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594 result(s) for "Norris, David J."
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Bright triplet excitons in caesium lead halide perovskites
The lowest-energy exciton state in caesium lead halide perovskite nanocrystals is shown to be a bright triplet state, contrary to expectations that lowest-energy excitons should always be dark. A bright future for semiconductors Lead halide perovskite semiconductor nanocrystals are attracting considerable interest as materials for solar cells and light-emitting diodes because of their excellent photophysical properties. But what makes them so special? Excitons are the electronic excitations that are ultimately responsible for the emissive properties of nanostructured semiconductors, and prevailing wisdom is that the lowest-energy excitonic state will be long-lived and hence poorly emitting (or 'dark'). Michael Becker et al . now show that caesium lead halide perovskites disobey this rule: the lowest-energy excitons are instead unusually 'bright', emitting much faster than any other semiconductor nanocrystal. Furthermore, they identify the structural and electronic factors responsible for this anomalous behaviour, providing vital clues for the identification of other semiconducting materials that might behave similarly. Nanostructured semiconductors emit light from electronic states known as excitons 1 . For organic materials, Hund’s rules 2 state that the lowest-energy exciton is a poorly emitting triplet state. For inorganic semiconductors, similar rules 3 predict an analogue of this triplet state known as the ‘dark exciton’ 4 . Because dark excitons release photons slowly, hindering emission from inorganic nanostructures, materials that disobey these rules have been sought. However, despite considerable experimental and theoretical efforts, no inorganic semiconductors have been identified in which the lowest exciton is bright. Here we show that the lowest exciton in caesium lead halide perovskites (CsPbX 3 , with X = Cl, Br or I) involves a highly emissive triplet state. We first use an effective-mass model and group theory to demonstrate the possibility of such a state existing, which can occur when the strong spin–orbit coupling in the conduction band of a perovskite is combined with the Rashba effect 5 , 6 , 7 , 8 , 9 , 10 . We then apply our model to CsPbX 3 nanocrystals 11 , and measure size- and composition-dependent fluorescence at the single-nanocrystal level. The bright triplet character of the lowest exciton explains the anomalous photon-emission rates of these materials, which emit about 20 and 1,000 times faster 12 than any other semiconductor nanocrystal at room 13 , 14 , 15 , 16 and cryogenic 4 temperatures, respectively. The existence of this bright triplet exciton is further confirmed by analysis of the fine structure in low-temperature fluorescence spectra. For semiconductor nanocrystals, which are already used in lighting 17 , lasers 18 and displays 19 , these excitons could lead to materials with brighter emission. More generally, our results provide criteria for identifying other semiconductors that exhibit bright excitons, with potential implications for optoelectronic devices.
Doped Nanocrystals
The critical role that dopants play in semiconductor devices has stimulated research on the properties and the potential applications of semiconductor nanocrystals, or colloidal quantum dots, doped with intentional impurities. We review advances in the chemical synthesis of doped nanocrystals, in the theoretical understanding of the fundamental mechanisms that control doping, and in the creation of highly conducting nanocrystalline films. Because impurities can be used to alter the properties of nanoscale materials in desirable and controllable ways, doped nanocrystals can address key problems in applications from solar cells to bioimaging.
An intrinsic growth instability in isotropic materials leads to quasi-two-dimensional nanoplatelets
Colloidal nanoplatelets are atomically flat, quasi-two-dimensional sheets of semiconductor that can exhibit efficient, spectrally pure fluorescence. Despite intense interest in their properties, the mechanism behind their highly anisotropic shape and precise atomic-scale thickness remains unclear, and even counter-intuitive for commonly studied nanoplatelets that arise from isotropic crystal structures (such as zincblende CdSe and lead halide perovskites). Here we show that an intrinsic instability in growth kinetics can lead to such highly anisotropic shapes. By combining experimental results on the synthesis of CdSe nanoplatelets with theory predicting enhanced growth on narrow surface facets, we develop a model that explains nanoplatelet formation as well as observed dependencies on time and temperature. Based on standard concepts of volume, surface and edge energies, the resulting growth instability criterion can be directly applied to other crystalline materials. Thus, knowledge of this previously unknown mechanism for controlling shape at the nanoscale can lead to broader libraries of quasi-two-dimensional materials. Quasi-two-dimensional CdSe nanoplatelets are shown to grow in concentrated solvent-free melts, without mixed surfactants. A model explaining such results proposes that nanoscale instability triggers anisotropic growth of isotropic materials.
Electrically tunable quantum confinement of neutral excitons
Confining particles to distances below their de Broglie wavelength discretizes their motional state. This fundamental effect is observed in many physical systems, ranging from electrons confined in atoms or quantum dots 1 , 2 to ultracold atoms trapped in optical tweezers 3 , 4 . In solid-state photonics, a long-standing goal has been to achieve fully tunable quantum confinement of optically active electron–hole pairs, known as excitons. To confine excitons, existing approaches mainly rely on material modulation 5 , which suffers from poor control over the energy and position of trapping potentials. This has severely impeded the engineering of large-scale quantum photonic systems. Here we demonstrate electrically controlled quantum confinement of neutral excitons in 2D semiconductors. By combining gate-defined in-plane electric fields with inherent interactions between excitons and free charges in a lateral p–i–n junction, we achieve exciton confinement below 10 nm. Quantization of excitonic motion manifests in the measured optical response as a ladder of discrete voltage-dependent states below the continuum. Furthermore, we observe that our confining potentials lead to a strong modification of the relative wave function of excitons. Our technique provides an experimental route towards creating scalable arrays of identical single-photon sources and has wide-ranging implications for realizing strongly correlated photonic phases 6 , 7 and on-chip optical quantum information processors 8 , 9 . Electrically controlled quantum confinement of excitons to below 10 nm is achieved in a 2D semiconductor by combining in-plane electric fields with interactions between excitons and free charges.
Ultrasmooth Patterned Metals for Plasmonics and Metamaterials
Surface plasmons are electromagnetic waves that can exist at metal interfaces because of coupling between light and free electrons. Restricted to travel along the interface, these waves can be channeled, concentrated, or otherwise manipulated by surface patterning. However, because surface roughness and other inhomogeneities have so far limited surface-plasmon propagation in real plasmonic devices, simple high-throughput methods are needed to fabricate high-quality patterned metals. We combined template stripping with precisely patterned silicon substrates to obtain ultrasmooth pure metal films with grooves, bumps, pyramids, ridges, and holes. Measured surface-plasmon-propagation lengths on the resulting surfaces approach theoretical values for perfectly flat films. With the use of our method, we demonstrated structures that exhibit Raman scattering enhancements above 10⁷ for sensing applications and multilayer films for optical metamaterials.
Hot-Electron Transfer from Semiconductor Nanocrystals
In typical semiconductor solar cells, photons with energies above the semiconductor bandgap generate hot charge carriers that quickly cool before all of their energy can be captured, a process that limits device efficiency. Although fabricating the semiconductor in a nanocrystalline morphology can slow this cooling, the transfer of hot carriers to electron and hole acceptors has not yet been thoroughly demonstrated. We used time-resolved optical second harmonic generation to observe hot-electron transfer from colloidal lead selenide (PbSe) nanocrystals to a titanium dioxide (TiO₂) electron acceptor. With appropriate chemical treatment of the nanocrystal surface, this transfer occurred much faster than expected. Moreover, the electric field resulting from sub-50-femtosecond charge separation across the PbSe-TiO₂ interface excited coherent vibrations of the TiO₂ surface atoms, whose motions could be followed in real time.
Confocal reference free traction force microscopy
The mechanical wiring between cells and their surroundings is fundamental to the regulation of complex biological processes during tissue development, repair or pathology. Traction force microscopy (TFM) enables determination of the actuating forces. Despite progress, important limitations with intrusion effects in low resolution 2D pillar-based methods or disruptive intermediate steps of cell removal and substrate relaxation in high-resolution continuum TFM methods need to be overcome. Here we introduce a novel method allowing a one-shot (live) acquisition of continuous in- and out-of-plane traction fields with high sensitivity. The method is based on electrohydrodynamic nanodrip-printing of quantum dots into confocal monocrystalline arrays, rendering individually identifiable point light sources on compliant substrates. We demonstrate the undisrupted reference-free acquisition and quantification of high-resolution continuous force fields, and the simultaneous capability of this method to correlatively overlap traction forces with spatial localization of proteins revealed using immunofluorescence methods. Traction force microscopy is an effective method of measuring forces between cells and their environment, but requires removing the cells to obtain a reference image. Here the authors use nanodrip printing of quantum dots into compliant substrates to provide a regular array of fiducial spots, removing the need for a reference image.
In vivo Imaging of Quantum Dots Encapsulated in Phospholipid Micelles
Fluorescent semiconductor nanocrystals (quantum dots) have the potential to revolutionize biological imaging, but their use has been limited by difficulties in obtaining nanocrystals that are biocompatible. To address this problem, we encapsulated individual nanocrystals in phospholipid block-copolymer micelles and demonstrated both in vitro and in vivo imaging. When conjugated to DNA, the nanocrystal-micelles acted as in vitro fluorescent probes to hybridize to specific complementary sequences. Moreover, when injected into Xenopus embryos, the nanocrystal-micelles were stable, nontoxic ($< 5 \\times 10^9$ nanocrystals per cell), cell autonomous, and slow to photobleach. Nanocrystal fluorescence could be followed to the tadpole stage, allowing lineage-tracing experiments in embryogenesis.
On-chip natural assembly of silicon photonic bandgap crystals
Photonic bandgap crystals can reflect light for any direction of propagation in specific wavelength ranges 1 , 2 , 3 . This property, which can be used to confine, manipulate and guide photons, should allow the creation of all-optical integrated circuits. To achieve this goal, conventional semiconductor nanofabrication techniques have been adapted to make photonic crystals 4 , 5 , 6 , 7 , 8 , 9 . A potentially simpler and cheaper approach for creating three-dimensional periodic structures is the natural assembly of colloidal microspheres 10 , 11 , 12 , 13 , 14 , 15 . However, this approach yields irregular, polycrystalline photonic crystals that are difficult to incorporate into a device. More importantly, it leads to many structural defects that can destroy the photonic bandgap 16 , 17 . Here we show that by assembling a thin layer of colloidal spheres on a silicon substrate, we can obtain planar, single-crystalline silicon photonic crystals that have defect densities sufficiently low that the bandgap survives. As expected from theory, we observe unity reflectance in two crystalline directions of our photonic crystals around a wavelength of 1.3 micrometres. We also show that additional fabrication steps, intentional doping and patterning, can be performed, so demonstrating the potential for specific device applications.
Multispectral quantum-dot photodetectors
The cost of infrared detectors has limited the deployment of multispectral imagers and sensors. Researchers now demonstrate simple quantum-dot devices that promise fast, sensitive and low-cost cameras that can switch between short- and mid-wavelength infrared.