This review traces nanocrystal quantum dot (QD) research from the early discoveries to the present day and into the future. We describe the extensive body of theoretical and experimental knowledge ...that comprises the modern science of QDs. Indeed, the spatial confinement of electrons, holes, and excitons in nanocrystals, coupled with the ability of modern chemical synthesis to make complex designed structures, is today enabling multiple applications of QD size-tunable electronic and optical properties.
Molybdenum disulfide (MoS2) of single- and few-layer thickness was exfoliated on SiO2/Si substrate and characterized by Raman spectroscopy. The number of S−Mo−S layers of the samples was ...independently determined by contact-mode atomic force microscopy. Two Raman modes, E1 2g and A1g, exhibited sensitive thickness dependence, with the frequency of the former decreasing and that of the latter increasing with thickness. The results provide a convenient and reliable means for determining layer thickness with atomic-level precision. The opposite direction of the frequency shifts, which cannot be explained solely by van der Waals interlayer coupling, is attributed to Coulombic interactions and possible stacking-induced changes of the intralayer bonding. This work exemplifies the evolution of structural parameters in layered materials in changing from the three-dimensional to the two-dimensional regime.
We have investigated the phase transformation of bulk MoS2 crystals from the metastable metallic 1T/1T′ phase to the thermodynamically stable semiconducting 2H phase. The metastable 1T/1T′ material ...was prepared by Li intercalation and deintercalation. The thermally driven kinetics of the phase transformation were studied with in situ Raman and optical reflection spectroscopies and yield an activation energy of 400 ± 60 meV (38 ± 6 kJ/mol). We calculate the expected minimum energy pathways for these transformations using DFT methods. The experimental activation energy corresponds approximately to the theoretical barrier for a single formula unit, suggesting that nucleation of the phase transformation is quite local. We also report that femtosecond laser writing converts 1T/1T′ to 2H in a single laser pass. The mechanisms for the phase transformation are discussed.
The ability to control the size of the electronic bandgap is an integral part of solid-state technology. Atomically thin two-dimensional crystals offer a new approach for tuning the energies of the ...electronic states based on the unusual strength of the Coulomb interaction in these materials and its environmental sensitivity. Here, we show that by engineering the surrounding dielectric environment, one can tune the electronic bandgap and the exciton binding energy in monolayers of WS
and WSe
by hundreds of meV. We exploit this behaviour to present an in-plane dielectric heterostructure with a spatially dependent bandgap, as an initial step towards the creation of diverse lateral junctions with nanoscale resolution.
Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that ...inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH_{3}NH_{3}PbBr_{3}) and all-inorganic (CsPbBr_{3}) lead-halide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. MD simulations indicate that head-to-head Cs motion coupled to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr_{3}.
We report variation of the work function for single and bilayer graphene devices measured by scanning Kelvin probe microscopy (SKPM). By use of the electric field effect, the work function of ...graphene can be adjusted as the gate voltage tunes the Fermi level across the charge neutrality point. Upon biasing the device, the surface potential map obtained by SKPM provides a reliable way to measure the contact resistance of individual electrodes contacting graphene.
Lead-halide perovskites have emerged as promising materials for photovoltaic and optoelectronic applications. Their significantly anharmonic lattice motion, in contrast to conventional harmonic ...semiconductors, presents a conceptual challenge in understanding the genesis of their exceptional optoelectronic properties. Here we report a strongly temperature dependent luminescence Stokes shift in the electronic spectra of both hybrid and inorganic lead-bromide perovskite single crystals. This behavior stands in stark contrast to that exhibited by more conventional crystalline semiconductors. We correlate the electronic spectra with the anti-Stokes and Stokes Raman vibrational spectra. Dielectric solvation theories, originally developed for excited molecules dissolved in polar liquids, reproduce our experimental observations. Our approach, which invokes a classical Debye-like relaxation process, captures the dielectric response originating from the incipient anharmonicity of the LO phonon at about 20 meV (160 cm
) in the lead-bromide framework. We reconcile this liquid-like model incorporating thermally-activated dielectric solvation with more standard solid-state theories of the emission Stokes shift in crystalline semiconductors.
We have identified excited exciton states in monolayers of MoS2 and WS2 supported on fused silica by means of photoluminescence excitation spectroscopy. In monolayer WS2, the positions of the excited ...A exciton states imply an exciton binding energy of 0.32 eV. In monolayer MoS2, excited exciton transitions are observed at energies of 2.24 and 2.34 eV. Assigning these states to the B exciton Rydberg series yields an exciton binding energy of 0.44 eV.
Optical transitions in carbon nanotubes are of central importance for nanotube characterization. They also provide insight into the nature of excited states in these one-dimensional systems. Recent ...work suggests that light absorption produces strongly correlated electron-hole states in the form of excitons. However, it has been difficult to rule out a simpler model in which resonances arise from the van Hove singularities associated with the one-dimensional bond structure of the nanotubes. Here, two-photon excitation spectroscopy bolsters the exciton picture. We found binding energies of approximately400 millielectron volts for semiconducting single-walled nanotubes with 0.8-nanometer diameters. The results demonstrate the dominant role of many-body interactions in the excited-state properties of one-dimensional systems.
Nanometer-scale graphene objects are attracting much research interest because of newly emerging properties originating from quantum confinement effects. We present Raman spectroscopy studies of ...graphene nanoribbons (GNRs), which are known to have nonzero electronic bandgap. GNRs of width ranging from 15 to 100 nm have been prepared by e-beam lithographic patterning of mechanically exfoliated graphene followed by oxygen plasma etching. Raman spectra of narrow GNRs can be characterized by an upshifted G band and a prominent disorder-related D band originating from scattering at the ribbon edges. The D-to-G band intensity ratio generally increases with decreasing ribbon width. However, its decrease in width of <25 nm, partly attributed to amorphization at the edges, provides a valuable experimental estimate on D mode relaxation length of <5 nm. The upshift in the G band of the narrowest GNRs can be attributed to confinement effect or chemical doping by functional groups on the GNR edges. Notably, GNRs are much more susceptible to photothermal effects resulting in reversible hole doping caused by atmospheric oxygen than bulk graphene sheets. Finally we show that the 2D band is still a reliable marker in determining the number of layers of GNRs despite its significant broadening for very narrow GNRs.
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