Dielectric Confinement and Excitonic Effects in Two-Dimensional Nanoplatelets.

Quasi-two-dimensional (2D) semiconductor nanoplatelets manifest strong quantum confinement with exceptional optical characteristics of narrow photoluminescence peaks with energies tunable by thickness with monolayer precision. We employed scanning tunneling spectroscopy (STS) in conjunction with optical measurements to probe the thickness-dependent band gap and density of excited states in a series of CdSe nanoplatelets. The tunneling spectra, measured in the double-barrier tunnel junction configuration, reveal the effect of quantum confinement on the band gap taking place mainly through a blue-shift of the conduction band edge, along with a signature of 2D electronic structure intermixed with finite lateral-size and/or defects effects. The STS fundamental band gaps are larger than the optical gaps as expected from the contributions of exciton binding in the absorption, as confirmed by theoretical calculations. The calculations also point to strong valence band mixing between the light- and split-off hole levels. Strikingly, the energy difference between the heavy-hole and light-hole levels in the tunneling spectra are significantly larger than the corresponding values extracted from the absorption spectra. Possible explanations for this, including an interplay of nanoplatelet charging, dielectric confinement, and difference in exciton binding energy for light and heavy holes, are analyzed and discussed.

Exciton Fine Structure in Perovskite Nanocrystals.

The bright emission observed in cesium lead halide perovskite nanocrystals (NCs) has recently been explained in terms of a bright exciton ground state [ Becker et al. Nature 2018 , 553 , 189 - 193 ], a claim that would make these materials the first known examples in which the exciton ground state is not an optically forbidden dark exciton. This unprecedented claim has been the subject of intense experimental investigation that has so far failed to detect the dark ground-state exciton. Here, we review the effective-mass/electron-hole exchange theory for the exciton fine structure in cubic and tetragonal CsPbBr3 NCs. In our calculations, the crystal field and the short-range electron-hole exchange constant were calculated using density functional theory together with hybrid functionals and spin-orbit coupling. Corrections associated with long-range exchange and surface image charges were calculated using measured bulk effective mass and dielectric parameters. As expected, within the context of the exchange model, we find an optically inactive ground exciton level. However, in this model, the level order for the optically active excitons in tetragonal CsPbBr3 NCs is opposite to what has been observed experimentally. An alternate explanation for the observed bright exciton level order in CsPbBr3 NCs is offered in terms of the Rashba effect, which supports the existence of a bright ground-state exciton in these NCs. The size dependence of the exciton fine structure calculated for perovskite NCs shows that the bright-dark level inversion caused by the Rashba effect is suppressed by the enhanced electron-hole exchange interaction in small NCs.

Dynamic cues for whisker-based object localization: An analytical solution to vibration during active whisker touch.

Vibrations are important cues for tactile perception across species. Whisker-based sensation in mice is a powerful model system for investigating mechanisms of tactile perception. However, the role vibration plays in whisker-based sensation remains unsettled, in part due to difficulties in modeling the vibration of whiskers. Here, we develop an analytical approach to calculate the vibrations of whiskers striking objects. We use this approach to quantify vibration forces during active whisker touch at a range of locations along the whisker. The frequency and amplitude of vibrations evoked by contact are strongly dependent on the position of contact along the whisker. The magnitude of vibrational shear force and bending moment is comparable to quasi-static forces. The fundamental vibration frequencies are in a detectable range for mechanoreceptor properties and below the maximum spike rates of primary sensory afferents. These results suggest two dynamic cues exist that rodents can use for object localization: vibration frequency and comparison of vibrational to quasi-static force magnitude. These complement the use of quasi-static force angle as a distance cue, particularly for touches close to the follicle, where whiskers are stiff and force angles hardly change during touch. Our approach also provides a general solution to calculation of whisker vibrations in other sensing tasks.

Bright triplet excitons in caesium lead halide perovskites.

Nanostructured semiconductors emit light from electronic states known as excitons. For organic materials, Hund's rules state that the lowest-energy exciton is a poorly emitting triplet state. For inorganic semiconductors, similar rules predict an analogue of this triplet state known as the 'dark exciton'. 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 (CsPbX3, 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. We then apply our model to CsPbX3 nanocrystals, 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 than any other semiconductor nanocrystal at room and cryogenic 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, lasers and displays, 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.

Quantum Dot-Peptide-Fullerene Bioconjugates for Visualization of in Vitro and in Vivo Cellular Membrane Potential.

We report the development of a quantum dot (QD)-peptide-fullerene (C60) electron transfer (ET)-based nanobioconjugate for the visualization of membrane potential in living cells. The bioconjugate is composed of (1) a central QD electron donor, (2) a membrane-inserting peptidyl linker, and (3) a C60 electron acceptor. The photoexcited QD donor engages in ET with the C60 acceptor, resulting in quenching of QD photoluminescence (PL) that tracks positively with the number of C60 moieties arrayed around the QD. The nature of the QD-capping ligand also modulates the quenching efficiency; a neutral ligand coating facilitates greater QD quenching than a negatively charged carboxylated ligand. Steady-state photophysical characterization confirms an ET-driven process between the donor-acceptor pair. When introduced to cells, the amphiphilic QD-peptide-C60 bioconjugate labels the plasma membrane by insertion of the peptide-C60 portion into the hydrophobic bilayer, while the hydrophilic QD sits on the exofacial side of the membrane. Depolarization of cellular membrane potential augments the ET process, which is manifested as further quenching of QD PL. We demonstrate in HeLa cells, PC12 cells, and primary cortical neurons significant QD PL quenching (ΔF/F0 of 2-20% depending on the QD-C60 separation distance) in response to membrane depolarization with KCl. Further, we show the ability to use the QD-peptide-C60 probe in combination with conventional voltage-sensitive dyes (VSDs) for simultaneous two-channel imaging of membrane potential. In in vivo imaging of cortical electrical stimulation, the optical response of the optimal QD-peptide-C60 configuration exhibits temporal responsivity to electrical stimulation similar to that of VSDs. Notably, however, the QD-peptide-C60 construct displays 20- to 40-fold greater ΔF/F0 than VSDs. The tractable nature of the QD-peptide-C60 system offers the advantages of ease of assembly, large ΔF/F0, enhanced photostability, and high throughput without the need for complicated organic synthesis or genetic engineering, respectively, that is required of traditional VSDs and fluorescent protein constructs.

Biexciton Auger Recombination in CdSe/CdS Core/Shell Semiconductor Nanocrystals.

A theoretical study of the positive and negative trion channels in the nonradiative Auger recombination of band-edge biexcitons (BXs) in CdSe/CdS core/shell nanocrystals (NCs) is presented. The theory takes into account the BX fine-structure produced by NC asymmetry and hole-hole exchange interaction. The calculations show that growth of CdS shell upon CdSe core suppresses the rate of the Auger recombination via negative trion channel, while the more efficient Auger recombination via positive trion channel shows much weaker dependence on the shell thickness. The demonstrated oscillatory dependence of the BX Auger rate on the core and shell sizes is explained qualitatively in terms of overlap of the ground and excited carrier wave functions. The calculations show that raise of temperature accelerates the Auger recombination in CdSe/CdS NCs due to reduction of the bulk energy gaps of CdSe and CdS.

Dynamics of Intraband and Interband Auger Processes in Colloidal Core-Shell Quantum Dots.

Conventional colloidal quantum dots (QDs) suffer from rapid energy losses by nonradiative (Auger) processes, leading to sub-ns lifetimes in all excited states but the lowest-energy single exciton. Suppression of interband Auger decay, such as biexciton Auger recombination, has been achieved with the design of heterostructured core-shell QDs. Auger-like processes are also believed to be responsible for rapid intraband hot-electron cooling in QDs. However, the simultaneous effect of shell growth on interband Auger recombination and intraband hot-electron cooling has not been addressed. Here we investigate how the growth of a CdS shell affects these two relaxation processes in CdSe/CdS core-shell QDs. Using a combination of ultrafast pump-push-probe spectroscopy on the QD ensemble and analysis of the photon statistics from single QDs, we find that Auger losses in the biexciton state are suppressed with increasing shell thickness, while hot-electron cooling remains unaffected. Calculations conducted within an eight-band k·p model confirm the experimental dependence of the biexciton Auger decay on the shell thickness, and provide insights into the factors determining the cooling rate of hot carriers.

Quantum Confinement Regimes in CdTe Nanocrystals Probed by Single Dot Spectroscopy: From Strong Confinement to the Bulk Limit.

Sufficiently large semiconductor nanocrystals are a useful model system to characterize bulk-like excitons, with the electron and hole bound predominantly by Coulomb interaction. We present optical characterization of excitons in individual giant CdTe nanocrystals with diameters up to 25.5 nm at 4.2 K under varying excitation power and magnetic field strength. We determine values for the biexciton binding energy, diamagnetic shift constant, and Landé g-factor, which approach the bulk values with increasing nanocrystal size.

Nonradiative Auger recombination in semiconductor nanocrystals.

We calculate the rate of nonradiative Auger recombination in negatively charged CdSe nanocrystals (NCs). The rate is nonmonotonic, strongly oscillating with NC size, and sensitive to the NC surface. The oscillations result in nonexponential decay of carriers in NC ensembles. Using a standard single-exponential approximation of the decay dynamics, we determine the apparent size dependence of the Auger rate in an ensemble and derive CdSe surface parameters consistent with the experimental dependence on size.

Size-dependent energy levels of InSb quantum dots measured by scanning tunneling spectroscopy.

The electronic structure of single InSb quantum dots (QDs) with diameters between 3 and 7 nm was investigated using atomic force microscopy (AFM) and scanning tunneling spectroscopy (STS). In this size regime, InSb QDs show strong quantum confinement effects which lead to discrete energy levels on both valence and conduction band states. Decrease of the QD size increases the measured band gap and the spacing between energy levels. Multiplets of equally spaced resonance peaks are observed in the tunneling spectra. There, multiplets originate from degeneracy lifting induced by QD charging. The tunneling spectra of InSb QDs are qualitatively different from those observed in the STS of other III-V materials, for example, InAs QDs, with similar band gap energy. Theoretical calculations suggest the electron tunneling occurs through the states connected with L-valley of InSb QDs rather than through states of the Γ-valley. This observation calls for better understanding of the role of indirect valleys in strongly quantum-confined III-V nanomaterials.

PbSe-Based Colloidal Core/Shell Heterostructures for Optoelectronic Applications.

Lead-based (IV-VI) colloidal quantum dots (QDs) are of widespread scientific and technological interest owing to their size-tunable band-gap energy in the near-infrared optical region. This article reviews the synthesis of PbSe-based heterostructures and their structural and optical investigations at various temperatures. The review focuses on the structures consisting of a PbSe core coated with a PbSexS1-x (0 ≤ x ≤ 1) or CdSe shell. The former-type shells were epitaxially grown on the PbSe core, while the latter-type shells were synthesized using partial cation-exchange. The influence of the QD composition and the ambient conditions, i.e., exposure to oxygen, on the QD optical properties, such as radiative lifetime, Stokes shift, and other temperature-dependent characteristics, was investigated. The study revealed unique properties of core/shell heterostructures of various compositions, which offer the opportunity of fine-tuning the QD electronic structure by changing their architecture. A theoretical model of the QD electronic band structure was developed and correlated with the results of the optical studies. The review also outlines the challenges related to potential applications of colloidal PbSe-based heterostructures.

Tuning of electronic properties in IV-VI colloidal nanostructures by alloy composition and architecture.

Colloidal lead chalcogenide (IV-VI) quantum dots and rods are of widespread scientific and technological interest, owing to their size tunable energy band gap at the near-infrared optical regime. This article reviews the development and investigation of IV-VI derivatives, consisting of a core (dot or rod) coated with an epitaxial shell, when either the core or the shell (or both) has an alloy composition, so the entire structure has the chemical formula PbSexS1-x/PbSeyS1-y (0 ≤ x(y) ≤ 1). The article describes synthesis procedures and an examination of the structures' chemical and temperature stability. The investigation of the optical properties revealed information about the quantum yield, radiative lifetime, emission's Stokes shift and electron-phonon interaction, on the variation of composition, core-to-shell division, temperature and environment. The study reflected the unique properties of core-shell heterostructures, offering fine electronic tuning (at a fixed size) by changing their architecture. The optical observations are supported by the electronic band structure theoretical model. The challenges related to potential applications of the colloidal lead chalcogenide quantum dots and rods are also briefly addressed in the article.

Fluorescence of colloidal PbSe/PbS QDs in NIR luminescent solar concentrators.

For applications in luminescent solar concentrators harvesting subgap photons, either via direct irradiation of solar cells with optimized band gap or via sensitization of an up-conversion process, exact knowledge and tunability of both the spectral shape and the intensity of the emission are of paramount importance. In this work, we investigate theoretically the photoluminescence spectra of colloidal core-shell PbSe/PbS QDs with type II alignments in the valence band. The method builds on a steady-state formulation of the non-equilibrium Greens function theory for a microscopic system of coupled electrons, photons and phonons interfaced with electronic structure calculations based on a k·p model for PbSe/PbS core-shell QDs. The resulting output spectral density of photons in a realistic QD ensemble is obtained via the renormalization of the incident spectrum according to the polarization of the system.

Anomalous independence of multiple exciton generation on different group IV-VI quantum dot architectures.

Multiple exciton generation (MEG) in PbSe quantum dots (QDs), PbSe(x)S(1-x) alloy QDs, PbSe/PbS core/shell QDs, and PbSe/PbSe(y)S(1-y) core/alloy-shell QDs was studied with time-resolved optical pump and probe spectroscopy. The optical absorption exhibits a red-shift upon the introduction of a shell around a PbSe core, which increases with the thickness of the shell. According to electronic structure calculations this can be attributed to charge delocalization into the shell. Remarkably, the measured quantum yield of MEG, the hot exciton cooling rate, and the Auger recombination rate of biexcitons are similar for pure PbSe QDs and core/shell QDs with the same core size and varying shell thickness. The higher density of states in the alloy and core/shell QDs provide a faster exciton cooling channel that likely competes with the fast MEG process due to a higher biexciton density of states. Calculations reveal only a minor asymmetric delocalization of holes and electrons over the entire core/shell volume, which may partially explain why the Auger recombination rate does not depend on the presence of a shell.

Composition-tunable optical properties of colloidal IV-VI quantum dots, composed of core/shell heterostructures with alloy components.

Colloidal quantum dots (CQDs) attract worldwide scientific and technological attention due to the ability to engineer their optical properties by the variation of their size. However, several important applications, such as biological tagging and photovoltaic cells, impose a limit on their size yet demand tunability and thermal stability of the optical band edge. This work introduces a new class of heterostructures, composed of PbSe or PbSe(y)S(1-y) cores, coated by PbS or PbSe(x)S(1-x) shells, with different core-radius/shell-width division, with a radial gradient composition (with 0 < y < 1, 0 < x < 1), which offer a control of the band edge properties by varying the CQDs' composition. Continuous-wave and transient photoluminescence measurements over a wide temperature range (1.4-300 K) revealed a distinct behavior of the heterostructures with respect to that of pure PbSe cores: (i) increase of the emission quantum yield; (ii) red-shift of the absorption edge but a decrease of the emission Stokes shift; (iii) alleviation of a dark exciton recombination, viz., a reduction of an exchange interaction; (iv) tuning of the radiative lifetime with shell width and composition; (v) reduction of the band edge temperature coefficient, dE/dT, viz., induction of thermal stability. The k·p envelope function calculation, considering abrupt or smooth alloying continuation of the potential at the core-shell interface, revealed a delocalization of the hole wave function over the entire volume of the CQDs, as a partial explanation for the marked tunability, nonetheless preserving a desired size.