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Register a new userPhotoinduced iodide repulsion and halides-demixing in layered perovskites
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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.
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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.
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.
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.
We perform a thorough first-principles study on superconductivity in yttrium carbide halide Y$_2$$X_2$C$_2$ ($X$=Cl, Br, I) whose maximum transition temperature ($T_{rm c}$) amounts to $sim$10 K. A detailed analysis on the optimized crystal structures reveals that the Y$_2$C$_2$ blocks are compressed uniaxially upon the halogen substitution from Cl, Br to I, contrary to the monotonic expansion of the lattice vectors. With a nonempirical method based on the density functional theory for superconductors within the conventional phonon mechanism, we successfully reproduce the halogen dependence of $T_{rm c}$. Anomalously enhanced coupling of one C$_2$ libration mode is observed in Y$_2$I$_2$C$_2$, which imply possible departure from the conventional pairing picture. Utilizing the Wannier representation of the electron-phonon coupling, we show that the halogen electronic orbitals and ionic vibrations scarcely contribute to the superconducting pairing. The halogen dependence of this system is hence an indirect effect of the halogen ions through the uniaxial compressive force on the superconducting Y$_2$C$_2$ blocks. We thus establish a quantitatively reliable picture of the superconducting physics of this system, extracting a unique effect of the atomic substitution which is potentially applicable to other superconductors.
Layered lead halide A2An-1PbnI3n+1 perovskites (2D LHPs) are attracting considerable attention as a more stable alternative with respect to APbI3 counterparts, a workhorse material for a new generation of solar cells. However, a critical analysis on the photostability of 2D perovskites comparing n = 1 to n > 3 and to APbI3 system is still missing. In this work, we perform a comparative study of BA$_2$MA$_{n-1}$Pb$_n$I$_{3n+1}$ (BA - butylammonium, MA - methylammonium) 2D LHPs with different layer number (n = 1-3), considered as study-case systems, and MAPbI3, as a reference. We discuss a stability testing protocol with general validity, comparing photometrical determination of iodine-containing products in nonpolar solvents, X-ray diffraction, and photoluminescence spectroscopy. We identify oxygen concentration as a critical factor affecting 2D perovskites photostability. This leads to a photocorrosion of LHPs that becomes highly dependent on the perovskite dimensionality and the chemical origin of atmosphere at the aging stage as confirmed by joint experimental and theoretical analyses. This mechanism, based on redox equilibriums with internal (I-/I2, Pb2+/Pb, RAH+/RA+H2) and external (O2/H2O) species, explains both a nonmonotonic dependence of 2D LHPs photostability in an inert atmosphere on the number n and a strong enhancement of photocorrosion rate under oxidizing environment.
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