ABSTRACT
Two-dimensional (2D) halide perovskites exhibit unique structural and optical properties because large organic molecular cations distort the perovskite structure and the excitons confined in the 2D layers are stable. Here, we report the temperature dependences of the absorption spectra, second harmonic generation (SHG) intensity, and lattice constants of 2D perovskite (BA)2(EA)2Pb3I10 single crystals, where BA is n-butylammonium and EA is ethylammonium. We found that the Urbach tail of the absorption spectrum significantly changes at around 200 K and that the change is correlated with the SHG intensity and the in-plane lattice distortion. We concluded that a random distribution of spontaneous polarizations in the ferroelectric phase modifies the linewidth of the band-edge exciton transition and is the cause of the anomalous temperature dependence of the steepness parameter of the Urbach tail.
ABSTRACT
Lead halide perovskite nanocrystals are attracting considerable interest as next-generation optoelectronic materials. Optical responses of nanocrystals are determined by excitons and exciton complexes such as trions and biexcitons. Understanding of their dynamics is indispensable for the optimal design of optoelectronic devices and the development of new functional properties. Here, we summarize the recent advances on the exciton and biexciton photophysics in lead halide perovskite nanocrystals revealed by femtosecond time-resolved spectroscopy and single-dot spectroscopy. We discuss the impact of the biexciton dynamics on controlling and improving the optical gain.
ABSTRACT
Monitoring of the spatially resolved exciton spin dynamics in two-dimensional semiconductors has revealed the formation of a spatial pattern and long-range transport of the spin-polarized excitons, which holds promise for exciton-based spin-optoelectronic applications. However, the spatial evolution has been restricted to cryogenic temperatures because of the short exciton spin relaxation times at room temperature. Here, we report that two-dimensional halide perovskites can overcome this limitation owing to their relatively long exciton spin relaxation times and substantial exciton-exciton interactions. We demonstrate the emergence of a halo-like spatial profile in spin-polarized exciton population and its ultrafast expansion at room temperature by performing time-resolved Faraday rotation imaging of spin-polarized excitons in two-dimensional perovskite (C4H9NH3)2(CH3NH3)3Pb4I13. Exciton-exciton exchange interactions induce density-dependent nonlinear relaxation and ultrafast transport of exciton spins and give rise to a rapidly expanding halo-like spatial pattern. The density-dependent spatial control suggests the potential of using two-dimensional halide perovskites for spin-optoelectronic applications.
ABSTRACT
Perovskite materials with tunable electronic and structural characteristics can realize various physical properties including electrical/ionic conduction, ferroelectricity, and luminescence. Integrating and coupling these properties in a single perovskite material offer new possibilities for fundamental research and applications. In particular, coupling ferroelectricity and luminescence would enable novel applications. Here, we report that the metal-free ferroelectric perovskite MDABCO (N-methyl-N'-diazabicyclo[2.2.2]octonium)-ammonium triiodide exhibits coupled superior ferroelectricity and visible photoluminescence (PL). Besides strong second-harmonic generation (SHG) associated with its ferroelectricity, MDABCO-ammonium triiodide shows long-lifetime PL at room temperature. Remarkably, the PL intensity depends strongly on the polarization of the excitation light. We found that this anisotropy is coupled to the local crystal orientation that was determined by polarization-resolved SHG. Our results suggest that the anisotropic PL property can be tuned in response to its ferroelectric state via an external field and, thereby, presents a previosuly unobserved functionality in perovskites.
ABSTRACT
Manipulation of excitons via coherent light-matter interaction is a promising approach for quantum state engineering and ultrafast optical modulation. Various excitation pathways in the excitonic multilevel systems provide controllability more efficient than that in the two-level system. However, these control schemes have been restricted to limited control-light wavelengths and cryogenic temperatures. Here, we report that lead halide perovskites can lift these restrictions owing to their multiband structure induced by strong spin-orbit coupling. Using CsPbBr3 perovskite nanocrystals, we observe an anomalous enhancement of the exciton energy shift at room temperature with increasing control-light wavelength from the visible to near-infrared region. The enhancement occurs because the interconduction band transitions between spin-orbit split states have large dipole moments and induce a crossover from the two-level optical Stark effect to the three-level Autler-Townes effect. Our finding establishes a basis for efficient coherent optical manipulation of excitons utilizing energy states with large spin-orbit splitting.
ABSTRACT
We investigate the impact of phonon excitations on the photoexcited carrier dynamics in a lead-halide perovskite CH_{3}NH_{3}PbI_{3}, which hosts unique low-energy phonons that can be directly excited by terahertz pulses. Our time-resolved photoluminescence measurements reveal that strong terahertz excitation prolongs the cooling time of hot carriers, providing direct evidence for the hot-phonon bottleneck effect. In contrast to the previous studies where phonons are treated as a passive heat bath, our results demonstrate that phonon excitation can significantly perturb the carrier relaxation dynamics in halide perovskites through the coupling between transverse- and longitudinal-optical phonons.
ABSTRACT
Ionization of nanocrystals (NCs) causes both photoluminescence intermittency and a reduction in luminescence quantum efficiency and thus plays a critical role in the optoelectronic performance of NC-based devices. Here, we study the ionization and neutralization processes of CsPbBr3 perovskite NCs under strong photoexcitation by means of double-pump transient absorption spectroscopy. A strong initial pulse is used to generate ionized NCs, and their optical responses are investigated by varying the excitation intensity and delay time of the second pump pulse. We find that charging can occur either via nonradiative Auger recombination of biexcitons or via any possible recombination of trions. The presence of the extra charge inside of an ionized perovskite NC significantly reduces its absorption cross section. The experiments reveal that ionized NCs exhibit two types of neutralization processes with time constants on the order of nanoseconds and microseconds. These results are useful for the optimal design of NC-based photonic devices.
ABSTRACT
Combining the superior optical properties of their bulk counterparts with quantum confinement effects, lead halide perovskite nanocrystals are unique laser materials with low-threshold optical gain. In such nonlinear optical regimes, multiple excitons are generated in the nanocrystals and strongly affect the optical gain through many-body interactions. Here, we investigate the exciton-exciton interactions in CsPbI3 nanocrystals by femtosecond transient absorption spectroscopy. From the analysis of the induced absorption signal observed immediately after the pump excitation, we estimated the binding energy for the hot biexcitons that are composed of an exciton at the band edge and a hot exciton generated by the pump pulse. We found that the exciton-exciton interaction becomes stronger for hot excitons with greater excess energies and that the optical gain can be controlled by changing the excess energy of the hot excitons.
Subject(s)
Cesium/radiation effects , Electrons , Iodides/radiation effects , Lead/radiation effects , Nanoparticles/radiation effects , Cesium/chemistry , Iodides/chemistry , Lead/chemistry , Light , Nanoparticles/chemistry , Particle Size , Spectrophotometry , ThermodynamicsABSTRACT
We investigated the ultrafast terahertz (THz) nonlinearity in a monolayer graphene under the strong magnetic field using THz pump-THz probe spectroscopy. An ultrafast suppression of the Faraday rotation associated with inter-Landau level (LL) transitions is observed, reflecting the Dirac electron character of nonequidistant LLs with large transition dipole moments. A drastic modulation of electron distribution in LLs is induced by far off-resonant THz pulse excitation in the transparent region. Numerical simulation based on the density matrix formalism without rotating-wave approximation reproduces the experimental results. Our results indicate that the strong light-matter coupling regime is realized in graphene, with the Rabi frequency exceeding the carrier wave frequency and even the relevant energy scale of the inter-LL transition.
