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Register a new userReal-Time Observation of Exciton-Phonon Coupling Dynamics in Self-Assembled Hybrid Perovskite Quantum Wells
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Self-assembled hybrid perovskite quantum wells have attracted attention due to their tunable emission properties, ease of fabrication and device integration. However, the dynamics of excitons in these materials, especially how they couple to phonons remains an open question. Here, we investigate two widely used materials, namely butylammonium lead iodide $(CH_3(CH_2)3NH_3)2PbI_4$ and hexylammonium lead iodide $(CH_3(CH_2)5NH_3)2PbI_4$, both of which exhibit broad photoluminescence tails at room temperature. We performed femtosecond vibrational spectroscopy to obtain a real-time picture of the exciton phonon interaction and directly identified the vibrational modes that couple to excitons. We show that the choice of the organic cation controls which vibrational modes the exciton couples to. In butylammonium lead iodide, excitons dominantly couple to a 100 cm-1 phonon mode, whereas in hexylammonium lead iodide, excitons interact with phonons with frequencies of 88 cm-1 and 137 cm-1. Using the determined optical phonon energies, we analyzed PL broadening mechanisms. At low temperatures (<100 K), the broadening is due to acoustic phonon scattering, whereas at high temperatures, LO phonon-exciton coupling is the dominant mechanism. Our results help explain the broad photoluminescence lineshapes observed in hybrid perovskite quantum wells and provide insights into the mechanism of exciton-phonon coupling in these materials.
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Understanding the nature and energy distribution of optical resonances is of central importance in low-dimensional materials$^{1-4}$ and its knowledge is critical for designing efficient optoelectronic devices. Ruddlesden-Popper halide perovskites are 2D solution-processed quantum wells with a general formula A$_2$A$_{n-1}$M$_n$X$_{3n+1}$, where optoelectronic properties can be tuned by varying the perovskite layer thickness (n value), and have recently emerged as efficient semiconductors with technologically relevant stability. However, fundamental questions concerning the nature of optical resonances (excitons or free-carriers) and the exciton reduced mass, and their scaling with quantum well thickness remains unresolved. Here, using optical spectroscopy and 60-Tesla magneto-absorption supported by modelling, we unambiguously demonstrate that the optical resonances arise from tightly bound excitons with unexpectedly high exciton reduced mass (0.20 m0) and binding energies varying from 470 meV to 125 meV with increasing thickness from n=1 to 5. Our work demonstrates the dominant role of Coulomb interactions in 2D solution-processed quantum wells and presents unique opportunities for next-generation optoelectronic and photonic devices.
Organic-inorganic layered perovskites are two-dimensional quantum wells with layers of lead-halide octahedra stacked between organic ligand barriers. The combination of their dielectric confinement and ionic sublattice results in excitonic excitations with substantial binding energies that are strongly coupled to the surrounding soft, polar lattice. However, the ligand environment in layered perovskites can significantly alter their optical properties due to the complex dynamic disorder of soft perovskite lattice. Here, we observe the dynamic disorder through phonon dephasing lifetimes initiated by ultrafast photoexcitation employing high-resolution resonant impulsive stimulated Raman spectroscopy of a variety of ligand substitutions. We demonstrate that vibrational relaxation in layered perovskite formed from flexible alkyl-amines as organic barriers is fast and relatively independent of the lattice temperature. Relaxation in aromatic amine based layered perovskite is slower, though still fast relative to pure inorganic lead bromide lattices, with a rate that is temperature dependent. Using molecular dynamics simulations, we explain the fast rates of relaxation by quantifying the large anharmonic coupling of the optical modes with the ligand layers and rationalize the temperature independence due to their amorphous packing. This work provides a molecular and time-domain depiction of the relaxation of nascent optical excitations and opens opportunities to understand how they couple to the complex layered perovskite lattice, elucidating design principles for optoelectronic devices.
In hybrid lead halide perovskites, the coupling between photogenerated charges and the ionic degrees of freedom plays a crucial role in defining the intrinsic limit of carrier mobility and lifetime. However, direct investigation of this fundamental interaction remains challenging because its relevant dynamics occur on ultrashort spatial and ultrafast temporal scales. Here, we unveil the coupled electron-lattice dynamics of a CH3NH3PbI3 single crystal upon intense photoexcitation through a unique combination of ultrafast electron diffraction, time-resolved photoelectron spectroscopy, and time-dependent ab initio calculations. We observe the structural signature of a hot-phonon bottleneck effect that prevents rapid carrier relaxation, and we uncover a phonon avalanche mechanism responsible for breaking the bottleneck. The avalanche involves a collective emission of low-energy phonons - mainly associated with the organic sub-lattice - that proceeds in a regenerative manner and correlates with the accumulation and confinement of photocarriers at the crystal surface. Our results indicate that in hybrid perovskites carrier transport and spatial confinement are key to controlling the electron-phonon interaction and their rational engineering is relevant for future applications in optoelectronic devices.
Using resonantly excited photoluminescence along with photoluminescence excitation spectroscopies, we study the carrier excitation processes in CdTe/ZnTe and CdSe/ZnSe self-assembled quantum dots. Photoluminescence excitation spectra of single CdTe quantum dots reflect two major mechanisms for carrier excitation: The first, associated with the presence of sharp and intense lines in the spectrum, is a direct excited state ? ground state transition. The second, associated with the appearance of up to four much broader excitation lines, is a LO phonon-assisted absorption directly into the quantum dot ground states. LO phonons with energies of both quantum dots and ZnTe barrier material are identified in the photoluminescence excitation spectra. Resonantly excited PL measurements for the dot ensemble as a function of excitation energy makes it possible to separate the contributions of these two mechanisms. We find that for CdTe quantum dots the distribution of excited states coupled to the ground states reflects the energy distribution of the quantum dot emission, but shifted up in energy by 100 meV. This large splitting between excited and ground states in CdTe quantum dots suggests strong spatial confinement. In contrast, the LO phonon-assisted absorption shows significant size selectivity. In the case of CdTe dots the exciton-LO phonon coupling is strongly enhanced for smaller-sized dots which have higher emission energies. In contrast, for CdSe quantum dots the exciton-LO phonon coupling is uniform over the ensemble ? that is, the energy distribution determines the intensities of LO phonon replicas. We show that for CdTe quantum dots after annealing, that is after an increase in the average dot size, the exciton-LO phonon interaction reflects the dot energy distribution, as observed for CdSe quantum dots.
Micro-photoluminescence spectroscopy at variable temperature, excitation intensity and energy was performed on a single InAs/AlAs self-assembled quantum dot. The exciton emission line (zero-phonon line, ZPL) exhibits a broad sideband due to exciton-acoustic phonon coupling by the deformation potential mechanism. Additionally, narrow low-energy sidebands at about 0.25 meV of the ZPL are attributed to exciton-acoustic phonon piezoelectric coupling. In lowering the excitation energy or intensity these bands gradually dominate the emission spectrum of the quantum dot while the ZPL disappears. At high excitation intensity the sidebands due to piezoelectric coupling decrease strongly and the ZPL dominates the spectrum as a consequence of screening of the piezoelectric coupling by the photocreated free carriers.
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