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 (CsPbX, 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 CsPbX 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.

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 CsPbBr 3 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 CsPbBr 3 NCs is opposite to what has been observed experimentally. An alternate explanation for the observed bright exciton level order in CsPbBr 3 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.

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.

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.

Quasi type-II PbSe/PbS quantum dots (QDs) are employed in a solid state high effi ciency QD/TiO 2 heterojunction solar cell. The QDs are deposited using layer-by-layer deposition on a half-micrometer-thick anatase TiO 2 nanosheet fi lm with (001) exposed facets. Theoretical calculations show that the carriers in PbSe/PbS quasi type-II QDs are delocalized over the entire core/shell structure, which results in better QD fi lm conductivity compared to PbSe QDs. Moreover, PbS shell permits better stability and facile electron injection from the QDs to the TiO 2 nanosheets. To complete the electrical circuit of the solar cell, a Au fi lm is evaporated as a back contact on top of the QDs. This PbSe/PbS QD/TiO 2 heterojunction solar cell produces a light to electric power conversion effi ciency ( η ) of 4% with short circuit photocurrent ( J sc ) of 17.3 mA/cm 2 . This report demonstrates highly effi cient core/shell near infrared QDs in a QD/TiO 2 heterojunction solar cell.

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.

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.

We calculate the rate of nonradiative Auger recombination in InGaN/GaN quantum wells with rectangular and smooth confining potentials. The calculations show that the rate of Auger recombination in rectangular quantum wells is sufficiently high to explain the efficiency droop in nitride-based light emitting diodes (LEDs). This rate, however, can be reduced by softening of the confining potential and a three-fold suppression is demonstrated in the studied quantum wells. The suppression of the Auger recombination rate improves LED radiative efficiency and reduces the droop effect, as we show using the standard recombination (ABC) model.