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145 result(s) for "Kovalenko, Maksym V."
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Properties and potential optoelectronic applications of lead halide perovskite nanocrystals
Semiconducting lead halide perovskites (LHPs) have not only become prominent thin-film absorber materials in photovoltaics but have also proven to be disruptive in the field of colloidal semiconductor nanocrystals (NCs). The most important feature of LHP NCs is their so-called defect-tolerance—the apparently benign nature of structural defects, highly abundant in these compounds, with respect to optical and electronic properties. Here, we review the important differences that exist in the chemistry and physics of LHP NCs as compared with more conventional, tetrahedrally bonded, elemental, and binary semiconductor NCs (such as silicon, germanium, cadmium selenide, gallium arsenide, and indium phosphide). We survey the prospects of LHP NCs for optoelectronic applications such as in television displays, light-emitting devices, and solar cells, emphasizing the practical hurdles that remain to be overcome.
Ultra-narrow room-temperature emission from single CsPbBr3 perovskite quantum dots
Semiconductor quantum dots have long been considered artificial atoms, but despite the overarching analogies in the strong energy-level quantization and the single-photon emission capability, their emission spectrum is far broader than typical atomic emission lines. Here, by using ab-initio molecular dynamics for simulating exciton-surface-phonon interactions in structurally dynamic CsPbBr 3 quantum dots, followed by single quantum dot optical spectroscopy, we demonstrate that emission line-broadening in these quantum dots is primarily governed by the coupling of excitons to low-energy surface phonons. Mild adjustments of the surface chemical composition allow for attaining much smaller emission linewidths of 35−65 meV (vs. initial values of 70–120 meV), which are on par with the best values known for structurally rigid, colloidal II-VI quantum dots (20−60 meV). Ultra-narrow emission at room-temperature is desired for conventional light-emitting devices and paramount for emerging quantum light sources. Narrow emission is desired for light-emitting devices. Here, Kovalenko et al. demonstrate that the emission line-broadening in perovskite quantum dots is dominated by the coupling between excitons and surface phonon modes which can be controlled by minimal surface modifications.
Reconfigurable halide perovskite nanocrystal memristors for neuromorphic computing
Many in-memory computing frameworks demand electronic devices with specific switching characteristics to achieve the desired level of computational complexity. Existing memristive devices cannot be reconfigured to meet the diverse volatile and non-volatile switching requirements, and hence rely on tailored material designs specific to the targeted application, limiting their universality. “Reconfigurable memristors” that combine both ionic diffusive and drift mechanisms could address these limitations, but they remain elusive. Here we present a reconfigurable halide perovskite nanocrystal memristor that achieves on-demand switching between diffusive/volatile and drift/non-volatile modes by controllable electrochemical reactions. Judicious selection of the perovskite nanocrystals and organic capping ligands enable state-of-the-art endurance performances in both modes – volatile (2 × 10 6 cycles) and non-volatile (5.6 × 10 3 cycles). We demonstrate the relevance of such proof-of-concept perovskite devices on a benchmark reservoir network with volatile recurrent and non-volatile readout layers based on 19,900 measurements across 25 dynamically-configured devices. Existing memristors cannot be reconfigured to meet the diverse switching requirements of various computing frameworks, limiting their universality. Here, the authors present a nanocrystal memristor that can be reconfigured on-demand to address these limitations
High-energy-density dual-ion battery for stationary storage of electricity using concentrated potassium fluorosulfonylimide
Graphite dual-ion batteries represent a potential battery concept for large-scale stationary storage of electricity, especially when constructed free of lithium and other chemical elements with limited natural reserves. Owing to their non-rocking-chair operation mechanism, however, the practical deployment of graphite dual-ion batteries is inherently limited by the need for large quantities of electrolyte solutions as reservoirs of all ions that are needed for complete charge and discharge of the electrodes. Thus far, lithium-free graphite dual-ion batteries have employed moderately concentrated electrolyte solutions (0.3–1 M), resulting in rather low cell-level energy densities of 20–70 Wh kg −1 . In this work, we present a lithium-free graphite dual-ion battery utilizing a highly concentrated electrolyte solution of 5 M potassium bis(fluorosulfonyl)imide in alkyl carbonates. The resultant battery offers an energy density of 207 Wh kg −1 , along with a high energy efficiency of 89% and an average discharge voltage of 4.7 V. Lithium-free graphite dual-ion battery offers a new means of energy storage. Here the authors show such device utilizing a highly concentrated electrolyte solution of KFSI in alkyl carbonates that exhibits a high energy density and high energy efficiency as well as an average discharge voltage of 4.7 V.
High-resolution remote thermometry and thermography using luminescent low-dimensional tin-halide perovskites
Although metal-halide perovskites have recently revolutionized research in optoelectronics through a unique combination of performance and synthetic simplicity, their low-dimensional counterparts can further expand the field with hitherto unknown and practically useful optical functionalities. In this context, we present the strong temperature dependence of the photoluminescence lifetime of low-dimensional, perovskite-like tin-halides and apply this property to thermal imaging. The photoluminescence lifetimes are governed by the heat-assisted de-trapping of self-trapped excitons, and their values can be varied over several orders of magnitude by adjusting the temperature (up to 20 ns °C−1). Typically, this sensitive range spans up to 100 °C, and it is both compound-specific and shown to be compositionally and structurally tunable from −100 to 110 °C going from [C(NH2)3]2SnBr4 to Cs4SnBr6 and (C4N2H14I)4SnI6. Finally, through the implementation of cost-effective hardware for fluorescence lifetime imaging, based on time-of-flight technology, these thermoluminophores have been used to record thermographic videos with high spatial and thermal resolution.
On the feasibility of all-solid-state batteries with LLZO as a single electrolyte
Replacement of Li-ion liquid-state electrolytes by solid-state counterparts in a Li-ion battery (LIB) is a major research objective as well as an urgent priority for the industry, as it enables the use of a Li metal anode and provides new opportunities to realize safe, non-flammable, and temperature-resilient batteries. Among the plethora of solid-state electrolytes (SSEs) investigated, garnet-type Li-ion electrolytes based on cubic Li 7 La 3 Zr 2 O 12 (LLZO) are considered the most appealing candidates for the development of future solid-state batteries because of their low electronic conductivity of ca . 10 −8  S cm −1 (RT) and a wide electrochemical operation window of 0–6 V vs. Li + /Li. However, high LLZO density (5.1 g cm −3 ) and its lower level of Li-ion conductivity (up to 1 mS cm −1 at RT) compared to liquid electrolytes (1.28 g cm −3 ; ca. 10 mS cm −1 at RT) still raise the question as to the feasibility of using solely LLZO as an electrolyte for achieving competitive energy and power densities. In this work, we analyzed the energy densities of Li-garnet all-solid-state batteries based solely on LLZO SSE by modeling their Ragone plots using LiCoO 2 as the model cathode material. This assessment allowed us to identify values of the LLZO thickness, cathode areal capacity, and LLZO content in the solid-state cathode required to match the energy density of conventional lithium-ion batteries (ca. 180 Wh kg −1 and 497 Wh L −1 ) at the power densities of 200 W kg −1 and 600 W L −1 , corresponding to ca . 1 h of battery discharge time (1C). We then discuss key challenges in the practical deployment of LLZO SSE in the fabrication of Li-garnet all-solid-state batteries.
Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites
Metal halide semiconductors with perovskite crystal structures have recently emerged as highly promising optoelectronic materials. Despite the recent surge of reports on microcrystalline, thin-film and bulk single-crystalline metal halides, very little is known about the photophysics of metal halides in the form of uniform, size-tunable nanocrystals. Here we report low-threshold amplified spontaneous emission and lasing from ∼10 nm monodisperse colloidal nanocrystals of caesium lead halide perovskites CsPbX 3 (X=Cl, Br or I, or mixed Cl/Br and Br/I systems). We find that room-temperature optical amplification can be obtained in the entire visible spectral range (440–700 nm) with low pump thresholds down to 5±1 μJ cm −2 and high values of modal net gain of at least 450±30 cm −1 . Two kinds of lasing modes are successfully observed: whispering-gallery-mode lasing using silica microspheres as high-finesse resonators, conformally coated with CsPbX 3 nanocrystals and random lasing in films of CsPbX 3 nanocrystals. Lead halide perovskite colloidal nanocrystals have promising optoelectronic properties, such as high photoluminescence quantum yields and narrow emission linewidths. Here, the authors report low-threshold amplified spontaneous emission and two kinds of lasing in nanostructured caesium lead halide perovskites.
Integrated photodetectors for compact Fourier-transform waveguide spectrometers
Extreme miniaturization of infrared spectrometers is critical for their integration into next-generation consumer electronics, wearables and ultrasmall satellites. In the infrared, there is a necessary compromise between high spectral bandwidth and high spectral resolution when miniaturizing dispersive elements, narrow band-pass filters and reconstructive spectrometers. Fourier-transform spectrometers are known for their large bandwidth and high spectral resolution in the infrared; however, they have not been fully miniaturized. Waveguide-based Fourier-transform spectrometers offer a low device footprint, but rely on an external imaging sensor such as bulky and expensive InGaAs cameras. Here we demonstrate a proof-of-concept miniaturized Fourier-transform waveguide spectrometer that incorporates a subwavelength and complementary-metal–oxide–semiconductor-compatible colloidal quantum dot photodetector as a light sensor. The resulting spectrometer exhibits a large spectral bandwidth and moderate spectral resolution of 50 cm−1 at a total active spectrometer volume below 100 μm × 100 μm × 100 μm. This ultracompact spectrometer design allows the integration of optical/analytical measurement instruments into consumer electronics and space devices.A Fourier-transform waveguide spectrometer is demonstrated by using HgTe-quantum-dot-based photoconductors with a spectral response up to a wavelength of 2 μm. The spectral resolution is 50 cm–1. The total active spectrometer volume is below 100 μm × 100 μm × 100 μm.
Single-photon superradiance in individual caesium lead halide quantum dots
The brightness of an emitter is ultimately described by Fermi’s golden rule, with a radiative rate proportional to its oscillator strength times the local density of photonic states. As the oscillator strength is an intrinsic material property, the quest for ever brighter emission has relied on the local density of photonic states engineering, using dielectric or plasmonic resonators 1 , 2 . By contrast, a much less explored avenue is to boost the oscillator strength, and hence the emission rate, using a collective behaviour termed superradiance. Recently, it was proposed 3 that the latter can be realized using the giant oscillator-strength transitions of a weakly confined exciton in a quantum well when its coherent motion extends over many unit cells. Here we demonstrate single-photon superradiance in perovskite quantum dots with a sub-100 picosecond radiative decay time, almost as short as the reported exciton coherence time 4 . The characteristic dependence of radiative rates on the size, composition and temperature of the quantum dot suggests the formation of giant transition dipoles, as confirmed by effective-mass calculations. The results aid in the development of ultrabright, coherent quantum light sources and attest that quantum effects, for example, single-photon emission, persist in nanoparticles ten times larger than the exciton Bohr radius. Excitonic single-photon superradiance is reported in individual perovskite quantum dots with a sub-100 ps radiative decay time, almost as short as the reported exciton coherence time.
Detection of X-ray photons by solution-processed lead halide perovskites
The evolution of real-time medical diagnostic tools such as angiography and computer tomography from radiography based on photographic plates was enabled by the development of integrated solid-state X-ray photon detectors made from conventional solid-state semiconductors. Recently, for optoelectronic devices operating in the visible and near-infrared spectral regions, solution-processed organic and inorganic semiconductors have also attracted a great deal of attention. Here, we demonstrate a possibility to use such inexpensive semiconductors for the sensitive detection of X-ray photons by direct photon-to-current conversion. In particular, methylammonium lead iodide perovskite (CH 3 NH 3 PbI 3 ) offers a compelling combination of fast photoresponse and a high absorption cross-section for X-rays, owing to the heavy Pb and I atoms. Solution-processed photodiodes as well as photoconductors are presented, exhibiting high values of X-ray sensitivity (up to 25 μC mGy air −1  cm −3 ) and responsivity (1.9 × 10 4  carriers/photon), which are commensurate with those obtained by the current solid-state technology. Solid-state X-ray detectors have enabled real-time diagnostics as well as reduced patient dose. Now researchers have shown that potentially inexpensive perovskites can be used for efficient X-ray imaging.