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Register a new userExciton and Carrier Dynamics in 2D Perovskites
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Two-dimensional Ruddlesden-Popper hybrid lead halide perovskites have become a major topic in perovskite optoelectronics. Here, we aim to unravel the ultrafast dynamics governing the evolution of charge carriers and excitons in these materials. Using a combination of ultrabroadband time-resolved THz (TRTS) and fluorescence upconversion spectroscopies, we find that sequential carrier cooling and exciton formation best explain the observed dynamics, where exciton-exciton interactions play an important role in the form of Auger heating and biexciton formation. We show that the presence of a longer-lived population of carriers is due to these processes and not to a Mott transition. Therefore, excitons still dominate at laser excitation densities. We use kinetic modeling to compare the phenethylammonium and butylammonium organic cations while investigating the stability of the resulting films. In addition, we demonstrate the capability of using ultrabroadband TRTS to study excitons in large binding energy semiconductors through spectral analysis at room temperature.
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In recent years, metal halide perovskites have generated tremendous interest for optoelectronic applications and their underlying fundamental properties. Due to the large electron-phonon coupling characteristic of soft lattices, self-trapping phenomena are expected to dominate hybrid perovskite photoexcitation dynamics. Yet, while the photogeneration of small polarons was proven in low dimensional perovskites, the nature of polaron excitations in technologically relevant 3D perovskites, and their influence on charge carrier transport, remain elusive. In this study, we used a combination of first principle calculations and advanced spectroscopy techniques spanning the entire optical frequency range to pin down polaron features in 3D metal halide perovskites. Mid-infrared photoinduced absorption shows the photogeneration of states associated to low energy intragap electronic transitions with lifetime up to the ms time scale, and vibrational mode renormalization in both frequency and amplitude. Density functional theory supports the assignment of the spectroscopic features to large polarons leading to new intra gap transitions, hardening of phonon mode frequency, and renormalization of the oscillator strength. Theory provides quantitative estimates of the charge carrier masses and mobilities increase upon polaron formation, confirming experimental results. Overall, this work contributes to complete the scenario of elementary photoexcitations in metal halide perovskites and highlights the importance of polaronic transport in perovskite-based optoelectronic devices.
Halide perovskites have emerged as disruptive semiconductors for applications including photovoltaics and light emitting devices, with modular optoelectronic properties realisable through composition and dimensionality tuning. Layered Ruddlesden-Popper perovskites of the form BA2MAn-1PbnI3n+1, where n is the number of lead-halide and methylammonium (MA) sheets spaced by longer butylammonium (BA) cations, are particularly interesting due to their unique two-dimensional character and charge carrier dynamics dominated by strongly bound excitons. However, long-range energy transport through exciton diffusion in these materials is not understood or realised. Here, we employ local time-resolved luminescence mapping techniques to visualise exciton transport in high-quality exfoliated flakes of the BA2MAn-1PbnI3n+1 perovskite family. We uncover two distinct transport regimes, depending on the temperature range studied. At temperatures above 100 K, diffusion is mediated by thermally activated hopping processes between localised states. At lower temperatures, a non-uniform energetic landscape emerges in which exciton transport is dominated by energy funnelling processes to lower energy states, leading to long range transport over hundreds of nanometres even in the absence of exciton-phonon coupling and in the presence of local optoelectronic heterogeneity. Efficient, long-range and switchable excitonic funnelling offers exciting possibilities of controlled directional long-range transport in these 2D materials for new device applications.
Mixing halides in metal halide perovskites (MHPs) is an effective approach to adjust MHPs bandgap for applications in tandem solar cells. However, mixed-halide (MH-) MHPs undergo light-induced-phase-segregation (LIPS) under continuous illumination. Therefore, understanding the mechanism of LIPS is necessary for developing stable MH-MHPs. In this work, we investigated LIPS in layered (L) MHPs and discovered a critical role of spacer cations in LIPS. Through probing chemical changes of LIPS, we unveil light-induced-iodide-repulsion and the formation of Br-rich-phase in illuminated regions during LIPS. This discovery also gives insight into LIPS process in three dimensional (3D) MHPs. By further investigating LIPS in 3D MHPs, we reveal that LIPS induces not only the formation of Br-rich and I-rich domains but also an overall change of halide distribution along the film thickness direction, which can affect the electronic energy alignment and consequently MHPs devices performance. Moreover, LIPS is more significant in the bulk due to larger population of photogenerated charge carriers. Overall, this study reveals the chemical mechanism of LIPS in MHPs and its potential effect on device performance, offering insight into understanding LIPS mechanism and improving the stability of MHPs.
The outstanding performance of organic-inorganic metal trihalide solar cells benefits from the exceptional photo-physical properties of both electrons and holes in the material. Here, we directly probe the free-carrier dynamics in Cs-doped FAPbI3 thin films by spatiotemporal photoconductivity imaging. Using charge transport layers to selectively quench one type of carriers, we show that the two relaxation times on the order of 1 microsecond and 10 microseconds correspond to the lifetimes of electrons and holes in FACsPbI3, respectively. Strikingly, the diffusion mapping indicates that the difference in electron/hole lifetimes is largely compensated by their disparate mobility. Consequently, the long diffusion lengths (3 ~ 5 micrometers) of both carriers are comparable to each other, a feature closely related to the unique charge trapping and de-trapping processes in hybrid trihalide perovskites. Our results unveil the origin of superior diffusion dynamics in this material, crucially important for solar-cell applications.
The vibrational modes in organic/inorganic layered perovskites are of fundamental importance for their optoelectronic properties. The hierarchical architecture of the Ruddlesden-Popper phase of these materials allows for distinct directionality of the vibrational modes withrespect to the main axes of the pseudocubic lattice in the octahedral plane. Here, we study the directionality of the fundamental phonon modes in single exfoliated Ruddlesden-Popper perovskite flakes with polarized Raman spectroscopy at ultralow-frequencies. A wealth of Raman bands is distinguished in the range from 15-150 cm-1 (2-15 meV), whose features depend on the organic cation species, on temperature, and on the direction of the linear polarization of the incident light. By controlling the angle of the linear polarization of the excitation laser with respect to the in-plane axes of the octahedral layer, we gain detailed information on the symmetry of the vibrational modes. The choice of two different organic moieties, phenethylammonium (PEA) and butylammonium (BA) allows to discern the influence of the linker molecules, evidencing strong anisotropy of the vibrations for the (PEA)2PbBr4 samples. Temperature dependent Raman measurements reveal that the broad phonon bands observed at room temperature consist of a series of sharp modes, and that such mode splitting strongly differs for the different organic moieties and vibrational bands.
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