Tailoring Interface Energies via Phosphonic Acids to Grow and Stabilize Cubic FAPbI3 Deposited by Thermal Evaporation.

Coevaporation of formamidinium lead iodide (FAPbI3) is a promising route for the fabrication of highly efficient and scalable optoelectronic devices, such as perovskite solar cells. However, it poses experimental challenges in achieving stoichiometric FAPbI3 films with a cubic structure (α-FAPbI3). In this work, we show that undesired hexagonal phases of both PbI2 and FAPbI3 form during thermal evaporation, including the well-known 2H-FAPbI3, which are detrimental for optoelectronic performance. We demonstrate the growth of α-FAPbI3 at room temperature via thermal evaporation by depositing phosphonic acids (PAc) on substrates and subsequently coevaporating PbI2 and formamidinium iodide. We use density-functional theory to develop a theoretical model to understand the relative growth energetics of the α and 2H phases of FAPbI3 for different molecular interactions. Experiments and theory show that the presence of PAc molecules stabilizes the formation of α-FAPbI3 in thin films when excess molecules are available to migrate during growth. This migration of molecules facilitates the continued presence of adsorbed organic precursors at the free surface throughout the evaporation, which lowers the growth energy of the α-FAPbI3 phase. Our theoretical analyses of PAc molecule-molecule interactions show that ligands can form hydrogen bonding to reduce the migration rate of the molecules through the deposited film, limiting the effects on the crystal structure stabilization. Our results also show that the phase stabilization with molecules that migrate is long-lasting and resistant to moist air. These findings enable reliable formation and processing of α-FAPbI3 films via vapor deposition.

Nematically Templated Vortex Lattices in Superconducting FeSe.

New pathways to controlling the morphology of superconducting vortex lattices─and their subsequent dynamics─are required to guide and scale vortex world-lines into a computing platform. We have found that the nematic twin boundaries align superconducting vortices in the adjacent terraces due to the incommensurate potential between vortices surrounding twin boundaries and those trapped within them. With the varying density and morphology of twin boundaries, the vortex lattice assumes several distinct structural phases, including square, regular, and irregular one-dimensional lattices. Through concomitant analysis of vortex lattice models, we have inferred the characteristic energetics of the twin boundary potential and furthermore predicted the existence of geometric size effects as a function of increasing confinement by the twin boundaries. These findings extend the ideas of directed control over vortex lattices to intrinsic topological defects and their self-organized networks, which have direct implications for the future design and control of strain-based topological quantum computing architectures.

Emergent Magnetism with Continuous Control in the Ultrahigh-Conductivity Layered Oxide PdCoO2.

The current challenge to realizing continuously tunable magnetism lies in our inability to systematically change properties, such as valence, spin, and orbital degrees of freedom, as well as crystallographic geometry. Here, we demonstrate that ferromagnetism can be externally turned on with the application of low-energy helium implantation and can be subsequently erased and returned to the pristine state via annealing. This high level of continuous control is made possible by targeting magnetic metastability in the ultrahigh-conductivity, nonmagnetic layered oxide PdCoO2 where local lattice distortions generated by helium implantation induce the emergence of a net moment on the surrounding transition metal octahedral sites. These highly localized moments communicate through the itinerant metal states, which trigger the onset of percolated long-range ferromagnetism. The ability to continuously tune competing interactions enables tailoring precise magnetic and magnetotransport responses in an ultrahigh-conductivity film and will be critical to applications across spintronics.

Polarization- and wavelength-resolved near-field imaging of complex plasmonic modes in Archimedean nanospirals.

Asymmetric nanophotonic structures enable a wide range of opportunities in optical nanotechnology because they support efficient optical nonlinearities mediated by multiple plasmon resonances over a broad spectral range. The Archimedean nanospiral is a canonical example of a chiral plasmonic structure because it supports even-order nonlinearities that are not generally accessible in locally symmetric geometries. However, the complex spiral response makes nanoscale experimental characterization of the plasmonic near-field structure highly desirable. Here we employ high-efficiency, high-spatial-resolution cathodoluminescence imaging in a scanning transmission electron microscope to describe the spatial, spectral, and polarization response of plasmon modes in the nanospiral geometry.

Bright and durable scintillation from colloidal quantum shells.

Efficient, fast, and robust scintillators for ionizing radiation detection are crucial in various fields, including medical diagnostics, defense, and particle physics. However, traditional scintillator technologies face challenges in simultaneously achieving optimal performance and high-speed operation. Herein we introduce colloidal quantum shell heterostructures as X-ray and electron scintillators, combining efficiency, speed, and durability. Quantum shells exhibit light yields up to 70,000 photons MeV-1 at room temperature, enabled by their high multiexciton radiative efficiency thanks to long Auger-Meitner lifetimes (>10 ns). Radioluminescence is fast, with lifetimes of 2.5 ns and sub-100 ps rise times. Additionally, quantum shells do not exhibit afterglow and maintain stable scintillation even under high X-ray doses (>109 Gy). Furthermore, we showcase quantum shells for X-ray imaging achieving a spatial resolution as high as 28 line pairs per millimeter. Overall, efficient, fast, and durable scintillation make quantum shells appealing in applications ranging from ultrafast radiation detection to high-resolution imaging.

Angular-Momentum Transfer Mediated by a Vibronic-Bound-State.

The notion that phonons can carry pseudo-angular momentum has many major consequences, including topologically protected phonon chirality, Berry curvature of phonon band structure, and the phonon Hall effect. When a phonon is resonantly coupled to an orbital state split by its crystal field environment, a so-called vibronic bound state forms. Here, a vibronic bound state is observed in NaYbSe2 , a quantum spin liquid candidate. In addition, field and polarization dependent Raman microscopy is used to probe an angular momentum transfer of ΔJz = ±â„ between phonons and the crystalline electric field mediated by the vibronic bound stat. This angular momentum transfer between electronic and lattice subsystems provides new pathways for selective optical addressability of phononic angular momentum via electronic ancillary states.

Hyperspectral mapping of nanoscale photophysics and degradation processes in hybrid perovskite at the single grain level.

With solar cells reaching 26.1% certified efficiency, hybrid perovskites are now the most efficient thin film photovoltaic material. Though substantial effort has focussed on synthesis approaches and device architectures to further improve perovskite-based solar cells, more work is needed to correlate physical properties of the underlying film structure with device performance. Here, using cathodoluminescence microscopy coupled with unsupervised machine learning, we quantify how nanoscale heterogeneity globally builds up within a large morphological grain of hybrid perovskite when exposed to extrinsic stimuli such as charge accumulation from electron beams or milder environmental factors like humidity. The converged electron-beam excitation allows us to map PbI2 and the emergence of other intermediate phases with high spatial and energy resolution. In contrast with recent reports of hybrid perovskite cathodoluminescence, we observe no significant change in the PbI2 signatures, even after high-energy electron beam excitation. In fact, we can exploit the stable PbI2 signatures to quantitatively map how hybrid perovskites degrade. Moreover, we show how our methodology allows disentangling of the photophysics associated with photon recycling and band-edge emission with sub-micron resolution using a fundamental understanding of electron interactions in hybrid perovskites.

Dual Emission Bands of a 2D Perovskite Single Crystal with Charge Transfer State Characteristics.

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 PEA2PbI4 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.

Disentangling Electronic Transport and Hysteresis at Individual Grain Boundaries in Hybrid Perovskites via Automated Scanning Probe Microscopy.

Underlying the rapidly increasing photovoltaic efficiency and stability of metal halide perovskites (MHPs) is the advancement in the understanding of the microstructure of polycrystalline MHP thin film. Over the past decade, intense efforts have been aimed at understanding the effect of microstructures on MHP properties, including chemical heterogeneity, strain disorder, phase impurity, etc. It has been found that grain and grain boundary (GB) are tightly related to lots of microscale and nanoscale behavior in MHP thin films. Atomic force microscopy (AFM) is widely used to observe grain and boundary structures in topography and subsequently to study the correlative surface potential and conductivity of these structures. For now, most AFM measurements have been performed in imaging mode to study the static behavior; in contrast, AFM spectroscopy mode allows us to investigate the dynamic behavior of materials, e.g., conductivity under sweeping voltage. However, a major limitation of AFM spectroscopy measurements is that they require manual operation by human operators, and as such only limited data can be obtained, hindering systematic investigations of these microstructures. In this work, we designed a workflow combining the conductive AFM measurement with a machine learning (ML) algorithm to systematically investigate grain boundaries in MHPs. The trained ML model can extract GBs locations from the topography image, and the workflow drives the AFM probe to each GB location to perform a current-voltage (IV) curve automatically. Then, we are able to have IV curves at all GB locations, allowing us to systematically understand the property of GBs. Using this method, we discovered that the GB junction points are less conductive, potentially more photoactive, and can play critical roles in MHP stability, while most previous works only focused on the difference between GB and grains.

Imaging Strain-Localized Single-Photon Emitters in Layered GaSe below the Diffraction Limit.

Nanoscale strain control of exciton funneling is an increasingly critical tool for the scalable production of single photon emitters (SPEs) in two-dimensional materials. However, conventional far-field optical microscopies remain constrained in spatial resolution by the diffraction limit and thus can provide only a limited description of nanoscale strain localization of SPEs. Here, we quantify the effects of nanoscale heterogeneous strain on the energy and brightness of GaSe SPEs on nanopillars with correlative cathodoluminescence, photoluminescence, and atomic force microscopy, supported by density functional theory simulations. We report the strain-localized SPEs have a broad range of emission wavelengths from 620 to 900 nm. We reveal substantial strain-controlled SPE wavelength tunability over a ∼100 nm spectral range and 2 orders of magnitude enhancement in the SPE brightness at the pillar center due to Type-I exciton funneling. In addition, we show that radiative biexciton cascade processes contribute to observed CL photon superbunching. Also, the GaSe SPEs show excellent stability, where their properties remain unchanged after electron beam exposure. We anticipate that this comprehensive study on the nanoscale strain control of two-dimensional SPEs will provide key insights to guide the development of truly deterministic quantum photonics.

Angle-resolved polarimetry of hybrid perovskite emission for photonic technologies.

Coupling between light and matter strongly depends on the polarization of the electromagnetic field and the nature of excitations in a material. As hybrid perovskites emerge as a promising class of materials for light-based technologies such as LEDs, LASERs, and photodetectors, it is critical to understand how their microstructure changes the intrinsic properties of the photon emission process. While the majority of optical studies have focused on the spectral content, quantum efficiency and lifetimes of emission in various hybrid perovskite thin films and nanostructures, few studies have investigated other properties of the emitted photons such as polarization and emission angle. Here, we use angle-resolved cathodoluminescence microscopy to access the full polarization state of photons emitted from large-grain hybrid perovskite films with spatial resolution well below the optical diffraction limit. Mapping these Stokes parameters as a function of the angle at which the photons are emitted from the thin film surface, we reveal the effect of a grain boundary on the degree of polarization and angle at which the photons are emitted. Such studies of angle- and polarization-resolved emission at the single grain level are necessary for future development of perovskite-based flat optics, where effects of grain boundaries and interfaces need to be mitigated.

Engineering Edge States of Graphene Nanoribbons for Narrow-Band Photoluminescence.

Solid-state narrow-band light emitters are on-demand for quantum optoelectronics. Current approaches based on defect engineering in low-dimensional materials usually introduce a broad range of emission centers. Here, we report narrow-band light emission from covalent heterostructures fused to the edges of graphene nanoribbons (GNRs) by controllable on-surface reactions from molecular precursors. Two types of heterojunction (HJ) states are realized by sequentially synthesizing GNRs and graphene nanodots (GNDs) and then coupling them together. HJs between armchair GNDs and armchair edges of the GNR are coherent and give rise to narrow-band photoluminescence. In contrast, HJs between the armchair GNDs and the zigzag ends of GNRs are defective and give rise to nonradiative states near the Fermi level. At low temperatures, sharp photoluminescence emissions with peak energy range from 2.03 to 2.08 eV and line widths of 2-5 meV are observed. The radiative HJ states are uniform, and the optical transition energy is controlled by the band gaps of GNRs and GNDs. As these HJs can be synthesized in a large quantity with atomic precision, this finding highlights a route to programmable and deterministic creation of quantum light emitters.

Spatially and spectrally resolved orbital angular momentum interactions in plasmonic vortex generators.

Understanding the near-field electromagnetic interactions that produce optical orbital angular momentum (OAM) is crucial for integrating twisted light into nanotechnology. Here, we examine the cathodoluminescence (CL) of plasmonic vortices carrying OAM generated in spiral nanostructures. The nanospiral geometry defines a photonic local density of states that is sampled by the electron probe in a scanning transmission electron microscope (STEM), thus accessing the optical response of the plasmonic vortex with high spatial and spectral resolution. We map the full spectral dispersion of the plasmonic vortex in spiral structures designed to yield increasing topological charge. Additionally, we fabricate nested nanospirals and demonstrate that OAM from one nanospiral can be coupled to the nested nanospiral, resulting in enhanced luminescence in concentric spirals of like handedness with respect to concentric spirals of opposite handedness. The results illustrate the potential for generating and coupling plasmonic vortices in chiral nanostructures for sensitive detection and manipulation of optical OAM.