive algorithm to control the material reaction based on real-time feedback on the system chemistry from in situ X-ray absorption spectroscopy. Without human intervention, the algorithm controlled O2:H2 gas partial pressures to approach a target average Cu oxidation state of 1+ for γ-Al2O3-supported Cu. This approach represents a new paradigm in autonomation for materials discovery and synthesis optimization; instead of iterating the parameters following the conclusion of each of a series of reactions, the iteration cycle has been scaled down to time points during an individual reaction. Application of the proof-of-concept illustrated here, using a feedback loop to couple in situ material characterization and the reaction conditions via a decision-making algorithm, can be readily envisaged in optimizing and understanding a broad range of systems including catalysis.

Effect of Low Pressure on Tetragonal to Cubic Phase Transition of Methylammonium Lead Iodide Perovskite.

The attractive optoelectronic properties of MAPbI3 (MA = CH3NH3), one of the most common halide perovskites, can be complicated by its tetragonal → cubic structural phase transition just above room temperature. We show that decreasing the ambient pressure can move that phase transition by ∼40 °C (at ∼10-3 mbar). Our report also includes control experiments, which show that desorption of water or oxygen can be excluded as possible causes for the change in phase transition temperature. On the basis of diffraction data, we postulate that an optimum volume is required to initiate a T → C phase transition. The pressure-induced phase change in effect stabilizes the tetragonal phase for work around room temperature, even if some natural heating occurs.

Ultrafast Charge Carrier Relaxation in Inorganic Halide Perovskite Single Crystals Probed by Two-Dimensional Electronic Spectroscopy.

Halide perovskites are promising optoelectronic materials. Despite impressive device performance, especially in photovoltaics, the femtosecond dynamics of elementary optical excitations and their interactions are still debated. Here we combine ultrafast two-dimensional electronic spectroscopy (2DES) and semiconductor Bloch equations (SBEs) to probe the room-temperature dynamics of nonequilibrium excitations in CsPbBr3 crystals. Experimentally, we distinguish between excitonic and free-carrier transitions, extracting a ∼30 meV exciton binding energy, in agreement with our SBE calculations and with recent experimental studies. The 2DES dynamics indicate remarkably short, <30 fs carrier relaxation at a ∼3 meV/fs rate, much faster than previously anticipated for this material, but similar to that in direct band gap semiconductors such as GaAs. Dynamic screening of excitons by free carriers also develops on a similarly fast <30 fs time scale, emphasizing the role of carrier-carrier interactions for this material's optical properties. Our results suggest that strong electron-phonon couplings lead to ultrafast relaxation of charge carriers, which, in turn may limit halide perovskites' carrier mobilities.

Self-Healing Inside APbBr3 Halide Perovskite Crystals.

Self-healing, where a modification in some parameter is reversed with time without any external intervention, is one of the particularly interesting properties of halide perovskites. While there are a number of studies showing such self-healing in perovskites, they all are carried out on thin films, where the interface between the perovskite and another phase (including the ambient) is often a dominating and interfering factor in the process. Here, self-healing in perovskite (methylammonium, formamidinium, and cesium lead bromide (MAPbBr3 , FAPbBr3 , and CsPbBr3 )) single crystals is reported, using two-photon microscopy to create damage (photobleaching) ≈110 µm inside the crystals and to monitor the recovery of photoluminescence after the damage. Self-healing occurs in all three perovskites with FAPbBr3 the fastest (≈1 h) and CsPbBr3 the slowest (tens of hours) to recover. This behavior, different from surface-dominated stability trends, is typical of the bulk and is strongly dependent on the localization of degradation products not far from the site of the damage. The mechanism of self-healing is discussed with the possible participation of polybromide species. It provides a closed chemical cycle and does not necessarily involve defect or ion migration phenomena that are often proposed to explain reversible phenomena in halide perovskites.

Tetragonal CH3NH3PbI3 is ferroelectric.

Halide perovskite (HaP) semiconductors are revolutionizing photovoltaic (PV) solar energy conversion by showing remarkable performance of solar cells made with HaPs, especially tetragonal methylammonium lead triiodide (MAPbI3). In particular, the low voltage loss of these cells implies a remarkably low recombination rate of photogenerated carriers. It was suggested that low recombination can be due to the spatial separation of electrons and holes, a possibility if MAPbI3 is a semiconducting ferroelectric, which, however, requires clear experimental evidence. As a first step, we show that, in operando, MAPbI3 (unlike MAPbBr3) is pyroelectric, which implies it can be ferroelectric. The next step, proving it is (not) ferroelectric, is challenging, because of the material's relatively high electrical conductance (a consequence of an optical band gap suitable for PV conversion) and low stability under high applied bias voltage. This excludes normal measurements of a ferroelectric hysteresis loop, to prove ferroelectricity's hallmark switchable polarization. By adopting an approach suitable for electrically leaky materials as MAPbI3, we show here ferroelectric hysteresis from well-characterized single crystals at low temperature (still within the tetragonal phase, which is stable at room temperature). By chemical etching, we also can image the structural fingerprint for ferroelectricity, polar domains, periodically stacked along the polar axis of the crystal, which, as predicted by theory, scale with the overall crystal size. We also succeeded in detecting clear second harmonic generation, direct evidence for the material's noncentrosymmetry. We note that the material's ferroelectric nature, can, but need not be important in a PV cell at room temperature.