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Hierarchical assemblies of ferroelectric nanodomains, so-called super-domains, can exhibit exotic morphologies that lead to distinct behaviours. Controlling these super-domains reliably is critical for realizing states with desired functional properties. Here we reveal the super-switching mechanism by using a biased atomic force microscopy tip, that is, the switching of the in-plane super-domains, of a model ferroelectric Pb 0.6 Sr 0.4 TiO 3 . We demonstrate that the writing process is dominated by a super-domain nucleation and stabilization process. A complex scanning-probe trajectory enables on-demand formation of intricate centre-divergent, centre-convergent and flux-closure polar structures. Correlative piezoresponse force microscopy and optical spectroscopy confirm the topological nature and tunability of the emergent structures. The precise and versatile nanolithography in a ferroic material and the stability of the generated structures, also validated by phase-field modelling, suggests potential for reliable multi-state nanodevice architectures and, thereby, an alternative route for the creation of tunable topological structures for applications in neuromorphic circuits., (© 2024. UT-Battelle, LLC, 2024.)

Several hybrid halide 2D-perovskite species emit light with an emergent and controversial broadband emission Stokes-shifted down from the narrow band emission. This paper uncovers the sub- and above-bandgap emission and absorption characteristics of PEA 2 PbI 4 prepared with gap states introduced during single crystal growth. Here, gap states led to coexistent intrinsic and heterostructured electronic frameworks that are selectively accessible with ultraviolet (UV) and infrared (IR) light, respectively, resulting in the phenomenon of photoluminescence (PL) switching from narrowband green to broadband red. Electron-energy dependent cathodoluminescence shows a relative increase in the broadband red PL intensity as the electron penetration depth increases from 30 nm to 2 μm, confirming the heterostructured framework is formed in the bulk of the crystal. Excitation-emission power slope of 2.5 and up-conversion pump transient absorption (TA) spectra suggest that the IR up-conversion excitation with red photoluminescence, peaked at 655 nm, is a multiphoton process occurring in the heterostructured framework through a nonlinear optical response. The energetic pathways toward the dual emission bands are revealed by pump-probe transient absorption spectroscopy, showing energetically broad gap states with high sensitivity to an IR pump are upconverted and subsequently quickly relax from high to low energy levels within 4 ps. Furthermore, the up-conversion red PL demonstrates a linear polarization with magnetic field effects, thus affirming that the band-like heterostructured framework is crystallographically aligned with characteristics of spatially extended charge-transfer states.

The dynamic nature of the metal halide perovskite lattice upon photoexcitation plays a vital role in their properties. Here we report an observation of light-induced structure dynamics in quasi-2D Ruddlesden-Popper phase perovskite thin films and its impact on the carrier transport properties. By a time-resolved X-ray scattering technique, we observe a rapid lattice expansion upon photoexcitation, followed by a slow relaxation over the course of 100 ns in the dark. Theoretical modeling suggests that the expansion originates from the lattice's thermal fluctuations caused by photon energy deposition. Power dependent optical spectroscopy and photoconductivity indicate that high laser powers triggered a strong local structural disorder, which increased the charge dissociation activation energy that results in localized transport. Our study investigates the impact of laser energy deposition on the lattices and the subsequent carrier transport properties, that are relevant to device operations.

Dual γ/neutron radiation sensors are a critical component of the nuclear security mission to prevent the proliferation of a special nuclear material (SNM). While high-performing semiconductors such as high purity germanium (HPGe) and CdZnTe (CZT) already exist in the nuclear security enterprise, their high cost and/or logistical burdens make widespread deployment difficult to achieve. Metal lead halide perovskites (MHPs) have attracted interest in recent years to address this challenge. In particular, methylammonium lead tribromide (CH 3 NH 3 PbBr 3 , MAPbBr 3 , or MAPB) has been widely evaluated for its radiation sensing capabilities. While previous studies have demonstrated low-energy X-ray and α particle sensing of MAPB-based detectors and several studies discuss the potential for γ ray sensing, neutron sensing of this material has been rarely explored. Here, we explore the incorporation of lithium in the form of LiCl into the MAPB structure to add thermal neutron sensitivity. Characterizations of the lithium-doped MAPB crystals demonstrate that quality growths are achievable with single crystals that exhibit high crystallinity, no phase change, and high macroscopic bulk quality. Finally, we report on the first demonstrated γ ray and thermal neutron sensing based on lithium-doped MAPB single crystals, which is a significant milestone in the development of 3D dual γ/neutron MHP sensors.

When periodically packing the intramolecular donor-acceptor structures to form ferroelectric-like lattice identified by second harmonic generation, our CD49 molecular crystal shows long-wavelength persistent photoluminescence peaked at 542 nm with the lifetime of 0.43 s, in addition to the short-wavelength prompt photoluminescence peaked at 363 nm with the lifetime of 0.45 ns. Interestingly, the long-wavelength persistent photoluminescence demonstrates magnetic field effects, showing as crystalline intermolecular charge-transfer excitons with singlet spin characteristics formed within ferroelectric-like lattice based on internal minority/majority carrier-balancing mechanism activated by isomer doping effects towards increasing electron-hole pairing probability. Our photoinduced Raman spectroscopy reveals the unusual slow relaxation of photoexcited lattice vibrations, indicating slow phonon effects occurring in ferroelectric-like lattice. Here, we show that crystalline intermolecular charge-transfer excitons are interacted with ferroelectric-like lattice, leading to exciton-lattice coupling within periodically packed intramolecular donor-acceptor structures to evolve ultralong-lived crystalline light-emitting states through slow phonon effects in ferroelectric light-emitting organic crystal.

Halide perovskites have undergone remarkable developments as highly efficient optoelectronic materials for a variety of applications. Several studies indicated the critical role of defects on the performance of perovskite devices. However, the parameters of defects and their interplay with free charge carriers remain unclear. In this study, we explored the dynamics of free holes in methylammonium lead tribromide (MAPbBr 3 ) single crystals using the time-of-flight (ToF) current spectroscopy. By combining ToF spectroscopy and Monte Carlo simulation, three energy states were detected in the bandgap of MAPbBr 3 In addition, we found the trapping and detrapping rates of free holes ranging from a few microseconds to hundreds of microseconds. Contrary to previous studies, we revealed a strong detrapping activity of traps. We showed that these traps substantially affect the transport properties of MAPbBr 3 , including mobility and mobility-lifetime product. Our results provide an insight on charge transport properties of perovskite semiconductors., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

This letter reports optomechanical effects occurring in a hybrid metal-halide perovskite single crystal (MAPbBr 3 ) based on resonant ultrasound spectroscopy (RUS) measurements under continuous wave (CW) laser illumination. The optomechanical effects are a new phenomenon in hybrid perovskite single crystals where the elastic constant of a single crystal is measured by RUS probed under varying excitation conditions. Our studies show that applying a CW laser (405 nm) to the single-crystal face shifts the RUS peaks to higher frequencies by about 1-4% in the perovskite single crystal at room temperature. The light-induced shift of the RUS peaks can be observed only when photoexcitation is occurring, rather than during heating, by positioning the laser wavelength within the optical absorption spectrum. In contrast, positioning the laser wavelength outside of the optical absorption spectrum leads to an absence of RUS peak shifting. Clearly, the laser-light-induced RUS peak shifts shows that the crystal elastic moduli can be changed by photoexcitation, leading to an optomechanical phenomenon via excited states. Essentially, the observed optomechanical phenomenon reflects the fact that the mechanical properties can be optically changed through internal repulsive and attractive force constants by external photoexcitation in a hybrid perovskite single crystal.