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At least 829 records · Page 46

Strongly Quantum Confined Colloidal Cesium Tin Iodide Perovskite Nanoplates: Lessons for Reducing Defect Density and Improving Stability

We report that within the last several years, metal halide perovskites such as methylammonium lead iodide, CH 3 NH 3 PbI 3 , have come to the forefront of scientific investigation as defect-tolerant, solution-processable semiconductors that exhibit excellent optoelectronic properties. The vast majority of study has focused on Pb-based perovskites, which have limited applications because of their inherent toxicity. To enable the broad application of these materials, the properties of lead-free halide perovskites must be explored. Here, two-dimensional, lead-free cesium tin iodide, (CsSnI 3 ), perovskite nanoplates have been synthesized and characterized for the first time. These CsSnI 3 nanoplates exhibit thicknesses of less than 4 nm and exhibit significant quantum confinement with photoluminescence at 1.59 eV compared to 1.3 eV in the bulk. Ab initio calculations employing the generalized gradient approximation of Perdew-Burke-Ernzerhof elucidate that although the dominant intrinsic defects in CsSnI 3 do not introduce deep levels inside the band gap, their concentration can be quite high. These simulations also highlight that synthesizing and processing CsSnI 3 in Sn-rich conditions can reduce defect density and increase stability, which matches insights gained experimentally. Lastly, this improvement in the understanding of CsSnI 3 represents a step toward the broader challenge of building a deeper understanding of Sn-based halide perovskites and developing design principles that will lead to their successful application in optoelectronic devices.

36 MATERIALS SCIENCE↗

Impact of Crystallographic Orientation Disorders on Electronic Heterogeneities in Metal Halide Perovskite Thin Films

Metal halide perovskite thin films have achieved remarkable performance in optoelectronic devices. To achieve higher device performance and reliability needed for wide-spread commercial deployment, spatial heterogeneity of optoelectronic properties in the perovskite thin films needs to be understood and controlled. However, clear identification of the causes underlying the heterogeneity has remained elusive. In this work, we employ a multimodal imaging approach to separate electronic heterogeneity from morphology variations in perovskite thin films. Our results reveal that disorders in the crystallographic orientation of grains and different surface terminations are the primary cause of the electronic heterogeneity. Therefore, a solution processed polycrystalline perovskite thin film with a negligible spatial variation in charge trap site density reaching that of single crystals can be achieved by minimizing crystallographic orientation disorder.

36 MATERIALS SCIENCE↗

Synthesis of Silver Nanowires with Reduced Diameters Using Benzoin-Derived Radicals to Make Transparent Conductors with High Transparency and Low Haze

Reducing the diameter of silver nanowires has been proven to be an effective way to improve their optoelectronic performance by lessening light attenuation. The state-of-the-art silver nanowires are typically around 20 nm in diameter. Here in this paper we report a modified polyol synthesis of silver nanowires with average diameters as thin as 13 nm and aspect ratios up to 3000. The success of this synthesis is based on the employment of benzoin-derived radicals in the polyol approach and does not require high-pressure conditions. The strong reducing power of radicals allows the reduction of silver precursors to occur at relatively low temperatures, wherein the lateral growth of silver nanowires is restrained because of efficient surface passivation. The optoelectronic performance of as-prepared 13 nm silver nanowires presents a sheet resistance of 28 Ω sq -1 at a transmittance of 95% with a haze factor of ~1.2%, comparable to that of commercial indium tin oxide (ITO).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Layer-Dependent Electronic Structure of Atomically Resolved Two-Dimensional Gallium Selenide Telluride

Alloying two-dimensional (2D) semiconductors provides a powerful method to tune their physical properties, especially those relevant to optoelectronic applications. However, as the crystal structure becomes more complex, it becomes increasingly difficult to accurately correlate response characteristics to detailed atomic structure. We investigate, via annular dark-field scanning transmission electron microscopy, electron energy loss spectroscopy, and second harmonic generation, the layered III-VI alloy GaSe 0.5 Te 0.5 as a function of layer number. The local atomic structure and stacking sequence for different layers is explicitly determined. We complement the measurements with first-principles calculations of the total energy and electronic band structure of GaSe 0.5 Te 0.5 for different crystal structures and layer number. The electronic band gap as well as the π and π + σ plasmons are found to be sensitive to layer number.

2D semiconductor alloys↗

Fabrication of Nickel Oxide Nanopillar Arrays on Flexible Electrodes for Highly Efficient Perovskite Solar Cells

Semiconductor nanomaterials with controlled morphologies and architectures are of critical importance for high-performance optoelectronic devices. However, the fabrication of such nanomaterials on polymer-based flexible electrodes is particularly challenging due to degradation of the flexible electrodes at a high temperature. In this paper, we report the fabrication of nickel oxide nanopillar arrays (NiO x NaPAs) on a flexible electrode by vapor deposition, which enables highly efficient perovskite solar cells (PSCs). The NiO x NaPAs exhibit an enhanced light transmittance for light harvesting, prohibit exciton recombination, promote irradiation-generated hole transport and collection, and facilitate the formation of large perovskite grains. These advantageous features result in a high efficiency of 20% and 17% for the rigid and flexible PSCs, respectively. Additionally, the NaPAs show no cracking after 500 times of bending, consistent with the mechanic simulation results. Lastly, this robust fabrication opens a new opportunity for the fabrication of a large area of high-performance flexible optoelectronic devices.

14 SOLAR ENERGY↗

Light-Induced Currents at Domain Walls in Multiferroic BiFeO3.

Multiferroic BiFeO3 (BFO) films with spontaneously formed periodic stripe domains can generate above-gap open circuit voltages under visible light illumination; nevertheless the underlying mechanism behind this intriguing optoelectronic response has not been understood to date. Here, we make contact-free measurements of light-induced currents in epitaxial BFO films via detecting terahertz radiation emanated by these currents, enabling a direct probe of the intrinsic charge separation mechanisms along with quantitative measurements of the current amplitudes and their directions. In the periodic stripe samples, we find that the net photocurrent is dominated by the charge separation across the domain walls, whereas in the monodomain samples the photovoltaic response arises from a bulk shift current associated with the non-centrosymmetry of the crystal. The peak current amplitude driven by the charge separation at the domain walls is found to be 2 orders of magnitude higher than the bulk shift current response, indicating the prominent role of domain walls acting as nanoscale junctions to efficiently separate photogenerated charges in the stripe domain BFO films. These findings show that domain-wall-engineered BFO thin films offer exciting prospects for ferroelectric-based optoelectronics, as well as bias-free strong terahertz emitters.

36 MATERIALS SCIENCE↗

Spectroscopic Comparison of Thermal Transport at Organic–Inorganic and Organic-Hybrid Interfaces Using CsPbBr 3 and FAPbBr 3 (FA = Formamidinium) Perovskite Nanocrystals

Thermal transport across interfaces depends on the matching of vibrational structure at the interface. This work examines the transfer of thermal excitation from an organic ligand coating to either all-inorganic cesium lead tribromide (CsPbBr 3 ) nanocrystals or hybrid organic-inorganic formamidinium lead tribromide (FAPbBr 3 ) nano crystals using selective infrared optical excitation. Here, these two semiconductors are directly compared because they (or similar semiconductors) are currently envisioned as strong candidates in many optoelectronic technologies and they differ due to the presence of an organic or inorganic cation, which introduces substantial differences in the phonon density of states in otherwise quite similar semiconductors. Infrared excitation of C-H vibrations of surface-bound ligands generates a temperature gradient between the organic ligand shell and nanocrystal core, which results in heat flow, measured by probing changes of the semiconductor band gap. Heat transfer to both perovskite compositions of comparable sizes is similar (25-30 ps), due to fast intramolecular vibrational relaxation and similar matching of low-energy phonons with the organic ligand, but FAPbBr 3 samples show a slow bleaching kinetic on the order of 1 ns. This slow, heat-induced change in the semiconductor band gap is attributed not to interfacial heat transfer but instead to thermal equilibration between the organic and inorganic sublattices of FAPbBr 3 . Ab initio molecular dynamics simulations support the hypothesis that low-energy inorganic sublattice phonon modes are populated initially in the heat transfer process, with a slow thermal population of the higher-energy phonon modes associated primarily with the organic cation. Slow thermal equilibration of FAPbBr 3 is likely to substantially impact the time-dependent response of optoelectronic devices that heat the semiconductor active layer and provide further evidence that the poor bulk thermal transport of hybrid perovskite materials extends to microscopic thermal processes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Photocarrier Dynamics in MoTe 2 Nanofilms with 2 H and Distorted 1 T Lattice Structures

Molybdenum telluride (MoTe 2 ), an emerging layered two-dimensional (2D) material, possesses excellent phase-changing properties. Previous studies revealed its reversible transition between 2H and 1T' phases with a transition energy as small as 35 meV. Since 1T'-MoTe 2 is metallic, it can serve as an electrical contact for semiconducting 2H-MoTe 2 -based optoelectronic devices. Here, the photocarrier dynamics in MoTe 2 nanofilms synthesized by a one-step method and with coexisting multiple phases are investigated by transient absorption measurements. Both the energy relaxation time and the recombination lifetime of the excitons are shorter in the 1T'-MoTe 2 compared to its 2H phase. Furthermore, these results provide information on the different photocarrier dynamical properties of these two phases, which is important for future 2D optoelectronic and phase-change electronic devices based on MoTe 2 .

36 MATERIALS SCIENCE↗

Double Perovskite Interlayer Stabilized Highly Efficient Perovskite Solar Cells

Metal halide perovskite solar cell (PSC) technology has an impressive power conversion efficiency (PCE) exceeding 26.1% and demonstrates cost-effective manufacturing. However, the stability of these PSCs poses a significant challenge, hindering their widespread manufacturing and commercialization. To tackle the degradation issue inherent in PSCs, surface passivation techniques, particularly employing a thin layer of two-dimensional (2D) perovskites, create a 2D/3D heterostructure. Beyond this, the exploration of metal halide double perovskites adds a new dimension to the chemical and band gap phase space of materials for optoelectronic applications. In this study, we leverage a wide band gap double perovskite interlayer to enhance the stability of 3D metal halide perovskite. Specifically, the double perovskite nanoparticle Cs 2 AgBiBr 6 , with its substantial band gap of 2.2 eV and exceptional air stability, is utilized. Through optimization, a Cs 2 AgBiBr 6 -treated PSC achieves an open-circuit voltage of 1.12 V and an impressive PCE of 19.52%. Additionally, the Cs 2 AgBiBr 6 passivation layer proves to be effective in bolstering the stability of PSCs. This work demonstrates an additional strategy and design motif to simultaneously increase the PCE of PSCs along with achieving improved stability.

14 SOLAR ENERGY↗

High-Quality AZO/Au/AZO Sandwich Film with Ultralow Optical Loss and Resistivity for Transparent Flexible Electrodes

Transparent flexible electrodes are in ever-growing demand for modern stretchable optoelectronic devices, such as, display technologies, solar cells, and smart window. Such sandwich-film-electrodes deposited on polymer substrates are unattainable because of the low quality of the films, inducing a relatively large optical loss and resistivity as well as a difficulty in elucidating the interference behavior of light. In this article, we report a high-quality AZO/Au/AZO sandwich film with excellent optoelectronic performance, e.g., an average transmittance of about 81.7% (including the substrate contribution) over the visible range, a sheet resistance of 5 Ω/sq and a figure-of-merit factor of ~55.1. These values are well ahead of those previously reported for sandwich-film-electrodes. Additionally, the interference behaviors of light modulated by the coat and metal layers have been explored with the employment of transmittance spectra and numerical simulations. In particular, a heater device based on an AZO/Au/AZO sandwich film exhibits high performance such as short response time (~5 s) and uniform temperature field. In conclusion, this work provides a deep insight into the improvement of the film quality of the sandwich electrodes and the design of high-performance transparent flexible devices by the application of a flexible substrate with an atomically smooth surface.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A single polymeric template-based full color organic electrochromic device

With low-cost and simple processing, organic electrochromic polymers have attracted considerable attention as a promising material platform for flexible and low-energy-consuming optoelectronic devices. However, typical electrochromic polymers can only be switched from natural-colored to oxidized-transparent states. As a result, the complexity of combining several distinct polymers to achieve a full-color gamut has significantly limited the niche applications of electrochromic polymers. Here in this paper we report an electrochromic polymer based on 4,7-di((3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine-3-yl)-3,4-ethylenedioxythiophene) (PEP), which exhibits fast full-color reversible tuning capability and good stability. Furthermore, a red-green-blue flexible electrochromic device just based on poly(PEP) was fabricated, which offers an effective approach to dynamically manipulate color and enables a variety of optoelectronic applications.

36 MATERIALS SCIENCE↗

Low Contact Barrier in 2H/1T' MoTe 2 In-Plane Heterostructure Synthesized by Chemical Vapor Deposition

Metal–semiconductor contact has been an important topic in the semiconductor industry because it influences device performance remarkably. Conventional metals have served as the major contact material in electronic and optoelectronic devices, but such a selection becomes increasingly inadequate for emerging novel materials such as two-dimensional (2D) materials. Deposited metals on semiconducting 2D channels usually form large resistance contacts due to the high Schottky barrier. A few approaches have been reported to reduce the contact resistance but they are not suitable for large-scale application or they cannot create a clean and sharp interface. Here, a chemical vapor deposition (CVD) technique is introduced to produce large-area semiconducting 2D material (2H MoTe 2 ) planarly contacted by its metallic phase (1T' MoTe 2 ). We demonstrate the phase-controllable synthesis and systematic characterization of large-area MoTe 2 films, including pure 2H phase or 1T' phase, and 2H/1T' in-plane heterostructure. Theoretical simulation reflects a lower Schottky barrier in 2H/1T' junction than in Ti/2H contact, which is confirmed by electrical measurement. This one-step CVD method to synthesize large-area, seamless-bonding 2D lateral metal–semiconductor junction can improve the performance of 2D electronic and optoelectronic devices, paving the way for large-scale 2D integrated circuits.

36 MATERIALS SCIENCE↗

Bidentate Ligand-Induced Oriented Transformation of CsPbBr 3 Perovskite Nanocrystals into Nanowires for X-ray Photodetectors

We report shape and dimensionality control by ligands is an efficient way to fabricate high-quality perovskite nanocrystals (NCs) with optoelectronic properties. Herein, to realize oriented transformations between different morphologies of CsPbBr 3 nanocrystals, we conceived of the use of defects and bidentate ligands to synergistically drive the reorientation of CsPbBr3nanocrystals into CsPbBr 3 nanowires (NWs). By employing aminocaproic acid as the bidentate ligand, CsPbBr 3 NWs were reconstructed from the CsPbBr 3 NCs (~7 nm) with 20-60 nm in width and several micrometers in length, as well as a 527 nm photoluminescence (PL) peak, 59% PL quantum yield, and 98.5 ns PL lifetime. The bidentate ligand-directed anisotropic shape evolution and growth of perovskite NWs from NCs was elucidated by transmission electronmicroscopy and PL studies. The photodetectors fabricated with the reconstructed CsPbBr 3 NWs displayed a photocurrent enhancement (2.75 × 10 -11 A) compared with that of the devices based on solution-synthesized NWs (2.28 × 10 -11 A). The device also showed a short response time, indicating its more sensitive photoelectric response. This process provides a viable approach to engineering diverse morphologies of perovskite nanocrystals for optoelectronic applications.

36 MATERIALS SCIENCE↗

Transient X-ray Diffraction Reveals Nonequilibrium Phase Transition in Thin Films of CH 3 NH 3 PbI 3 Perovskite

Advantageous optoelectronic properties of methylammonium lead triiodide likely arise from coupling between photogenerated charge-carriers and the soft, deformable lattice. We investigate structural dynamics of MAPbI 3 films using time-resolved X-ray diffraction versus pump-probe time delay and pump intensity. During the first nanosecond, the lattice anisotropically distorts from tetragonal to cubic at excitation intensities that are insufficient to thermally induce the first-order thermodynamic phase transition at 330K. Further, the high-symmetry structure then relaxes back to the starting phase with 11 and 236-ns time constants via a different transition pathway than observed either in the first nanosecond or in previous reports for MAPbI 3 . Early-time dynamics are consistent with polaron formation and lattice strain stabilization while the slower recovery dynamics outlive radiative recombination and relates metastability. Fluence-independence of these lattice deformations in the low-power regime conveys relevance to optoelectronics including photovoltaics and highlights sustained involvement of non-equilibrium, photoinduced lattice reorganization in MAPbI 3 under functional conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Density of States Broadening in CH 3 NH 3 PbI 3 Hybrid Perovskites Understood from ab Initio Molecular Dynamics Simulations

Lead-halide perovskites are promising materials in optoelectronic devices for their unique properties including direct band gap, strong light absorption, high carrier mobility, and low fabrication cost. Here, by using ab inito molecular dynamics and electronic structure calculations, we report a systematic study on the broadening density of states (DOS) deep in the valence bands that has been experimentally observed but absent in static calculations. We quantify the broadening DOS reduction from the cubic phase to lower-temperature tetragonal and orthorhombic phases and attribute observed effects to the molecular vibrations and the anharmonicity of iodine atoms motion. Specifically, the MA cations’ vibrations are strongly linked to the moderate C–N stretch and CH 3 bend, as well as the strong CH 3 and NH 3 + stretches. Furthermore, these results present a theoretical perspective on the structural dynamics in lead-halide perovskites which may be valuable for future studies toward desired functionalities in perovskite-based optoelectronic devices.

36 MATERIALS SCIENCE↗

Hot-Hole versus Hot-Electron Transport at Cu/GaN Heterojunction Interfaces

Among all plasmonic metals, copper (Cu) has the greatest potential for realizing optoelectronic and photochemical hot-carrier devices, thanks to its CMOS compatibility and outstanding catalytic properties. Yet, relative to gold (Au) or silver (Ag), Cu has rarely been studied and the fundamental properties of its photoexcited hot carriers are not well understood. Here, we demonstrate that Cu nanoantennas on p-type gallium nitride (p-GaN) enable hot-hole-driven photodetection across the visible spectrum. Importantly, we combine experimental measurements of the internal quantum efficiency (IQE) with ab initio theoretical modeling to clarify the competing roles of hot-carrier energy and mean-free path on the performance of hot-hole devices above and below the interband threshold of the metal. We also examine Cu-based plasmonic photodetectors on corresponding n-type GaN substrates that operate via the collection of hot electrons. By comparing hot hole and hot electron photodetectors that employ the same metal/semiconductor interface (Cu/GaN), we further elucidate the relative advantages and limitations of these complementary plasmonic systems. In particular, we find that harnessing hot holes with p-type semiconductors is a promising strategy for plasmon-driven photodetection across the visible and ultraviolet regimes. Given the technological relevance of Cu and the fundamental insights provided by our combined experimental and theoretical approach, we anticipate that our studies will have a broad impact on the design of hot-carrier optoelectronic devices and plasmon-driven photocatalytic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Localized Excitons in NbSe 2 -MoSe 2 Heterostructures

Neutral and charged excitons (trions) in atomically thin materials offer important capabilities for photonics, from ultrafast photodetectors to highly efficient light-emitting diodes and lasers. Recent studies of van der Waals (vdW) heterostructures comprised of dissimilar monolayer materials have uncovered a wealth of optical phenomena that are predominantly governed by interlayer interactions. Here, we examine the optical properties in NbSe 2 -MoSe 2 vdW hetero- structures, which provide an important model system to study metal–semiconductor interfaces, a common element in optoelectronics. Through low-temperature photoluminescence (PL) microscopy, we discover a sharp emission feature, L1, that is localized at the NbSe 2 -capped regions of MoSe 2 . L1 is observed at energies below the commonly studied MoSe 2 excitons and trions and exhibits temperature- and power-dependent PL consistent with exciton localization in a confining potential. This PL feature is robust, observed in a variety of samples fabricated with different stacking geometries and cleaning procedures. Using first-principles calculations, we reveal that the confinement potential required for exciton localization naturally arises from the in-plane band bending due to the changes in the electron affinity between pristine MoSe 2 and NbSe 2 -MoSe 2 heterostructure. Here, we discuss the implications of our studies for atomically thin optoelectronics devices with atomically sharp interfaces and tunable electronic structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗