Composition-Defined Optical Properties and the Direct-to-Indirect Transition in Core-Shell In1-xGaxP/ZnS Colloidal Quantum Dots.

Semiconductors are commonly divided into materials with direct or indirect band gaps based on the relative positions of the top of the valence band and the bottom of the conduction band in crystal momentum (k) space. It has, however, been debated if k is a useful quantum number to describe the band structure in quantum-confined nanocrystalline systems, which blur the distinction between direct and indirect gap semiconductors. In bulk III-V semiconductor alloys like In1-xGaxP, the band structure can be tuned continuously from the direct- to indirect-gap by changing the value of x. The effect of strong quantum confinement on the direct-to-indirect transition in this system has yet to be established because high-quality colloidal nanocrystal samples have remained inaccessible. Herein, we report one of the first systematic studies of ternary III-V nanocrystals by utilizing an optimized molten-salt In-to-Ga cation exchange protocol to yield bright In1-xGaxP/ZnS core-shell particles with photoluminescence quantum yields exceeding 80%. We performed two-dimensional solid-state NMR studies to assess the alloy homogeneity and the extent of surface oxidation in In1-xGaxP cores. The radiative decay lifetime for In1-xGaxP/ZnS monotonically increases with higher gallium content. Transient absorption studies on In1-xGaxP/ZnS nanocrystals demonstrate signatures of direct- and indirect-like behavior based on the presence or absence, respectively, of excitonic bleach features. Atomistic electronic structure calculations based on the semi-empirical pseudopotential model are used to calculate absorption spectra and radiative lifetimes and evaluate band-edge degeneracy; the resulting calculated electronic properties are consistent with experimental observations. By studying photoluminescence characteristics at elevated temperatures, we demonstrate that a reduced lattice mismatch at the III-V/II-VI core-shell interface can enhance the thermal stability of emission. These insights establish cation exchange in molten inorganic salts as a viable synthetic route to nontoxic, high-quality In1-xGaxP/ZnS QD emitters with desirable optoelectronic properties.

Diffusion-Limited Kinetics of Isovalent Cation Exchange in III-V Nanocrystals Dispersed in Molten Salt Reaction Media.

The goal of this work is to determine the kinetic factors that govern isovalent cation exchange in III-V colloidal quantum dots using molten salts as the solvent and cation source. We focus on the reactions of InP + GaI3→ In1-xGaxP and InAs + GaI3→ In1-xGaxAs to create technologically important ternary III-V phases. We find that the molten salt reaction medium causes the transformation of nearly spherical InP nanocrystals to tetrahedron-shaped In1-xGaxP nanocrystals. Furthermore, we determine that the activation energy for the cation exchange reaction is 0.9 eV for incorporation of Ga into InP and 1.2 eV for incorporation of Ga into InAs, both much lower than the measured values in bulk semiconductors. Next, we use powder XRD simulations to constrain our understanding of the structure of the In1-xGaxP nanocrystals. Together our results reveal several important features of molten salt-mediated cation exchange and provide guidance for future development of these materials.

Engineering Long-Lived Blue Photoluminescence from InP Quantum Dots Using Isomers of Naphthoic Acid.

Leveraging triplet excitons in semiconductor quantum dots (QDs) in concert with surface-anchored molecules to produce long-lifetime thermally activated delayed photoluminescence (TADPL) continues to emerge as a promising technology in diverse areas including photochemical catalysis and light generation. All QDs presently used to generate TADPL in QD/molecule constructs contain toxic metals including Cd(II) and Pb(II), ultimately limiting potential real-world applications. Here, we report newly conceived blue-emitting TADPL-producing nanomaterials featuring InP QDs interfaced with 1- and 2-naphthoic acid (1-NA and 2-NA) ligands. These constitutional isomers feature similar triplet energies but disparate triplet lifetimes, translating into InP-based TADPL processes displaying two distinct average lifetime ranges upon cooling from 293 to 193 K. The time constants fall between 4.4 and 59.2 µs in the 2-NA-decorated InP QDs while further expanding between 84.2 and 733.2 µs in the corresponding 1-NA-ligated InP materials, representing a 167-fold time window. The resulting long-lived excited states enabled facile bimolecular triplet sensitization of 1O2 phosphorescence in the near-IR and promoted sensitized triplet-triplet annihilation photochemistry in 2,5-diphenyloxazole. We speculate that the discovery of new nanomaterials exhibiting TADPL lies on the horizon as myriad QDs can be readily derivatized using isomers of numerous classes of surface-anchoring chromophores yielding precisely regulated photophysical properties.

Quantum dot solids showing state-resolved band-like transport.

Improving charge mobility in quantum dot (QD) films is important for the performance of photodetectors, solar cells and light-emitting diodes. However, these applications also require preservation of well defined QD electronic states and optical transitions. Here, we present HgTe QD films that show high mobility for charges transported through discrete QD states. A hybrid surface passivation process efficiently eliminates surface states, provides tunable air-stable n and p doping and enables hysteresis-free filling of QD states evidenced by strong conductance modulation. QD films dried at room temperature without any post-treatments exhibit mobility up to µ ~ 8 cm2 V-1 s-1 at a low carrier density of less than one electron per QD, band-like behaviour down to 77 K, and similar drift and Hall mobilities at all temperatures. This unprecedented set of electronic properties raises important questions about the delocalization and hopping mechanisms for transport in QD solids, and introduces opportunities for improving QD technologies.

Origin of Broad Emission Spectra in InP Quantum Dots: Contributions from Structural and Electronic Disorder.

The ensemble emission spectra of colloidal InP quantum dots are broader than achievable spectra of cadmium- and lead-based quantum dots, despite similar single-particle line widths and significant efforts invested in the improvement of synthetic protocols. We seek to explain the origin of persistently broad ensemble emission spectra of colloidal InP quantum dots by investigating the nature of the electronic states responsible for luminescence. We identify a correlation between red-shifted emission spectra and anomalous broadening of the excitation spectra of luminescent InP colloids, suggesting a trap-associated emission pathway in highly emissive core-shell quantum dots. Time-resolved pump-probe experiments find that electrons are largely untrapped on photoluminescence relevant time scales pointing to emission from recombination of localized holes with free electrons. Two-dimensional electronic spectroscopy on InP quantum dots reveals multiple emissive states and increased electron-phonon coupling associated with hole localization. These localized hole states near the valence band edge are hypothesized to arise from incomplete surface passivation and structural disorder associated with lattice defects. We confirm the presence and effect of lattice disorder by X-ray absorption spectroscopy and Raman scattering measurements. Participation of localized electronic states that are associated with various classes of lattice defects gives rise to phonon-coupled defect related emission. These findings explain the origins of the persistently broad emission spectra of colloidal InP quantum dots and suggest future strategies to narrow ensemble emission lines comparable to what is observed for cadmium-based materials.

New Forms of CdSe: Molecular Wires, Gels, and Ordered Mesoporous Assemblies.

This work investigates the structure and properties of soluble chalcogenidocadmates, a molecular form of cadmium chalcogenides with unprecedented one-dimensional bonding motifs. The single crystal X-ray structure reveals that sodium selenocadmate consists of infinite one-dimensional wires of (Cd2Se3)n2n- charge balanced by Na+ and stabilized by coordinating solvent molecules. Exchanging the sodium cation with tetraethylammonium or didodecyldimethylammonium expands the versatility of selenocadmate by improving its solubility in a variety of polar and nonpolar solvents without changing the anion structure and properties. The introduction of a micelle-forming cationic surfactant allows for the templating of selenocadmate, or the analogous telluride species, to create ordered organic-inorganic hybrid CdSe or CdTe mesostructures. Finally, the interaction of selenocadmate "wires" with Cd2+ ions creates an unprecedented gel-like form of stoichiometric CdSe. We also demonstrate that these low-dimensional CdSe species show characteristic semiconductor behavior, and can be used in photodetectors and field-effect transistors.

Self-assembly of nanocrystals into strongly electronically coupled all-inorganic supercrystals.

Colloidal nanocrystals of metals, semiconductors, and other functional materials can self-assemble into long-range ordered crystalline and quasicrystalline phases, but insulating organic surface ligands prevent the development of collective electronic states in ordered nanocrystal assemblies. We reversibly self-assembled colloidal nanocrystals of gold, platinum, nickel, lead sulfide, and lead selenide with conductive inorganic ligands into supercrystals exhibiting optical and electronic properties consistent with strong electronic coupling between the constituent nanocrystals. The phase behavior of charge-stabilized nanocrystals can be rationalized and navigated with phase diagrams computed for particles interacting through short-range attractive potentials. By finely tuning interparticle interactions, the assembly was directed either through one-step nucleation or nonclassical two-step nucleation pathways. In the latter case, the nucleation was preceded by the formation of two metastable colloidal fluids.

Conduction Band Fine Structure in Colloidal HgTe Quantum Dots.

HgTe colloidal quantum dots (QDs) are of interest because quantum confinement of semimetallic bulk HgTe allows one to synthetically control the bandgap throughout the infrared. Here, we synthesize highly monodisperse HgTe QDs and tune their doping both chemically and electrochemically. The monodispersity of the QDs was evaluated using small-angle X-ray scattering (SAXS) and suggests a diameter distribution of ∼10% across multiple batches of different sizes. Electron-doped HgTe QDs display an intraband absorbance and bleaching of the first two excitonic features. We see splitting of the intraband peaks corresponding to electronic transitions from the occupied 1Se state to a series of nondegenerate 1Pe states. Spectroelectrochemical studies reveal that the degree of splitting and relative intensity of the intraband features remain constant across doping levels up to two electrons per QD. Theoretical modeling suggests that the splitting of the 1Pe level arises from spin-orbit coupling and reduced QD symmetry. The fine structure of the intraband transitions is observed in the ensemble studies due to the size uniformity of the as-synthesized QDs and strong spin-orbit coupling inherent to HgTe.