Impacts of Ion Segregation on Local Optical Properties in Mixed Halide Perovskite Films

Despite the recent astronomical success of organic–inorganic perovskite solar cells (PSCs), the impact of microscale film inhomogeneities on device performance remains poorly understood. In this work, we study CH₃NH₃PbI₃ perovskite films using cathodoluminescence in scanning transmission electron microscopy and show that localized regions with increased cathodoluminescence intensity correspond to iodide-enriched regions. These observations constitute direct evidence that nanoscale stoichiometric variations produce corresponding inhomogeneities in film cathodoluminescence intensity. Moreover, we observe the emergence of high-energy transitions attributed to beam induced iodide segregation, which may mirror the effects of ion migration during PSC operation. Our results demonstrate that such ion segregation can fundamentally change the local optical and microstructural properties of organic–inorganic perovskite films in the course of normal device operation and therefore address the observed complex and unpredictable behavior in PSC devices

Fundamental Insights into Nanowire Diameter Modulation and the Liquid/Solid Interface

Controlled modulation of diameter along the axis of nanowires can enhance nanowire-based device functionality, but the potential for achieving such structures with arbitrary diameter ratios has not been explored. Here, we use a theoretical approach that considers changes in the volume, wetting angle, and three-dimensional morphology of seed particles during nanowire growth to understand and guide nanowire diameter modulation. We use our experimental results from diameter-modulated InN and GaN nanowires and extend our analysis to consider the potential and limitations for diameter modulation in other materials systems. We show that significant diameter modulations can be promoted for seed materials that enable substantial compositional and surface energy changes. Furthermore, we apply our model to provide insights into the morphology of the liquid/solid interface. Our approach can be used to understand and guide nanowire diameter modulation, as well as probe fundamental phenomena during nanowire growth

Mapping of Strain Fields in GaAs/GaAsP Core–Shell Nanowires with Nanometer Resolution

We report the nanoscale quantification of strain in GaAs/GaAsP core–shell nanowires. By tracking the shifting of higher-order Laue zone (HOLZ) lines in convergent beam electron diffraction patterns, we observe unique variations in HOLZ line separation along different facets of the core–shell structure, demonstrating the nonuniform strain fields created by the heterointerface. Furthermore, through the use of continuum mechanical modeling and Bloch wave analysis we calculate expected HOLZ line shift behavior, which are directly matched to experimental results. This comparison demonstrates both the power of electron microscopy as a platform for nanoscale strain characterization and the reliability of continuum models to accurately calculate complex strain fields in nanoscale systems

Phalaena plecta

Semiconducting nanowires have unique properties that are distinct from their bulk counterparts, but realization of their full potential will be ultimately dictated by the ability to control nanowire structure, composition, and size with high accuracy. Here, we report a simple, yet versatile, approach to modulate in situ the diameter, length, and composition of individual segments within (In,Ga)N nanowires by tuning the seed particle supersaturation and size via the supply of III and V sources during the growth. By elucidating the underlying mechanisms controlling structural evolution, we demonstrate the synthesis of axial InN/InGaN nanowire heterojunctions in the nonpolar <i>m</i>-direction. Our approach can be applied to other materials systems and provides a foundation for future development of complex nanowire structures with enhanced functionality

Self-Seeded Growth of GaAs Nanowires by Metal–Organic Chemical Vapor Deposition

Self-seeded growth of semiconducting nanowires offers significant advantages over foreign metal-seeded growth by eliminating seed-associated impurities. However, density and diameter control of self-seeded nanowires has proven challenging although it is required for integration of nanowires into optoelectronic devices. We report the self-seeded growth of GaAs nanowire arrays on GaAs (111)­B, (110), and (111)­A substrates by metal–organic chemical vapor deposition. Our approach involves two steps: the <i>in situ</i> deposition of Ga seed particles and subsequent GaAs nanowire growth. Control of nanowire diameter and array density is achieved via Ga seed deposition temperature and substrate orientation; increased seed deposition temperatures or changing substrate orientation from (111)­A to (110) and (111)B yields reduced areal density and larger nanowire diameters. The density and diameter control approaches could be extended to other self-seeded III–V nanowire material systems

Dimensional Tailoring of Hydrothermally Grown Zinc Oxide Nanowire Arrays

Hydrothermally synthesized ZnO nanowire arrays are critical components in a range of nanostructured semiconductor devices. The device performance is governed by relevant nanowire morphological parameters that cannot be fully controlled during bulk hydrothermal synthesis due to its transient nature. Here, we maintain homeostatic zinc concentration, pH, and temperature by employing continuous flow synthesis and demonstrate independent tailoring of nanowire array dimensions including areal density, length, and diameter on device-relevant length scales. By applying diffusion/reaction-limited analysis, we separate the effect of local diffusive transport from the <i>c</i>-plane surface reaction rate and identify direct incorporation as the <i>c</i>-plane growth mechanism. Our analysis defines guidelines for precise and independent control of the nanowire length and diameter by operating in rate-limiting regimes. We validate its utility by using surface adsorbents that limit reaction rate to obtain spatially uniform vertical growth rates across a patterned substrate

Role of Au in the Growth and Nanoscale Optical Properties of ZnO Nanowires

Metallic nanoparticles play a crucial role in nanowire growth and have profound consequences on nanowire morphology and their physical properties. Here, we investigate the evolving role of the Au nanoparticle during ZnO nanowire growth and its effects on nanoscale photoemission of the nanowires. We observe the transition from Au-assisted to non-assisted growth mechanisms during a single nanowire growth, with significant changes in growth rates during these two regimes. This transition occurs through the reduction of oxygen partial pressure, which modifies the ZnO facet stability and increases Au diffusion. Nanoscale quenching of ZnO cathodoluminescence occurs near the Au nanoparticle due to excited electron diffusion to the nanoparticle. Thus, the Au nanoparticle is critically linked to the nanowire growth mechanism and corresponding growth rate through the energy of its interface with the ZnO nanowire, and its presence modifies nanowire optical properties on the nanoscale

Minority Carrier Transport in Lead Sulfide Quantum Dot Photovoltaics

Lead sulfide quantum dots (PbS QDs) are an attractive material system for the development of low-cost photovoltaics (PV) due to their ease of processing and stability in air, with certified power conversion efficiencies exceeding 11%. However, even the best PbS QD PV devices are limited by diffusive transport, as the optical absorption length exceeds the minority carrier diffusion length. Understanding minority carrier transport in these devices will therefore be critical for future efficiency improvement. We utilize cross-sectional electron beam-induced current (EBIC) microscopy and develop methodology to quantify minority carrier diffusion length in PbS QD PV devices. We show that holes are the minority carriers in tetrabutylammonium iodide (TBAI)-treated PbS QD films due to the formation of a p–n junction with an ethanedithiol (EDT)-treated QD layer, whereas a heterojunction with n-type ZnO forms a weaker n⁺–n junction. This indicates that modifying the standard device architecture to include a p-type window layer would further boost the performance of PbS QD PV devices. Furthermore, quantitative EBIC measurements yield a lower bound of 110 nm for the hole diffusion length in TBAI-treated PbS QD films, which informs design rules for planar and ordered bulk heterojunction PV devices. Finally, the low-energy EBIC approach developed in our work is generally applicable to other emerging thin-film PV absorber materials with nanoscale diffusion lengths

From GaN to ZnGa₂O₄ through a Low-Temperature Process: Nanotube and Heterostructure Arrays

We demonstrate a method to synthesize GaN–ZnGa₂O₄ core–shell nanowire and ZnGa₂O₄ nanotube arrays by a low-temperature hydrothermal process using GaN nanowires as templates. Transmission electron microscopy and X-ray photoelectron spectroscopy results show that a ZnGa₂O₄ shell forms on the surface of GaN nanowires and that the shell thickness is controlled by the time of the hydrothermal process and thus the concentration of Zn ions in the solution. Furthermore, ZnGa₂O₄ nanotube arrays were obtained by depleting the GaN core from GaN–ZnGa₂O₄ core–shell nanowire arrays during the reaction and subsequent etching with HCl. The GaN–ZnGa₂O₄ core–shell nanowires exhibit photoluminescence peaks centered at 2.60 and 2.90 eV attributed to the ZnGa₂O₄ shell, as well as peaks centered at 3.35 and 3.50 eV corresponding to the GaN core. We also demonstrate the synthesis of GaN–ZnGa₂O₄ heterojunction nanowires by a selective formation process as a simple route toward development of heterojunction nanodevices for optoelectronic applications

Diffusion-Mediated Synthesis of MoS₂/WS₂ Lateral Heterostructures

Controlled growth of two-dimensional transition metal dichalcogenide (TMD) lateral heterostructures would enable on-demand tuning of electronic and optoelectronic properties in this new class of materials. Prior to this work, compositional modulations in lateral TMD heterostructures have been considered to depend solely on the growth chronology. We show that in-plane diffusion can play a significant role in the chemical vapor deposition of MoS₂/WS₂ lateral heterostructures leading to a variety of nontrivial structures whose composition does not necessarily follow the growth order. Optical, structural, and compositional studies of TMD crystals captured at different growth temperatures and in different diffusion stages suggest that compositional mixing versus segregation are favored at high and low growth temperatures, respectively. The observed diffusion mechanism will expand the realm of possible lateral heterostructures, particularly ones that cannot be synthesized using traditional methods