Oriented attachment of synthetic semiconductor nanocrystals is emerging as a route for obtaining new semiconductors that can have Dirac-type electronic bands such as graphene, but also strong spin-orbit coupling. The two-dimensional (2D) assembly geometry will require both atomic coherence and long-range periodicity of the superlattices. We show how the interfacial self-assembly and oriented attachment of nanocrystals results in 2D metal chalcogenide semiconductors with a honeycomb superlattice. We present an extensive atomic and nanoscale characterization of these systems using direct imaging and wave scattering methods. The honeycomb superlattices are atomically coherent and have an octahedral symmetry that is buckled; the nanocrystals occupy two parallel planes. Considerable necking and large-scale atomic motion occurred during the attachment process.

Lanthanide-doped upconversion (UC) phosphors absorb low-energy infrared light and convert it into higher-energy visible light. Despite over 10 years of development, it has not been possible to synthesize nanocrystals (NCs) with UC efficiencies on a par with what can be achieved in bulk materials. To guide the design and realization of more efficient UC NCs, a better understanding is necessary of the loss pathways competing with UC. Here we study the excited-state dynamics of the workhorse UC material β-NaYF4 co-doped with Yb3+ and Er3+. For each of the energy levels involved in infrared-to-visible UC, we measure and model the competition between spontaneous emission, energy transfer between lanthanide ions, and other decay processes. An important quenching pathway is energy transfer to high-energy vibrations of solvent and/or ligand molecules surrounding the NCs, as evidenced by the effect of energy resonances between electronic transitions of the lanthanide ions and vibrations of the solvent molecules. We present a microscopic quantitative model for the quenching dynamics in UC NCs. It takes into account cross-relaxation at high lanthanide-doping concentration as well as Förster resonance energy transfer from lanthanide excited states to vibrational modes of molecules surrounding the UC NCs. Our model thereby provides insight in the inert-shell thickness required to prevent solvent quenching in NCs. Overall, the strongest contribution to reduced UC efficiencies in core–shell NCs comes from quenching of the near-infrared energy levels (Er3+: 4I11/2 and Yb3+: 2F5/2), which is likely due to vibrational coupling to OH– defects incorporated in the NCs during synthesis.

Oriented attachment of PbSe nanocubes can result in the formation of two-dimensional (2D) superstructures with long-range nanoscale and atomic order. This questions the applicability of classic models in which the superlattice grows by first forming a nucleus, followed by sequential irreversible attachment of nanocrystals, as one misaligned attachment would disrupt the 2D order beyond repair. Here, we demonstrate the formation mechanism of 2D PbSe superstructures with square geometry by using in situ grazing-incidence X-ray scattering (small angle and wide angle), ex situ electron microscopy, and Monte Carlo simulations. We observed nanocrystal adsorption at the liquid/gas interface, followed by the formation of a hexagonal nanocrystal monolayer. The hexagonal geometry transforms gradually through a pseudo-hexagonal phase into a phase with square order, driven by attractive interactions between the {100} planes perpendicular to the liquid substrate, which maximize facet-to-facet overlap. The nanocrystals then attach atomically via a necking process, resulting in 2D square superlattices.

Luminescent copper indium sulfide (CIS) nanocrystals are a potential solution to the toxicity issues associated with Cd- and Pb-based nanocrystals. However, the development of high-quality CIS nanocrystals has been complicated by insufficient knowledge of the electronic structure and of the factors that lead to luminescence quenching. Here we investigate the exciton decay pathways in CIS nanocrystals using time-resolved photoluminescence and transient absorption spectroscopy. Core-only CIS nanocrystals with low quantum yield are compared to core/shell nanocrystals (CIS/ZnS and CIS/CdS) with higher quantum yield. Our measurements support the model of photoluminescence by radiative recombination of a conduction band electron with a localized hole. Moreover, we find that photoluminescence quenching in low-quantum-yield nanocrystals involves initially uncoupled decay pathways for the electron and hole. The electron decay pathway determines whether the exciton recombines radiatively or nonradiatively. The development of high-quality CIS nanocrystals should therefore focus on the elimination of electron traps.

The efficiency and stability of emission from semiconductor nanocrystal quantum dots (QDs) is negatively affected by "blinking" on the single-nanocrystal level, that is, random alternation of bright and dark periods. The time scales of these fluctuations can be as long as many seconds, orders of magnitude longer than typical lifetimes of exciton states in QDs. In this work, we investigate photoluminescence from QDs delayed over microseconds to milliseconds. Our results prove the existence of long-lived charge-separated states in QDs. We study the properties of delayed emission as a direct way to learn about charge carrier separation and recovery of the exciton state. A new microscopic model is developed to connect delayed emission to exciton recombination and blinking from which we conclude that bright periods in blinking are in fact not characterized by uninterrupted optical cycling as often assumed.

Luminescent colloidal CdSe nanoplatelets with atomically defined thicknesses have recently been developed, and their potential for various applications has been shown. To understand their special properties, experiments have until now focused on the relatively short time scales of at most a few nanoseconds. Here, we measure the photoluminescence decay dynamics of colloidal nanoplatelets on time scales up to tens of microseconds. The excited state dynamics are found to be dominated by the slow (∼μs) dynamics of temporary exciton storage in a charge-separated state, previously overlooked. We study the processes of charge carrier separation and exciton recovery in pure CdSe nanoplatelets as well as in core-crown and core-shell CdSe/CdS nanoplatelets with high ensemble quantum yields of 50%, and discuss the implications. Our work highlights the importance of reversible charge carrier trapping and experiments over a wide range of time scales for the understanding of colloidal nanoemitters in general and nanoplatelets in particular.

Electronic transitions in luminescent molecules or centers in crystals couple to vibrations. This results in broadening of absorption and emission bands, as well as in the occurence of a Stokes shift E Stokes . In principle, one can derive from E Stokes the Huang-Rhys parameter S, which describes the microscopic details of the vibrational coupling and can be related to the equilibrium position offset DQ e between the ground state and excited state. The commonly used textbook relations E Stokes = (2S À 1) ho and E Stokes = 2S ho are only approximately valid. In this paper we investigate how E Stokes is related to S, taking into account the effects of a finite temperature. We show that in different ranges of temperature, different approximate relations between E Stokes and S are appropriate. Moreover, we demonstrate that the difference between the barycenters of absorption and emission bands can be used to determine S in an unambiguous way.The position of the barycenter is, contrary to the Stokes shift, unaffected by temperature.

Luminescent CuInS2 nanocrystals are prepared by partial cation exchange in Cu2‐xS nanocrystals (NCs) suspended in toluene using a MeOH solution of In(NO3)3 in the molar ratio of In/Cu of ≈1.