The Underlying Chemical Mechanism of Selective Chemical Etching in CsPbBr3 Nanocrystals for Reliably Accessing Near-Unity Emitters.

Reliably accessing nanocrystal luminophores with near-unity efficiencies aids in the ability to understand the upper performance limits in optoelectronic applications that require minimal nonradiative losses. Constructing structure-function relationships at the atomic level, while accounting for inevitable defects, allows for the development of robust strategies to achieve near-unity quantum yield luminophores. For CsPbBr3 perovskite nanocrystals, bromine vacancies leave behind undercoordinated lead atoms that act as traps, limiting the achievable optical performance of the material. We show that selective etching represents a promising path for mitigating the consequences of optical defects in CsPbBr3 nanocrystals. A mechanistic understanding of the etching reaction is essential for developing strategies to finely control the reaction. We report a study of the selective etching mechanism of CsPbBr3 nanocrystal cubes by controlling the etchant chemical potential. We observe optical absorption and luminescence trajectories while varying the extent and rate of lead removal, removing in some cases up to 75% of the lead from the original nanocrystal ensemble. At modest etchant chemical potentials, the size and shape uniformity of the nanocrystal ensemble improves in addition to the quantum yield, proceeding through a layer-by-layer etching mechanism. Operating with excessively high etchant chemical potentials is detrimental to the overall optical performance as the etching transitions to nonselective, while too low of a chemical potential results in incomplete etching. Through this general approach, we show how to finely control selective etching to consistently access a steady state or chemical stability zone of near-unity quantum yield CsPbBr3 nanocrystals postsynthetically, suggesting a practical framework to extend this treatment to other perovskite compositions and sizes

Ultrahigh Hot Carrier Transient Photocurrent in Nanocrystal Arrays by Auger Recombination.

In this report, we show that a new mechanism for carrier transport in solution-processed colloidal semiconductor nanocrystal arrays exists at high excitation intensity on ultrafast time scales and allows for facile intrinsic transport between as-prepared nanocrystals over long distances. By combining a high speed photoconductive switch with an ultrafast laser excitation in a sub-40 ps photoconductor, we observed transient photocurrents with peak densities of 3 × 104 - 106 mA/cm2 in self-assembled PbSe nanocrystals capped with long native oleic acid ligands. The ratio between the transient photocurrent peak and the steady-state dark current is 10 orders of magnitude. The transient mobility at the peak current is estimated to range between 0.5-17.5 cm2/(V s) for the various nanocrystal sizes studied, which is 6 to 9 orders of magnitude higher than the dark current steady-state mobility in PbSe, CdSe, and CdTe nanocrystals capped with native ligands. The results are analyzed using a kinetic model which attributes the ultrahigh transient photocurrent to multiple photogenerated excitons undergoing on-particle Auger recombination, followed by rapid tunneling at high energies. This mechanism is demonstrated for a wide range of PbSe nanocrystals sizes (diameters from 2.7 to 7.1 nm) and experimental parameters. Our observations indicate that native ligand-capped nanocrystal arrays are promising for optoelectronics applications wherein multiple carriers are photoinjected to interband states

Resilient Pathways to Atomic Attachment of Quantum Dot Dimers and Artificial Solids from Faceted CdSe Quantum Dot Building Blocks.

The goal of this work is to identify favored pathways for preparation of defect-resilient attached wurtzite CdX (X = S, Se, Te) nanocrystals. We seek guidelines for oriented attachment of faceted nanocrystals that are most likely to yield pairs of nanocrystals with either few or no electronic defects or electronic defects that are in and of themselves desirable and stable. Using a combination of in situ high-resolution transmission electron microscopy (HRTEM) and electronic structure calculations, we evaluate the relative merits of atomic attachment of wurtzite CdSe nanocrystals on the {11̅00} or {112̅0} family of facets. Pairwise attachment on either facet can lead to perfect interfaces, provided the nanocrystal facets are perfectly flat and the angles between the nanocrystals can adjust during the assembly. Considering defective attachment, we observe for {11̅00} facet attachment that only one type of edge dislocation forms, creating deep hole traps. For {112̅0} facet attachment, we observe that four distinct types of extended defects form, some of which lead to deep hole traps whereas others only to shallow hole traps. HRTEM movies of the dislocation dynamics show that dislocations at {11̅00} interfaces can be removed, albeit slowly. Whereas only some extended defects at {112̅0} interfaces could be removed, others were trapped at the interface. Based on these insights, we identify the most resilient pathways to atomic attachment of pairs of wurtzite CdX nanocrystals and consider how these insights can translate to the creation of electronically useful materials from quantum dots with other crystal structures

Magnetic Domains and Surface Effects in Hollow Maghemite Nanoparticles

In the present work, we investigate the magnetic properties of ferrimagnetic and noninteracting maghemite (g-Fe2O3) hollow nanoparticles obtained by the Kirkendall effect. From the experimental characterization of their magnetic behavior, we find that polycrystalline hollow maghemite nanoparticles are characterized by low superparamagnetic-to-ferromagnetic transition temperatures, small magnetic moments, significant coercivities and irreversibility fields, and no magnetic saturation on external magnetic fields up to 5 T. These results are interpreted in terms of the microstructural parameters characterizing the maghemite shells by means of an atomistic Monte Carlo simulation of an individual spherical shell model. The model comprises strongly interacting crystallographic domains arranged in a spherical shell with random orientations and anisotropy axis. The Monte Carlo simulation allows discernment between the influence of the structure polycrystalline and its hollow geometry, while revealing the magnetic domain arrangement in the different temperature regimes.Comment: 26 pages, 8 figures. In press in Phys. Rev.

Photovoltaic Performance of Ultrasmall PbSe Quantum Dots

We investigated the effect of PbSe quantum dot size on the performance of Schottky solar cells made in an ITO/PEDOT/PbSe/aluminum structure, varying the PbSe nanoparticle diameter from 1 to 3 nm. In this highly confined regime, we find that the larger particle bandgap can lead to higher open-circuit voltages (~0.6 V), and thus an increase in overall efficiency compared to previously reported devices of this structure. To carry out this study, we modified existing synthesis methods to obtain ultrasmall PbSe nanocrystals with diameters as small as 1 nm, where the nanocrystal size is controlled by adjusting the growth temperature. As expected, we find that photocurrent decreases with size due to reduced absorption and increased recombination, but we also find that the open-circuit voltage begins to decrease for particles with diameters smaller than 2 nm, most likely due to reduced collection efficiency. Owing to this effect, we find peak performance for devices made with PbSe dots with a first exciton energy of ~1.6 eV (2.3 nm diameter), with a typical efficiency of 3.5%, and a champion device efficiency of 4.57%. Comparing the external quantum efficiency of our devices to an optical model reveals that the photocurrent is also strongly affected by the coherent interference in the thin film due to Fabry-Pérot cavity modes within the PbSe layer. Our results demonstrate that even in this simple device architecture, fine-tuning of the nanoparticle size can lead to substantial improvements in efficiency

Unsaturated Ligands Seed an Order to Disorder Transition in Mixed Ligand Shells of CdSe/CdS Quantum Dots.

A phase transition within the ligand shell of core/shell quantum dots is studied in the prototypical system of colloidal CdSe/CdS quantum dots with a ligand shell composed of bound oleate (OA) and octadecylphosphonate (ODPA). The ligand shell composition is tuned using a ligand exchange procedure and quantified through proton NMR spectroscopy. Temperature-dependent photoluminescence spectroscopy reveals a signature of a phase transition within the organic ligand shell. Surprisingly, the ligand order to disorder phase transition triggers an abrupt increase in the photoluminescence quantum yield (PLQY) and full-width at half-maximum (FWHM) with increasing temperature. The temperature and width of the phase transition show a clear dependence on ligand shell composition, such that QDs with higher ODPA fractions have sharper phase transitions that occur at higher temperatures. In order to gain a molecular understanding of the changes in ligand ordering, Fourier transform infrared and vibrational sum frequency generation spectroscopies are performed. These measurements confirm that an order/disorder transition in the ligand shell tracks with the photoluminescence changes that accompany the ligand phase transition. The phase transition is simulated through a lattice model that suggests that the ligand shell is well-mixed and does not have completely segregated domains of OA and ODPA. Furthermore, we show that the unsaturated chains of OA seed disorder within the ligand shell

First-principles modeling of unpassivated and surfactant-passivated bulk facets of wurtzite CdSe: a model system for studying the anisotropic growth of CdSe nanocrystals.

Equilibrium geometries, surface energies, and surfactant binding energies are calculated for selected bulk facets of wurtzite CdSe with a first-principles approach. Passivation of the surface Cd atoms with alkyl phosphonic acids or amines lowers the surface energy of all facets, except for the polar 0001 facet. On the nonpolar facets, the most stable configuration corresponds to full coverage of surface Cd atoms with surfactants, while on the polar 0001 facet it corresponds only to a partial coverage. In addition, the passivated surface energies of the nonpolar facets are in general lower than the passivated polar 0001 facet. Therefore, the polar facets are less stable and less efficiently passivated than the nonpolar facets, and this can rationalize the observed anisotropic growth mechanism of wurtzite nanocrystals in the presence of suitable surfactants

Design of Nanostructured Solar Cells Using Coupled Optical and Electrical Modeling

Nanostructured light trapping has emerged as a promising route toward improved efficiency in solar cells. We use coupled optical and electrical modeling to guide optimization of such nanostructures. We study thin-film n-i-p a-Si:H devices and demonstrate that nanostructures can be tailored to minimize absorption in the doped a-Si:H, improving carrier collection efficiency. This suggests a method for device optimization in which optical design not only maximizes absorption, but also ensures resulting carriers are efficiently collected