Superfluorescence from Electron-Hole Plasma at Moderate Temperatures of 175 K.

Superfluorescence, a cooperative coherent spontaneous emission, is of great importance to the understanding of many-body correlation in optical processes. Even though superfluorescence has been demonstrated in many diverse systems, it is hard to observe in electron-hole plasma (EHP) due to its rapid dephasing and hence needs strong magnetic fields or complex microcavities. Herein, we report the first experimental observation of superfluorescence from EHP up to a moderate temperature of 175 K without external stimuli in a coupled metal halide perovskite quantum dots film. The EHP exhibits macroscopic quantum coherence through spontaneous synchronization. The coherence of the excited state decays by superfluorescence, which is redshifted 40 meV from the spontaneous emission with a ∼1700 times faster decay rate and exhibits quadratic fluence dependence. Notably, the excited state population's delayed growth and abrupt decay, which are strongly influenced by the pump fluence and the Burnham-Chiao ringing, are the characteristics of the superfluorescence. Our findings will open up a new frontier for cooperative emission and light beam-based technologies.

Carboranethiol-Protected Propeller-Shaped Photoresponsive Silver Nanomolecule.

We report the synthesis, structural characterization, and photophysical properties of a propeller-shaped Ag21 nanomolecule with six rotary arms, protected with m-carborane-9-thiol (MCT) and triphenylphosphine (TPP) ligands. Structural analysis reveals that the nanomolecule has an Ag13 central icosahedral core with six directly connected silver atoms and two more silver atoms connected through three Ag-S-Ag bridging motifs. While 12 MCT ligands protect the core through metal-thiolate bonds in a 3-6-3-layered fashion, two TPP ligands solely protect the two bridging silver atoms. Interestingly, the rotational orientation of a silver sulfide staple motif is opposite to the orientation of carborane ligands, resembling the existence of a bidirectional rotational orientation in the nanomolecule. Careful analysis reveals that the orientation of carborane ligands on the cluster's surface resembles an assembly of double rotors. The zero circular dichroism signal indicates its achiral nature in solution. There are multiple absorption peaks in its UV-vis absorption spectrum, characteristic of a quantized electronic structure. The spectrum appears as a fingerprint for the cluster. High-resolution electrospray ionization mass spectrometry proves the structure and composition of the nanocluster in solution, and systematic fragmentation of the molecular ion starts with the loss of surface-bound ligands with increasing collision energy. Its multiple optical absorption features are in good agreement with the theoretically calculated spectrum. The cluster shows a narrow near-IR emission at 814 nm. The Ag21 nanomolecule is thermally stable at ambient conditions up to 100 °C. However, white-light illumination (lamp power = 120-160 W) shows photosensitivity, and this induces structural distortion, as confirmed by changes in the Raman and electronic absorption spectra. Femtosecond and nanosecond transient absorption studies reveal an exceptionally stable excited state having a lifetime of 3.26 ± 0.02 µs for the carriers, spread over a broad wavelength region of 520-650 nm. The formation of core-centered long-lived carriers in the excited state is responsible for the observed light-activated structural distortion.

Room-Temperature Anomalous Coherent Excitonic Optical Stark Effect in Metal Halide Perovskite Quantum Dots.

Nonresonant optical driving of confined semiconductors can open up exciting opportunities for experimentally realizing strongly interacting photon-dressed (Floquet) states through the optical Stark effect (OSE) for coherent modulation of the exciton state. Here we report the first room-temperature observation of the Floquet biexciton-mediated anomalous coherent excitonic OSE in CsPbBr3 quantum dots (QDs). Remarkably, the strong exciton-biexciton interaction leads to a coherent red shift and splitting of the exciton resonance as a function of the drive photon frequency, similar to Autler-Townes splitting in atomic and molecular systems. The large biexciton binding energy of ∼71 meV and exciton-biexciton transition dipole moment of ∼25 D facilitate the hallmark observations, even at large detuning energies of >300 meV. This is accompanied by an unusual crossover from linear to nonlinear fluence dependence of the OSE as a function of the drive photon frequency. Our findings reveal crucial information on the unexplored many-body coherent interacting regime, making perovskite QDs suitable for room temperature quantum devices.