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Abstract:

Lead halide perovskite nanocrystals have emerged as promising candidates for classical light-emitting devices and single-photon sources, owing to their high photoluminescence quantum yield, narrow emission line width and tunable emission. Judicious choice of ligands to passivate nanocrystal surfaces has proven to be critical to the structural stability and optoelectronic performance of such nanocrystals. While many ligands have been deployed, the resulting quality of the nanocrystal surface can be difficult to assess directly. Here, we demonstrate ultralow frequency Raman spectroscopy as a powerful tool to resolve surface-sensitive changes in size and ligand choice in perovskite nanocrystals. By investigating a size series of CsPbBr3 nanocrystals from the strong (5 nm) to the weak (28 nm) confinement range, we show that the line width of Raman-active modes provides a highly selective metric for surface disorder and quality. We further examine a series of 28 nm diameter nanocrystals with four different zwitterionic ligands, unravelling clear links between varying steric effects and surface quality evident from Raman analysis. Photoluminescence and THz photoconductivity probes reveal an evident correlation of charge-carrier dynamics and radiative emission yields with ligand chemistry and surface quality inferred from phonon broadening. We further show that surface defects preferentially trap hot charge carriers, which affects exciton stability and radiative emission yields. Overall, our approach offers powerful insights into optimizing nanocrystal-ligand boundaries to enhance the performance of nanoscale quantum light sources and optoelectronic devices.

Abstract:

Inorganic cesium‐based metal halide perovskite (MHP) semiconductors have great potential as active layers in optoelectronic devices, such as perovskite light‐emitting diodes (PeLEDs) and perovskite lasers. However, precise control of crystal type, quality, and thickness is required to create high‐performance and reproducible devices. Vapor‐phase vacuum deposition enables fabrication of MHP thin films and devices with excellent uniformity and control over layer thickness, although a full understanding of crystal growth mechanisms and products has proved elusive. Here, conditions of vapor co‐deposition of CsBr and PbBr are related with the optical performance and atomic microstructure of resulting CsPbBr3 thin films. It is found that the structure is predominantly photoactive γ‐CsPbBr3 over a wide range of conditions, but the presence of impurity phases and Ruddlesden–Popper (RP) planar defects both degrade optical performance as quantified through measured amplified spontaneous emission (ASE) thresholds. Furthermore, the atomic structure of the dominant impurity phases is resolved: CsPb2Br5 and Cs4PbBr6. It is revealed that a small nominal excess of CsBr‐precursor flux during co‐evaporation can significantly enhance the nucleation of thin films, resulting in well‐defined grains greater than 500 nm in size and the relative suppression of RP planar defects. Such films exhibit intensified photoluminescence (PL) emission and a reduced ASE threshold of 30.9 µJ cm−2.

Abstract:

Tin-halide perovskites currently offer the best photovoltaic performance of lead-free metal-halide semiconductors. However, their transport properties are mostly dominated by holes, owing to ubiquitous self-doping. Here we demonstrate a noncontact, optical spectroscopic method to determine the effective mass of the dominant hole species in FASnI3, by investigating a series of thin films with hole densities finely tuned through either SnF2 additive concentration or controlled exposure to air. We accurately determine the plasma frequency from mid-infrared reflectance spectra by modeling changes in the vibrational response of the FA cation as the plasma edge shifts through the molecular resonance. Our approach yields a hole effective mass of 0.28m e for FASnI3 and demonstrates parabolicity within ∼100 meV of the valence band edge. An absence of Fano contributions further highlights insignificant coupling between the hole plasma and FA cation. Overall, this approach enables noncontact screening of thin-film materials for optimized charge-carrier transport properties.

Abstract:

Lattice dynamics are critical to photovoltaic material performance, governing dynamic disorder, hot-carrier cooling, charge-carrier recombination, and transport. Soft metal-halide perovskites exhibit particularly intriguing dynamics, with Raman spectra exhibiting an unusually broad low-frequency response whose origin is still much debated. Here, we utilize ultra-low frequency Raman and infrared terahertz time-domain spectroscopies to provide a systematic examination of the vibrational response for a wide range of metal-halide semiconductors: FAPbI3, MAPbI x Br3–x , CsPbBr3, PbI2, Cs2AgBiBr6, Cu2AgBiI6, and AgI. We rule out extrinsic defects, octahedral tilting, cation lone pairs, and “liquid-like” Boson peaks as causes of the debated central Raman peak. Instead, we propose that the central Raman response results from an interplay of the significant broadening of Raman-active, low-energy phonon modes that are strongly amplified by a population component from Bose–Einstein statistics toward low frequency. These findings elucidate the complexities of light interactions with low-energy lattice vibrations in soft metal-halide semiconductors emerging for photovoltaic applications.