Understanding the energy flow in quantum dot solids represents an important step toward designing artificial systems with configurable optoelectronic properties. The growing complexity of nanoparticle assemblies and deposition techniques calls for advanced methods of characterization and control of the underlying exciton diffusion, which is pervasive in these materials. Along these lines, the Perspective will review recent strategies for measuring the energy transfer processes in assemblies of semiconductor nanocrystals with particular emphasis on emerging avant-garde characterization techniques. We will also shed light on novel experimental methods for controlling the energy diffusion in quantum dots solids, highlighting the role of assembly architecture in ensuing processes of exciton diffusion and dissociation. Novel energy transfer mechanisms recently observed in perovskite quantum dots and triplet-sensitizer nanocrystals will also be discussed.

Colloidal nanocrystal solids represent an emerging class of functional materials that hold strong promise for device applications. The macroscopic properties of these disordered assemblies are determined by complex trajectories of exciton diffusion processes, which are still poorly understood. Owing to the lack of theoretical insight, experimental strategies for probing the exciton dynamics in quantum dot solids are in great demand. Here, we develop an experimental technique for mapping the motion of excitons in semiconductor nanocrystal films with a subdiffraction spatial sensitivity and a picosecond temporal resolution. This was accomplished by doping PbS nanocrystal solids with metal nanoparticles that force the exciton dissociation at known distances from their birth. The optical signature of the exciton motion was then inferred from the changes in the emission lifetime, which was mapped to the location of exciton quenching sites. By correlating the metal-metal interparticle distance in the film with corresponding changes in the emission lifetime, we could obtain important transport characteristics, including the exciton diffusion length, the number of predissociation hops, the rate of interparticle energy transfer, and the exciton diffusivity. The benefits of this approach to device applications were demonstrated through the use of two representative film morphologies featuring weak and strong interparticle coupling.

One of the key challenges facing the realization of functional nanocrystal devices concerns the development of techniques for depositing colloidal nanocrystals into electrically coupled nanoparticle solids. This work compares several alternative strategies for the assembly of such films using an all-optical approach to the characterization of electron transport phenomena. By measuring excited carrier lifetimes in either ligand-linked or matrix-encapsulated PbS nanocrystal films containing a tunable fraction of insulating ZnS domains, we uniquely distinguish the dynamics of charge scattering on defects from other processes of exciton dissociation. The measured times are subsequently used to estimate the diffusion length and the carrier mobility for each film type within the hopping transport regime. It is demonstrated that nanocrystal films encapsulated into semiconductor matrices exhibit a lower probability of charge scattering than that of nanocrystal solids cross-linked with either 3-mercaptopropionic acid or 1,2-ethanedithiol molecular linkers. The suppression of carrier scattering in matrix-encapsulated nanocrystal films is attributed to a relatively low density of surface defects at nanocrystal/matrix interfaces.

Digestive ripening (DR) represents a powerful strategy for improving the size homogeneity of colloidal nanostructures. It relies on the ligand-mediated dissolution of larger nanoparticles in favor of smaller ones and is often considered to be the opposite of Ostwald ripening. Despite its successful application to size-focusing of metal colloids, digestive ripening of semiconductor nanocrystals has received little attention to date. Here, we explore this synthetic niche and demonstrate that ligand-induced ripening of semiconductor nanocrystals exhibits an unusual reaction path. The unique aspect of the DR process in semiconductors lies in the thermally activated particle coalescence, which leads to a significant increase in the nanocrystal size for temperatures above the threshold value (T th = 200–220 °C). Below this temperature, nanoparticle sizes focus to an ensemble average diameter just like in the case of metal colloids. The existence of the thermal threshold for coalescence offers an expedient strategy for controlling both the particle size and the size dispersion. Such advanced shape control was demonstrated using colloids of CdS, CdSe, CsPbBr3, and CuZnSnS4, where monodisperse samples were obtained across broad diameter ranges. We expect the demonstrated approach to be extended to other semiconductors as a simple strategy for tuning the nanoparticle morphology.

The ability of metal nanoparticles to concentrate light via the plasmon resonance represents a unique opportunity for funneling the solar energy in photovoltaic devices. The absorption enhancement in plasmonic solar cells is predicted to be particularly prominent when the size of metal features falls below 20 nm, causing the strong confinement of radiation modes. Unfortunately, the ultrashort lifetime of such near-field radiation makes harvesting the plasmon energy in small-diameter nanoparticles a challenging task. Here, we develop plasmonic solar cells that harness the near-field emission of 5 nm Au nanoparticles by transferring the plasmon energy to band gap transitions of PbS semiconductor nanocrystals. The interfaces of Au and PbS domains were designed to support a rapid energy transfer at rates that outpace the thermal dephasing of plasmon modes. We demonstrate that central to the device operation is the inorganic passivation of Au nanoparticles with a wide gap semiconductor, which reduces carrier scattering and simultaneously improves the stability of heat-prone plasmonic films. The contribution of the Au near-field emission toward the charge carrier generation was manifested through the observation of an enhanced short circuit current and improved power conversion efficiency of mixed (Au, PbS) solar cells, as measured relative to PbS-only devices.