Infrared Imaging Using Thermally Stable HgTe/CdS Nanocrystals.

Transferring nanocrystals (NCs) from the laboratory environment toward practical applications has raised new challenges. HgTe appears as the most spectrally tunable infrared colloidal platform. Its low-temperature synthesis reduces the growth energy cost yet also favors sintering.

In Situ X-ray Scattering Reveals Coarsening Rates of Superlattices Self-Assembled from Electrostatically Stabilized Metal Nanocrystals Depend Nonmonotonically on Driving Force.

Self-assembly of colloidal nanocrystals (NCs) into superlattices (SLs) is an appealing strategy to design hierarchically organized materials with promising functionalities. Mechanistic studies are still needed to uncover the design principles for SL self-assembly, but such studies have been difficult to perform due to the fast time and short length scales of NC systems. To address this challenge, we developed an apparatus to directly measure the evolving phases and in real time of an electrostatically stabilized Au NC solution before, during, and after it is quenched to form SLs using small-angle X-ray scattering.

Inside a nanocrystal-based photodiode using photoemission microscopy.

As nanocrystal-based devices gain maturity, a comprehensive understanding of their electronic structure is necessary for further optimization. Most spectroscopic techniques typically examine pristine materials and disregard the coupling of the active material to its actual environment, the influence of an applied electric field, and possible illumination effects. Therefore, it is critical to develop tools that can probe device and .

Mapping the Energy Landscape from a Nanocrystal-Based Field Effect Transistor under Operation Using Nanobeam Photoemission Spectroscopy.

As the field of nanocrystal-based optoelectronics matures, more advanced techniques must be developed in order to reveal the electronic structure of nanocrystals, particularly with device-relevant conditions. So far, most of the efforts have been focused on optical spectroscopy, and electrochemistry where an absolute energy reference is required. Device optimization requires probing not only the pristine material but also the material in its actual environment (i.

Zwitterions in 3D Perovskites: Organosulfide-Halide Perovskites.

Although sulfide perovskites usually require high-temperature syntheses, we demonstrate that organosulfides can be used in the milder syntheses of halide perovskites. The zwitterionic organosulfide, cysteamine (CYS; NH(CH)S), serves as both the X site and A site in the ABX halide perovskites, yielding the first examples of 3D organosulfide-halide perovskites: (CYS)PbX (X = Cl or Br). Notably, the band structures of (CYS)PbX capture the direct bandgaps and dispersive bands of APbX perovskites.

Helmholtz Resonator Applied to Nanocrystal-Based Infrared Sensing.

While the integration of nanocrystals as an active medium for optoelectronic devices progresses, light management strategies are becoming required. Over recent years, several photonic structures (plasmons, cavities, mirrors, etc.) have been coupled to nanocrystal films to shape the absorption spectrum, tune the directionality, and so on.

Vanishing Confinement Regime in Terahertz HgTe Nanocrystals Studied under Extreme Conditions of Temperature and Pressure.

While HgTe nanocrystals (NCs) in the mid-infrared region have reached a high level of maturity, their far-infrared counterparts remain far less studied, raising the need for an in-depth investigation of the material before efficient device integration can be considered. Here, we explore the effect of temperature and pressure on the structural, spectroscopic, and transport properties of HgTe NCs displaying an intraband absorption at 10 THz. The temperature leads to a very weak modulation of the spectrum as opposed to what was observed for strongly confined HgTe NCs.

Nanoscale Disorder Generates Subdiffusive Heat Transport in Self-Assembled Nanocrystal Films.

Investigating the impact of nanoscale heterogeneity on heat transport requires a spatiotemporal probe of temperature on the length and time scales intrinsic to heat navigating nanoscale defects. Here, we use stroboscopic optical scattering microscopy to visualize nanoscale heat transport in disordered films of gold nanocrystals. We find that heat transport appears subdiffusive at the nanoscale.

The Motion of Trapped Holes on Nanocrystal Surfaces.

This Perspective discusses the phenomenon of trapped-hole diffusion in colloidal semiconductor nanocrystals. Surface charge-carrier traps are ubiquitous in nanocrystals and often dictate the fate of photoexcited carriers. New measurements and calculations are unveiling the nature of the nanocrystal surface, but many challenges to understanding the dynamics of trapped carriers remain.

Nonequilibrium Thermodynamics of Colloidal Gold Nanocrystals Monitored by Ultrafast Electron Diffraction and Optical Scattering Microscopy.

Metal nanocrystals exhibit important optoelectronic and photocatalytic functionalities in response to light. These dynamic energy conversion processes have been commonly studied by transient optical probes to date, but an understanding of the atomistic response following photoexcitation has remained elusive. Here, we use femtosecond resolution electron diffraction to investigate transient lattice responses in optically excited colloidal gold nanocrystals, revealing the effects of nanocrystal size and surface ligands on the electron-phonon coupling and thermal relaxation dynamics.

Electron Transfer from Semiconductor Nanocrystals to Redox Enzymes.

This review summarizes progress in understanding electron transfer from photoexcited nanocrystals to redox enzymes. The combination of the light-harvesting properties of nanocrystals and the catalytic properties of redox enzymes has emerged as a versatile platform to drive a variety of enzyme-catalyzed reactions with light. Transfer of a photoexcited charge from a nanocrystal to an enzyme is a critical first step for these reactions.

Temperature-Dependent Transient Absorption Spectroscopy Elucidates Trapped-Hole Dynamics in CdS and CdSe Nanorods.

Charge-carrier traps play a central role in the excited-state dynamics of semiconductor nanocrystals, but their influence is often difficult to measure directly. In CdS and CdSe nanorods of nonuniform width, spatially separated electrons and trapped holes display relaxation dynamics that follow a power-law function in time that is consistent with a recombination process limited by trapped-hole diffusion. However, power-law relaxation can originate from mechanisms other than diffusion.

On the Nature of Trapped-Hole States in CdS Nanocrystals and the Mechanism of Their Diffusion.

Recent transient absorption experiments on CdS nanorods suggest that photoexcited holes rapidly trap to the surface of these particles and then undergo diffusion along the rod surface. In this Letter, we present a semiperiodic density functional theory model for the CdS nanocrystal surface, analyze it, and comment on the nature of both the hole-trap states and the mechanism by which the holes diffuse. Hole states near the top of the valence band form an energetic near continuum with the bulk and localize to the nonbonding sp orbitals on surface sulfur atoms.

Relationships between Exciton Dissociation and Slow Recombination within ZnSe/CdS and CdSe/CdS Dot-in-Rod Heterostructures.

Type-II and quasi type-II heterostructure nanocrystals are known to exhibit extended excited-state lifetimes compared to their single material counterparts because of reduced wave function overlap between the electron and hole. However, due to fast and efficient hole trapping and nonuniform morphologies, the photophysics of dot-in-rod heterostructures are more rich and complex than this simple picture. Using transient absorption spectroscopy, we observe that the behavior of electrons in the CdS "rod" or "bulb" regions of nonuniform ZnSe/CdS and CdSe/CdS dot-in-rods is similar regardless of the "dot" material, which supports previous work demonstrating that hole trapping and particle morphology drive electron dynamics.

Observation of trapped-hole diffusion on the surfaces of CdS nanorods.

In CdS nanocrystals, photoexcited holes rapidly become trapped at the particle surface. The dynamics of these trapped holes have profound consequences for the photophysics and photochemistry of these materials. Using a combination of transient absorption spectroscopy and theoretical modelling, we demonstrate that trapped holes in CdS nanorods are mobile and execute a random walk at room temperature.

Competition between electron transfer, trapping, and recombination in CdS nanorod-hydrogenase complexes.

Electron transfer from photoexcited CdS nanorods to [FeFe]-hydrogenase is a critical step in photochemical H2 production by CdS-hydrogenase complexes. By accounting for the distributions in the numbers of electron traps and enzymes adsorbed, we determine rate constants and quantum efficiencies for electron transfer from transient absorption measurements.

Conformation of self-assembled porphyrin dimers in liposome vesicles by phase-modulation 2D fluorescence spectroscopy.

By applying a phase-modulation fluorescence approach to 2D electronic spectroscopy, we studied the conformation-dependent exciton coupling of a porphyrin dimer embedded in a phospholipid bilayer membrane. Our measurements specify the relative angle and separation between interacting electronic transition dipole moments and thus provide a detailed characterization of dimer conformation. Phase-modulation 2D fluorescence spectroscopy (PM-2D FS) produces 2D spectra with distinct optical features, similar to those obtained using 2D photon-echo spectroscopy.