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Loreta A. Muscarella

Publications and source records attributed to Loreta A. Muscarella.

11 recordsLinked to original sources

Milled to order: toward predictive mechanochemistry of halide perovskites

Mechanochemical milling is regarded as a scalable, solvent-free method that makes halide perovskites that solution processing cannot. Its deeper promise, though, is that mechanical force could become a new axis of synthetic control to turn milling from an empirical method into a predictive science. Halide perovskites are the ideal platform to establish this: their soft lattices and low formation energies make them intrinsically responsive to mechanical activation. Realising this requires settling what milling actually makes, and how: can a milled phase genuinely be trapped outside equilibrium, or is it just a convenient way to the equilibrium phase, and by what atomistic pathway does it work? These questions are mostly answered by assumption, while the in-situ and computational tools that resolved them for other material classes already exist. Closing this gap will unlock two design capabilities: mechanical energy used as a synthetic variable to tune phase selection, and metastability made programmable, producing trapped phases, specific intermediates, and compositions that have no possible solution route. Finally, two tests decide whether that control reaches practice: the state engineered during milling must survive into a working device, and the method must prove genuinely greener across the full device life cycle, rather than just solvent-free.

cond-mat.mtrl-sci↗

Room Temperature Optically and Magnetically Active Edges in Phosphorene Nanoribbons

Nanoribbons - nanometer wide strips of a two-dimensional material - are a unique system in condensed matter physics. They combine the exotic electronic structures of low-dimensional materials with an enhanced number of exposed edges, where phenomena including ultralong spin coherence times, quantum confinement and topologically protected states can emerge. An exciting prospect for this new material concept is the potential for both a tunable semiconducting electronic structure and magnetism along the nanoribbon edge. This combination of magnetism and semiconducting properties is the first step in unlocking spin-based electronics such as non-volatile transistors, a route to low-energy computing, and has thus far typically only been observed in doped semiconductor systems and/or at low temperatures. Here, we report the magnetic and semiconducting properties of phosphorene nanoribbons (PNRs). Static (SQUID) and dynamic (EPR) magnetization probes demonstrate that at room temperature, films of PNRs exhibit macroscopic magnetic properties, arising from their edge, with internal fields of ~ 250 to 800 mT. In solution, a giant magnetic anisotropy enables the alignment of PNRs at modest sub-1T fields. By leveraging this alignment effect, we discover that upon photoexcitation, energy is rapidly funneled to a dark-exciton state that is localized to the magnetic edge and coupled to a symmetry-forbidden edge phonon mode. Our results establish PNRs as a unique candidate system for studying the interplay of magnetism and semiconducting ground states at room temperature and provide a stepping-stone towards using low-dimensional nanomaterials in quantum electronics.

cond-mat.mes-hall↗

Which Ion Dominates Temperature and Pressure Response of Halide Perovskites and Elpasolites?

Halide perovskite and elpasolite semiconductors are extensively studied for optoelectronic applications due to their excellent performance together with significant chemical and structural flexibility. However, there is still limited understanding of their basic elastic properties and how they vary with composition and temperature, which is relevant for synthesis and device operation. To address this, we performed temperature- and pressure-dependent synchrotron-based powder X-ray diffraction (XRD). In contrast to previous pressure-dependent XRD studies, our relatively low pressures (ambient to 0.06 GPa) enabled us to investigate the elastic properties of halide perovskites and elpasolites in their ambient crystal structure. We find that halide perovskites and elpasolites show common trends in the bulk modulus and thermal expansivity. Both materials become softer as the halide ionic radius increases from Cl to Br to I, exhibiting higher compressibility and larger thermal expansivity. The mixed-halide compositions show intermediate properties to the pure compounds. Contrary, cations show a minor effect on the elastic properties. Finally, we observe that thermal phase transitions in e.g., MAPbI3 and CsPbCl3 lead to a softening of the lattice, together with negative expansivity for certain crystal axes, already tens of degrees away from the transition temperature. Hence, the range in which the phase transition affects thermal and elastic properties is substantially broader than previously thought. These findings highlight the importance of considering the temperature-dependent elastic properties of these materials, since stress induced during manufacturing or temperature sweeps can significantly impact the stability and performance of the corresponding devices.

cond-mat.mtrl-sci↗

Conduction band tuning by controlled alloying of Fe into Cs2AgBiBr6 double perovskite powders

Halide double perovskite semiconductors such as Cs2AgBiBr6 are widely investigated as a more stable, less toxic alternative to lead-halide perovskites in light conversion applications including photovoltaics and photoredox catalysis. However, the relatively large and indirect bandgap of Cs2AgBiBr6 limits efficient sunlight absorption. Here, we show that controlled replacement of Bi3+ with Fe3+ via mechanochemical synthesis results in a remarkable tunable absorption onset between 2.1 and ~1 eV. Our first-principles density functional theory (DFT) calculations suggest that this bandgap reduction originates primarily from a lowering of the conduction band upon introduction of Fe3+. Furthermore, we find that the tunability of the conduction band energy is reflected in the photoredox activity of these semiconductors. Finally, our DFT calculations predict a direct bandgap when >50% of Bi3+ is replaced with Fe3+. Our findings open new avenues for enhancing the sunlight absorption of double perovskite semiconductors and for harnessing their full potential in sustainable energy applications.

cond-mat.mtrl-sci↗

Accelerated hot-carrier cooling in MAPbI3 perovskite by pressure-induced lattice compression

Hot-carrier cooling (HCC) in metal halide perovskites in the high-density regime is significantly slower compared to conventional semiconductors. This effect is commonly attributed to a hot-phonon bottleneck but the influence of the lattice properties on the HCC behaviour is poorly understood. Using pressure-dependent transient absorption spectroscopy (fs-TAS) we find that at an excitation density below Mott transition, pressure does not affect the HCC. On the contrary, above Mott transition, HCC in methylammonium lead iodide (MAPbI3) is around two times as fast at 0.3 GPa compared to ambient pressure. Our electron-phonon coupling calculations reveal about two times stronger electron-phonon coupling for the inorganic cage mode at 0.3 GPa. However, our experiments reveal that pressure promotes faster HCC only above Mott transition. Altogether, these findings suggest a change in the nature of excited carriers in the high-density regime, providing insights on the electronic behavior of devices operating at such high charge-carrier density.

cond-mat.mtrl-sci↗

Lattice compression increases the activation barrier for phase segregation in mixed-halide perovskites

The bandgap tunability of mixed-halide perovskites makes them promising candidates for light emitting diodes and tandem solar cells. However, illuminating mixed-halide perovskites results in the formation of segregated phases enriched in a single-halide. This segregation occurs through ion migration, which is also observed in single-halide compositions, and whose control is thus essential to enhance the lifetime and stability. Using pressure-dependent transient absorption spectroscopy, we find that the formation rates of both iodide- and bromide-rich phases in MAPb(BrxI1-x)3 reduce by two orders of magnitude on increasing the pressure to 0.3 GPa. We explain this reduction from a compression-induced increase of the activation energy for halide migration, which is supported by first-principle calculations. A similar mechanism occurs when the unit cell volume is reduced by incorporating a smaller cation. These findings reveal that stability with respect to halide segregation can be achieved either physically through compressive stress or chemically through compositional engineering.

physics.app-ph↗

Thermodynamic stabilization of mixed-halide perovskites against phase segregation

Mixing iodide and bromide in halide perovskite semiconductors is an effective strategy to tune their bandgap, therefore mixed-halide perovskites hold great promise for color-tunable LEDs and tandem solar cells. However, the bandgap of mixed-halide perovskites is unstable under (sun-)light, since the halides segregate into domains of different bandgaps. Using pressure-dependent ultrafast transient absorption spectroscopy, we show that high external pressure increases the range of thermodynamically stable halide mixing ratios. Chemical pressure, by inserting a smaller cation, has the same effect, which means that any iodide-to-bromide ratio can be thermodynamically stabilized by tuning the crystal volume and compressibility. We interpret this stabilization by an alteration of the Helmholtz free energy via the largely overlooked PdeltaV term.

physics.chem-ph↗

The impact of exciton delocalization on exciton-vibration interactions in organic semiconductors

Organic semiconductors exhibit properties of individual molecules and extended crystals simultaneously. The strongly bound excitons they host are typically described in the molecular limit, but excitons can delocalize over many molecules, raising the question of how important the extended crystalline nature is. Using accurate Green's function based methods for the electronic structure and non-perturbative finite difference methods for exciton-vibration coupling, we describe exciton interactions with molecular and crystal degrees of freedom concurrently. We find that the degree of exciton delocalization controls these interactions, with thermally activated crystal phonons predominantly coupling to delocalized states, and molecular quantum fluctuations predominantly coupling to localized states. Based on this picture, we quantitatively predict and interpret the temperature and pressure dependence of excitonic peaks in the acene series of organic semiconductors, which we confirm experimentally, and we develop a simple experimental protocol for probing exciton delocalization. Overall, we provide a unified picture of exciton delocalization and vibrational effects in organic semiconductors, reconciling the complementary views of finite molecular clusters and periodic molecular solids.

cond-mat.mtrl-sci↗

Local Crystal Misorientation Influences Non-Radiative Recombination

We use ultrasensitive electron backscatter diffraction (EBSD) to map the local crystal orientations, grains, and grain boundaries in CH3NH3PbI3 (MAPI) perovskite thin films. Although the true grain structure is broadly consistent with the morphology visible in scanning electron microscopy (SEM), the inverse pole figure maps taken with EBSD reveal grain structure and internal misorientation that is otherwise hidden. Local crystal misorientation is consistent with the presence of local strain which varies from one grain to the next. We acquire co-aligned confocal optical photoluminescence (PL) microscopy images on the same MAPI samples used for EBSD. We correlate optical and EBSD data, showing that PL is anticorrelated with the local grain orientation spread, suggesting that grains with higher degrees of crystalline orientational heterogeneity (local strain) exhibit more non-radiative recombination. We find that larger grains tend to have larger grain orientation spread, consistent with higher degrees of strain and non-radiative recombination.

cond-mat.mtrl-sci↗

Crystal orientation and grain size: do they determine optoelectronic properties of MAPbI3 perovskite?

It is thought that growing large, oriented grains of perovskite can lead to more efficient devices. We study MAPbI3 films fabricated via Flash Infrared Annealing (FIRA) consisting of highly oriented, large grains. Domains observed in the SEM are often misidentified with crystallographic grains, but SEM images don't provide diffraction information. We measure the grain size, crystal structure and grain orientation using Electron Back-Scattered Diffraction (EBSD) and we study how these affect the optoelectronic properties as characterized by local photoluminescence (PL) and time-resolved microwave conductivity measurements (TRMC). We find a spherulitic growth yielding large (tens of micron), highly oriented grains along the (112) and (400) planes in contrast to randomly oriented, smaller (400 nm) grains observed in films fabricated via conventional antisolvent (AS) dripping. We observe a local enhancement and shift of the photoluminescence emission at different regions of the FIRA clusters, but these can be explained with a combination of light-outcoupling and self-absorption. We observe no effect of crystal orientation on the optoelectronic properties. Additionally, despite a substantial difference in grain size between our FIRA sample and a conventional AS sample, we find similar photoluminescence and charge carrier mobilities and lifetime for the two films. These findings show that the optoelectronic quality is not necessarily related to the orientation and size of crystalline domains in perovskite films indicating that fabrication requirements may be more relaxed for perovskites.

physics.app-ph↗

Quantification of Ion Migration in CH3NH3PbI3 Perovskite Solar Cells by Transient Capacitance Measurements

Solar cells based on organic-inorganic metal halide perovskites show efficiencies close to highly-optimized silicon solar cells. However, ion migration in the perovskite films leads to device degradation and impedes large scale commercial applications. We use transient ion-drift measurements to quantify activation energy, diffusion coefficient, and concentration of mobile ions in methylammonium lead triiodide (MAPbI3) perovskite solar cells, and find that their properties change close to the tetragonal-to-orthorhombic phase transition temperature. We identify three migrating ion species which we attribute to the migration of iodide (I-) and methylammonium (MA+). We find that the concentration of mobile MA+ ions is one order of magnitude higher than the one of mobile I- ions, and that the diffusion coefficient of mobile MA+ ions is three orders of magnitude lower than the one for mobile I- ions. We furthermore observe that the activation energy of mobile I- ions (0.29 eV) is highly reproducible for different devices, while the activation energy of mobile MA+ depends strongly on device fabrication. This quantification of mobile ions in MAPbI3 will lead to a better understanding of ion migration and its role in operation and degradation of perovskite solar cells.

cond-mat.mtrl-sci↗