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Low‐dimensional organic–inorganic metal halide hybrids (OMHHs) exhibit remarkable optical properties and enhanced environmental stability. We investigate a 1D OMHH with formula C4N2H14PbBr4, consisting of Pb–Br chains separated by organic cations, which shows a large Stokes shift (0.83 eV) and broadband emission. Through first‐principles calculations and polarized Raman spectroscopy, we characterize the material's vibrational properties and identify the specific phonon modes that drive exciton self‐trapping. Our novel GW/Bethe‐Salpeter equation force formalism reveals that low‐frequency phonons (100 cm−1, primarily involving Pb–Br motions) couple strongly with excitons, with a remarkably high Huang‐Rhys factor of 137 ± 4, and gives a pathway for ultrafast structural analysis during the absorption process. This phonon‐exciton coupling mechanism explains the material's broadband emission and provides a pathway for controlling optical properties through vibrations and for tuning vibrations through optical excitations. The material also exhibits highly anisotropic optical properties and electronic transport, with bands that are dispersive along the Pb–Br chains but nearly flat in perpendicular directions, resulting in direction‐dependent electrical conductivity that is calculated to be an order of magnitude higher along the chain direction and consistent with measurements. These combined properties make this system an excellent platform for polarization‐sensitive optoelectronic devices.more » « lessFree, publicly-accessible full text available April 16, 2027
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Abstract 2D memristors have demonstrated attractive resistive switching characteristics recently but also suffer from the reliability issue, which limits practical applications. Previous efforts on 2D memristors have primarily focused on exploring new material systems, while damage from the metallization step remains a practical concern for the reliability of 2D memristors. Here, the impact of metallization conditions and the thickness of MoS2films on the reliability and other device metrics of MoS2‐based memristors is carefully studied. The statistical electrical measurements show that the reliability can be improved to 92% for yield and improved by ≈16× for average DC cycling endurance in the devices by reducing the top electrode (TE) deposition rate and increasing the thickness of MoS2films. Intriguing convergence of switching voltages and resistance ratio is revealed by the statistical analysis of experimental switching cycles. An “effective switching layer” model compatible with both monolayer and few‐layer MoS2, is proposed to understand the reliability improvement related to the optimization of fabrication configuration and the convergence of switching metrics. The Monte Carlo simulations help illustrate the underlying physics of endurance failure associated with cluster formation and provide additional insight into endurance improvement with device fabrication optimization.more » « less
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Confining materials to two-dimensional forms changes the behaviour of the electrons and enables the creation of new devices. However, most materials are challenging to produce as uniform, thin crystals. Here we present a synthesis approach where thin crystals are grown in a nanoscale mould defined by atomically flat van der Waals (vdW) materials. By heating and compressing bismuth in a vdW mould made of hexagonal boron nitride, we grow ultraflat bismuth crystals less than 10 nm thick. Due to quantum confinement, the bismuth bulk states are gapped, isolating intrinsic Rashba surface states for transport studies. The vdW-moulded bismuth shows exceptional electronic transport, enabling the observation of Shubnikov–de Haas quantum oscillations originating from the (111) surface state Landau levels. By measuring the gate-dependent magnetoresistance, we observe multi-carrier quantum oscillations and Landau level splitting, with features originating from both the top and bottom surfaces. Our vdW mould growth technique establishes a platform for electronic studies and control of bismuth’s Rashba surface states and topological boundary modes1,2,3. Beyond bismuth, the vdW-moulding approach provides a low-cost way to synthesize ultrathin crystals and directly integrate them into a vdW heterostructure.more » « less
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Abstract The fine-tuning of topologically protected states in quantum materials holds great promise for novel electronic devices. However, there are limited methods that allow for the controlled and efficient modulation of the crystal lattice while simultaneously monitoring the changes in the electronic structure within a single sample. Here, we apply significant and controllable strain to high-quality HfTe5samples and perform electrical transport measurements to reveal the topological phase transition from a weak topological insulator phase to a strong topological insulator phase. After applying high strain to HfTe5and converting it into a strong topological insulator, we found that the resistivity of the sample increased by 190,500% and that the electronic transport was dominated by the topological surface states at cryogenic temperatures. Our results demonstrate the suitability of HfTe5as a material for engineering topological properties, with the potential to generalize this approach to study topological phase transitions in van der Waals materials and heterostructures.more » « less
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1D organic metal halide hybrids (OMHHs) exhibit strongly anisotropic optical properties, highly efficient light emission, and large Stokes shift, holding promise for novel photodetection and lighting applications. However, the fundamental mechanisms governing their unique optical properties and in particular the impacts of surface effects are not understood. Herein, 1D C4N2H14PbBr4 by polarization-dependent time-averaged and time-resolved photoluminescence (TRPL) spectroscopy, as a function of photoexcitation energy, is investigated. Surprisingly, it is found that the emission under photoexcitation polarized parallel to the 1D metal halide chains can be either stronger or weaker than that under perpendicular polarization, depending on the excitation energy. The excitation-energy-dependent anisotropic emission is attributed to fast surface recombination, supported by first-principles calculations of optical absorption in this material. The fast surface recombination is directly confirmed by TRPL measurements, when the excitation is polarized parallel to the chains. The comprehensive studies provide a more complete picture for a deeper understanding of the optical anisotropy in 1D OMHHs.more » « less
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Abstract Resistive switching (RS) devices with ultra‐low‐voltage threshold and reliable switching repeatability exhibits great potential applications in energy‐efficient data storage and neuromorphic computing. Understanding switching mechanisms at nanoscale is critical to design RS devices with improved performance. In this work, a lamella memristive device using focused ion beam (FIB) method based on the metal/TiOx/TiN/Si structure device is fabricated. In situ transmission electron microscopy (TEM) and current–voltage (I–V) characteristic demonstrate that the lamella device shows a volatile RS behavior with a threshold switching at ≈ ± 0.4 V. In situ scanning transmission electron microscopy (STEM) experiments with electron energy loss spectroscopy (EELS) reveal that the charge carriers such as oxygen vacancies migrate under positive/negative DC bias and modulate Schottky barriers at the top and bottom metal/semiconductor interfaces. The RS mechanism of the lamella device is based on the Schottky barriers modulation and Joule heating assisted electric field triggered thermal runaway (FTTR) occurred at the metal/semiconductor interfaces. The fundamental insights gained from this study presents a perspective on interface‐type RS devices processing and opens up new technological opportunities of fabricating ultra‐low‐energy memristive devices.more » « lessFree, publicly-accessible full text available April 1, 2027
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