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We report a colloidal synthesis of blue emissive, stable cube-shaped CsPbBr3 quantum dots (QDs) in the strong quantum confinement regime via a dissolution-recrystallization starting from pre-synthesized (KxCs1-x)4PbBr6 nanocrystals which are then reacted with PbBr2. This is markedly different from the known case of Cs4PbBr6 nanocrystals that react within seconds with PbBr2 and get transformed into much larger, green emitting CsPbBr3 nanocrystals. Here, instead, the conversion of (KxCs1-x)4PbBr6 nanocrystals to CsPbBr3 QDs occurs in a time span of hours, and tuning of the QDs size is achieved by adjusting the concentration of precursors. The QDs exhibit excitonic features in optical absorption that are tunable in the 420 - 452 nm range, accompanied by blue photoluminescence with quantum yield around 60%. Detailed spectroscopic investigations in both the single and multi-exciton regime reveal the exciton fine structure and the effect of Auger recombination of these CsPbBr3 QDs, confirming theoretical predictions for this system.

The use of semiconductor nanocrystals in scalable quantum technologies requires characterization of the exciton coherence dynamics in an \emph{ensemble} of electronically isolated crystals in which system-bath interactions are nevertheless strong. In this communication, we identify signatures of Fano-like interference between excitons and photocarriers in the coherent two-dimensional photoluminescence excitation spectral lineshapes of mixed lead-halide perovskite nanocrystals in dilute solution. Specifically, by tuning the femtosecond-pulse spectrum, we show such interference in an intermediate coupling regime, which is evident in the coherent lineshape when simultaneously exciting the exciton and the free-carrier band at higher energy. We conclude that this interference is an intrinsic effect that will be consequential in the quantum dynamics of the system and will thus dictate decoherence dynamics, with consequences in their application in quantum technologies., Comment: Submitted to The Journal of Chemical Physics. The Supplemental Materials document SI.pdf can be downloaded from the Tex Source link

Understanding the nature of the photoexcitation and ultrafast charge dynamics pathways in organic halide perovskite nanocubes and their aggregation into superlattices is key for the potential applications as tunable light emitters, photon harvesting materials and light-amplification systems. In this work, we apply two-dimensional coherent electronic spectroscopy (2DES) to track in real time the formation of near-infrared optical excitons and their ultrafast relaxation in CH(NH2)2PbI3 nanocube superlattices. Our results unveil that the coherent ultrafast dynamics is limited by the combination of the inherent short exciton decay time ~40 fs and the dephasing due to the coupling with selective optical phonon modes at higher temperatures. On the picosecond timescale, we observe the progressive formation of long-lived localized trap states. The analysis of the temperature dependence of the excitonic intrinsic linewidth, as extracted by the anti-diagonal components of the 2D spectra, unveils a dramatic change of the excitonic coherence time across the cubic to tetragonal structural transition. Our results offer a new way to control and enhance the ultrafast coherent dynamics of photocarrier generation in hybrid halide perovskite synthetic solids.

The development of Quantum Simulators, artificial platforms where the predictions of many-body theories of correlated quantum materials can be tested in a controllable and tunable way, is one of the main challenges of condensed matter physics. Here we introduce artificial lattices made of lead halide perovskite nanocubes as a new platform to simulate and investigate the physics of correlated quantum materials. The ultrafast optical injection of quantum confined excitons plays the role of doping in real materials. We show that, at large photo-doping, the exciton gas undergoes an excitonic Mott transition, which fully realizes the magnetic-field-driven insulator-to-metal transition described by the Hubbard model. At lower photo-doping, the long-range interactions drive the formation of a collective superradiant state, in which the phases of the excitons generated in each single perovskite nanocube are coherently locked. Our results demonstrate that time-resolved experiments span a parameter region of the Hubbard model in which long-range and phase-coherent orders emerge out of a doped Mott insulating phase. This physics is relevant for a broad class of phenomena, such as superconductivity and charge-density waves in correlated materials whose properties are captured by doped Hubbard models.

The understanding of depletion layers is of major importance to control the optical and electronic properties of metal oxide (MO) nanocrystals (NCs). Here, we show that depletion layer engineering is the main mechanism of photodoping of MO NCs. We show that the introduction of different electronic interfaces induces a double-bending of the electronic bands and a distinct carrier density profile. We found that the light-induced depletion layer modulation and bending of the bands close to the surface of the nanocrystal is the main mechanism responsible for the storage of extra electrons after photodoping in MO NCs. We support our results by a combined experimental and theoretical approach in the case of Sn:In2O3/In2O3 core-shell NCs, in which we compare numerical simulations with empirical modeling and experiments. This allows not only to extract the main mechanism of photodoping in MO NCs but also to engineer the charge storage capability of MO NCs after photodoping. Our results are transferable to other core-multishell systems, opening up a novel direction to control the optoelectronic properties of nanoscale MOs by designing their energetic band profiles through depletion layer engineering.

Metal halide perovskites represent a flourishing area of research, driven by both their potential application in photo-voltaics and optoelectronics, and for the fundamental science underpinning their unique optoelectronic properties. The advent of colloidal methods for the synthesis of halide perovskite nanocrystals has brought to the attention inter-esting aspects of this new type of materials, above all their defect-tolerance. This review aims to provide an updated survey of this fast-moving field, with a main focus on their colloidal synthesis. We examine the chemistry and the ca-pability of different colloidal synthetic routes to control the shape, size and optical properties of the resulting nano-crystals. We also provide an up to date overview of their post-synthesis transformations, and summarize the various so-lution processes aimed at fabricating halide perovskite-based nanocomposites. We then review the fundamental optical properties of halide perovskite nanocrystals, by focusing on their linear optical properties, on the effects of quantum confinement and, then, on the current knowledge of their exciton binding energies. We also discuss the emergence of non-linear phenomena such as multiphoton absorption, biexcitons and carrier multiplication. At last, we provide an outlook in the field, with the most cogent open questions and possible future directions.

Excitonic/electronic coupling and cooperative interactions in self-assembled lead halide perovskite nanocrystals were reported to give rise to a collective low energy emission peak with accelerated dynamics. Here we report that similar spectroscopic features could appear as a result of the nanocrystal reactivity within the self-assembled superlattices. This is demonstrated by using CsPbBr3 nanocrystal superlattices under room temperature and cryogenic micro-photoluminescence spectroscopy. It is shown that keeping such structures under vacuum, a gradual contraction of the superlattices and subsequent coalescence of the nanocrystals occurs over several days. As a result, a narrow, low energy emission peak is observed at 4 K with a concomitant shortening of the photoluminescence lifetime due to the energy transfer between nanocrystals. When exposed to air, self-assembled CsPbBr3 nanocrystals develop bulk-like CsPbBr3 particles on top of the superlattices. At 4 K, these particles produce a distribution of narrow, low energy emission peaks with short lifetimes and excitation fluence-dependent, oscillatory decays, resembling the features of superfluorescence. Overall, the reactivity of CsPbBr3 nanocrystals dramatically alters the emission of their assemblies, which should not be overlooked when studying collective optoelectronic properties nor confused with superfluorescence effects., Comment: 50 pages, 26 figures

Inorganic lead halide perovskites are promising candidates for optoelectronic applications, due to their bandgap tunability, high photoluminescence quantum yield, and narrow emission line widths. In particular, they offer the possibility to vary the bandgap as a function of the halide composition and dimension/shape of the crystals at the nanoscale. Here we present an aberration-corrected scanning transmission microscopy (STEM) study of extended nanosheets of CsPbBr3 directly demonstrating their orthorhombic crystal structure and their lateral termination with Cs-Br planes. The bandgaps from individual nanosheets are measured by monochromated electron energy loss spectroscopy (EELS). We find an increase of the bandgap starting at thicknesses below 10 nm, confirming the less dramatic effect of 1D confinement in nanosheets compared to the 3D confinement observed in quantum dots, as predicted by density functional theory calculations and optical spectroscopy data from ensemble measurements.

Two-dimensional colloidal halide perovskite nanocrystals are promising materials for light emitting applications. In addition, they can be used as components to create a variety of materials through physical and chemical transformations. Recent studies focused on nanoplatelets that are able to self-assemble and transform on solid substrates. Yet, the mechanism behind the process and the atomic arrangement of their assemblies remain unclear. Here, we present the transformation of self-assembled stacks of CsPbBr$_3$ nanoplatelets in solution, capturing the different stages of the process by keeping the solutions at room temperature and monitoring the nanocrystal morphology over a period of a few months. Using ex-situ transmission electron microscopy and surface analysis, we demonstrate that the transformation mechanism can be understood as oriented attachment, proceeding through the following steps: i) desorption of the ligands from the particles surfaces, causing the merging of nanoplatelet stacks, which first form nanobelts; ii) merging of neighboring nanobelts that form more extended nanoplates; and iii) attachment of nanobelts and nanoplates, which create objects with an atomic structure that resemble a mosaic made of broken nanotiles. We reveal that the starting nanoplatelets merge seamlessly and defect-free on an atomic scale in small and thin nanobelts. However, aged nanobelts and nanoplates, which are mainly stabilized by amine/ammonium ions, link through a bilayer of CsBr. In this case, the atomic columns of neighboring perovskite lattices shift by a half-unit-cell, forming Ruddlesden-Popper planar faults., Comment: 28 pages, 5 Figures

The photoluminescence (PL), color purity, and stability of lead halide perovskite nanocrystals depend critically on the surface passivation. We present a study on the temperature dependent PL and PL decay dynamics of lead bromide perovskite nanocrystals characterized by different types of A cations, surface ligands, and nanocrystal sizes. Throughout, we observe a single emission peak from cryogenic to ambient temperature. The PL decay dynamics are dominated by the surface passivation, and a post-synthesis ligand exchange with a quaternary ammonium bromide (QAB) results in a more stable passivation over a larger temperature range. The PL intensity is highest from 50K-250K, which indicates that the ligand binding competes with the thermal energy at ambient temperature. Despite the favorable PL dynamics of nanocrystals passivated with QAB ligands (monoexponential PL decay over a large temperature range, increased PL intensity and stability), the surface passivation still needs improvement toward increased emission intensity in nanocrystal films., Comment: 19 pages, 5 figures

The vibrational modes in organic/inorganic layered perovskites are of fundamental importance for their optoelectronic properties. The hierarchical architecture of the Ruddlesden-Popper phase of these materials allows for distinct directionality of the vibrational modes withrespect to the main axes of the pseudocubic lattice in the octahedral plane. Here, we study the directionality of the fundamental phonon modes in single exfoliated Ruddlesden-Popper perovskite flakes with polarized Raman spectroscopy at ultralow-frequencies. A wealth of Raman bands is distinguished in the range from 15-150 cm-1 (2-15 meV), whose features depend on the organic cation species, on temperature, and on the direction of the linear polarization of the incident light. By controlling the angle of the linear polarization of the excitation laser with respect to the in-plane axes of the octahedral layer, we gain detailed information on the symmetry of the vibrational modes. The choice of two different organic moieties, phenethylammonium (PEA) and butylammonium (BA) allows to discern the influence of the linker molecules, evidencing strong anisotropy of the vibrations for the (PEA)2PbBr4 samples. Temperature dependent Raman measurements reveal that the broad phonon bands observed at room temperature consist of a series of sharp modes, and that such mode splitting strongly differs for the different organic moieties and vibrational bands., Comment: 25 pages, 4 figures

We demonstrate patterning of metal surfaces based on lift-off of perovskite nanocrystals that enables the fabrication of nanometer-size features without the use of resist-based nanolithography. The perovskite nanocrystals act as templates for defining the shape of the apertures in metal layers, and we exploit the variety of sizes and shapes that can be controlled in the colloidal synthesis to demonstrate the fabrication of nanoholes, nanogaps and guides with size smaller than the wavelength of light in the visible spectrum. The process can be readily integrated with standard lithography and etching techniques for the creation of more complex structures., Comment: 10 pages, 4 figures

Colloidal core/shell nanocrystals are key materials for optoelectronics, enabling control over essential properties via precise engineering of the shape, thickness, and crystal lattice structure of their shell. Here, we apply the growth protocol for CdS branched nanocrystals on CdSe nanoplatelet seeds and obtain bone-shaped heterostructures with a highly anisotropic shell. Surprisingly, the nanoplatelets withstand the high growth temperature of 350 {\deg}C and we obtain structures with a CdSe nanoplatelet core that is overcoated by a shell of cubic CdS, on top of which tetrahedral CdS structures with hexagonal lattice are formed. These complex core/shell nanocrystals show a bandedge emission around 657 nm with a photoluminescence quantum yield of ca. 42 % in solution, which is also retained in thin films. Interestingly, the nanocrystals manifest simultaneous red and green emission, and the relatively long wavelength of the green emission indicates charge recombination at the cubic/hexagonal interface of the CdS shell. The nanocrystal films show amplified spontaneous emission, random lasing, and distributed feedback lasing when the material is deposited on suitable gratings. Our work stimulates the design and fabrication of more exotic core/shell heterostructures where charge carrier delocalization, dipole moment, and other optical and electrical properties can be engineered., Comment: 26 pages, 6 figures, 1 table

The design of efficient electrocatalysts for electrochemical water splitting with minimal amount of precious metal is crucial to attain renewable and sustainable energy conversion. Here, we report the use of a network of CdSe branched colloidal nanocrystals, made of a CdSe core and eight CdSe pods (so-called octapods), able to host on their pods Pt particles, and thus catalyzing water splitting reactions. Thanks to the octapod shape, the resulting Pt-hosting network is mechanically trapped onto carbon nanotube buckypaper, providing mechanically flexible and binder-free electrodes. We found that such hierarchical configuration maximizes the mass activity and the utilization efficiency of Pt for the hydrogen evolution reaction (HER). At a potential of -0.15 V vs. reversible hydrogen electrode, the Pt/octapod network-based electrodes display a Pt mass activity on the HER of 166 A mg-1 and 42 A mg-1 in acidic and alkaline media, respectively. These values correspond to turnover frequencies of 168 s-1 and 42 s-1, respectively, which are in that order 14 and 21 times higher compared to commercially available Pt/C benchmarks. The strong chemical and mechanical interactions between the Pt and the octapod surface, along with pod-aided adhesion of the Pt/octapod network to the buckypaper, result in a long-term durability (>20 h) of the HER-activity in both media. These results experimentally prove that the exploitation of our network of branched nanocrystals hosting Pt particles can circumvent the durability issues of the catalysts while adopting either ultralow Pt loadings or benchmarking carbon-supported Pt nanocrystals. Our work opens up prospects for using porous networks made by branched nanocrystals as catalysts with ultralow amount of noble metals and controlled catalytic properties.

Copper binary compounds are often intrinsic p-type semiconductors due to the presence of Cu(I) vacancies, with corresponding hole carriers in the valence band. If the free carrier concentration is high enough, localized plasmon resonances can be sustained in nanocrystals, with frequencies in the infra-red (<1 eV), with respect to the typical resonances seen in the visible range in the case of metals (Ag, Au, ...). The localization of the resonances can be demonstrated with scanning transmission electron energy loss spectroscopy (STEM-EELS) by combining high spatial and high energy resolutions. Here we demonstrate that Cu(I) vacancies can be directly measured from the STEM images in Cu(3-x)P hexagonal nanocrystals. Two localized resonances can be seen from STEM-EELS, which are in agreement with the resonances calculated from the vacancy concentration obtained from the STEM., Comment: 10 pages, 3 figures

We study the nature of photo-excited charge carriers in CsPbBr3 nanocrystal thin films by ultrafast optical pump - THz probe spectroscopy. We observe a deviation from a pure Drude dispersion of the THz dielectric response that is ascribed to the polaronic nature of carriers; a transient blueshift of observed phonon frequencies is indicative of the coupling between photogenerated charges and stretching-bending modes of the deformed inorganic sublattice, as confirmed by DFT calculations.

Excitonic 0D and 2D lead-halide perovskites have been recently developed and investigated as new materials for light generation. Here we report broadband (> 1 eV) emission from newly synthesised zero-dimensional (0D) lead-free colloidal Cs3Bi2I9 nanocrystals. We investigate the nature of their emissive states as well as the relative dynamics which are currently hotly debated. In particular, we find that the broadband emission is made by the coexistence of emissive excitons and sub-bandgap emissive trap-states. Remarkably, we observe evidence of enhanced Raman scattering from the ligands when attached to the nanocrystals surface, an effect that we preliminary attribute to strong exciton-ligands electronic coupling in these systems.

The ultrathin nature of two-dimensional monolayer semiconductors yields optoelectronic properties which are highly responsive to changes in free-carrier density, making it imperative to masterfully control their doping levels. We report a new photo-doping scheme that quasi-permanently dopes the monolayer MoS2 to extents competing with electrostatic gating. The photo-doping is achieved by coupling monolayer MoS2 with indium tin oxide nanocrystals that can store multiple electrons per nanocrystal after UV illumination. In the hybrid structure, the photo-generated valence band holes in the nanocrystals are filled by MoS2 electrons, photo-doping the MoS2 with holes. Reductions in carrier density by ~6x10^12 cm^-2 are observed, equivalent to the storage of ~40 electrons per nanocrystal. Long-range changes proliferating up to 40 micrometers away from the localized photodoping result from local bandstructure variations in MoS2. These studies reveal novel all-optical carrier density control in monolayer semiconductors, enabling remote-control of local charge density and innovative energy storage technologies.

The liquid-phase exfoliation (LPE) of black phosphorus (BP) is a strategic route for the large-scale production of phosphorene and few-layer BP (FL-BP) flakes. The exploitation of this exfoliated material in cutting-edge technologies, e.g., in flexible electronics and energy storage, is however limited by the fact that the LPE of BP is usually carried out at a high boiling point and in toxic solvents. In fact, the solvent residual is detrimental to device performance in real applications; thus, complete solvent removal is critical. Here, we tackle these issues by exfoliating BP in different low boiling-point solvents. Among these solvents, we find that acetone also provides a high concentration of exfoliated BP, leading to the production of FL-BP flakes with an average lateral size and thickness of c.a. 30 and 7 nm, respectively. The use of acetone to produce less defective few-layer BP flakes (FL-BPacetone) from bulk crystals is a straightforward process which enables the rapid preparation of homogeneous thin films thanks to the fast solvent evaporation. The ratio of edge to bulk atoms for the BP flakes here produced, combined with the use of low-boiling-point solvents for the exfoliation process suggests that these thin films are promising anodes for lithium-ion batteries. To this end, we tested Li-ion half cells with FL-BPacetone anodes achieving a reversible specific capacity of 480 mAh/g at a current density of 100 mA/g, over 100 charge/discharge cycles. Moreover, a reversible specific capacity of 345 mAh/g is achieved for the FL-BPacetone-based anode at a high current density (i.e., 1 A/g). These findings indicate that the FL-BPacetone-based battery is promising with regards to the design of fast charge/discharge devices. Overall, the presented process is a step forward toward the fabrication of phosphorene-based devices., Comment: 30 pages, 11 images

Core-shell CdSe/CdS nanocrystals are a very promising material for light emitting applications. Their solution-phase synthesis is based on surface-stabilizing ligands that makes them soluble in organic solvents, like toluene or chloroform. However, solubility of these materials in water provides many advantages, such as additional process routes and easier handling. So far, solubilization of CdSe/CdS nanocrystals in water that avoids detrimental effects on the luminescent properties, poses a major challenge. This work demonstrates how core-shell CdSe/CdS quantum dot-in-rods can be transferred into water using a ligand exchange method employing mercaptopropionic acid (MPA). Key to maintaining the light-emitting properties is an enlarged CdS rod diameter, which prevents potential surface defects formed during the ligand exchange from affecting the photophysics of the dot-in-rods. Films made from water-soluble dot-in-rods show amplified spontaneous emission (ASE) with a similar threshold (130 microJ/cm2) as the pristine material (115 microJ/cm2). To demonstrate feasibility for lasing applications, self-assembled micro lasers are fabricated via the coffee-ring effect that display single-mode operation and a very low threshold of around 10 microJ/cm2. The performance of these micro lasers is enhanced by the small size of MPA ligands, enabling a high packing density of the dot-in-rods., Comment: 20 pages, 4 figures, published paper with supporting information

In the past couple of decades, colloidal inorganic nanocrystals and, more specifically, semiconductor quantum dots have emerged as crucial materials for the development of nanoscience and nanotechnology, with applications in very diverse areas such as optoelectronics and biotechnology. Films made of inorganic NCs deposited on a substrate can be patterned by e-beam lithography, altering the structure of their capping ligands and thus allowing exposed areas to remain on the substrate while non-exposed areas are redispersed in a solvent, as in a standard lift-off process. This methodology can be described as a direct lithography process, since the exposure is performed directly on the material of interest, in contrast with conventional lithography which uses a polymeric resist as a mask for subsequent material deposition or etching. A few reports from the late 1990 and early 2000 used such direct lithography to fabricate electrical wires from metallic NCs. However, the poor conductivity obtained through this process hindered the widespread use of the technique. In the early 2010, the same method was used to define fluorescent patterns on QD films, allowing for further applications in biosensing. For the past 2 ,3 years, direct lithography on NC films with e-beams and X rays has gone through an important development as it has been demonstrated that it can tune further transformations on the NCs, leading to more complex patternings and opening a whole new set of possible applications., Comment: 21 pages, 8 figures

Degenerately doped semiconductor nanocrystals (NCs) are of recent interest to the NC community due to their tunable localized surface plasmon resonances (LSPRs) in the near infrared (NIR). The high level of doping in such materials with carrier densities in the range of 1021 cm^-3 leads to degeneracy of the doping levels and intense plasmonic absorption in the NIR. The lower carrier density in degenerately doped semiconductor NCs compared to noble metals enables LSPR tuning over a wide spectral range, since even a minor change of the carrier density strongly affects the spectral position of the LSPR. We focus on copper chalcogenide NCs and impurity doped metal oxide NCs as the most investigated alternatives to noble metals. We shed light on the structural changes upon LSPR tuning in vacancy doped copper chalcogenide NCs and deliver a picture for the fundamentally different mechanism of LSPR modification of impurity doped metal oxide NCs. We review on the peculiar optical properties of plasmonic degenerately doped NCs by highlighting the variety of different optical measurements and optical modeling approaches. These findings are merged in an exhaustive section on new and exciting applications based on the special characteristics that plasmonic semiconductor NCs bring along., Comment: 97 pages, 33 figures

We report the colloidal synthesis of strongly fluorescent CsPbBr3 perovskite nanowires (NWs) with rectangular section and with tuneable width, from 20 nm (exhibiting no quantum confinement, hence emitting in the green) down to around 3 nm (in the strong quan-tum-confinement regime, emitting in the blue), by introducing in the synthesis a short acid (octanoic acid or hexanoic acid) together with alkyl amines (octylamine and oleylamine). Temperatures below 70 {\deg}C promoted the formation of monodisperse, few unit cell thick NWs that were free from byproducts. The photoluminescence quantum yield of the NW samples went from 12% for non-confined NWs emitting at 524 nm to a maximum of 77% for the 5 nm diameter NWs emitting at 497 nm, down to 30% for the thinnest NWs (diameter ~ 3nm), in the latter sample most likely due to aggregation occurring in solution., Comment: 5 pages, 4 figures

The structural and compositional stabilities of two dimensional 2D Bi2Te3 and Bi2Se3 nanocrystals, produced by both colloidal synthesis and by liquid phase exfoliation, were studied by in situ transmission electron microscopy TEM during annealing at temperatures between 350 and 500 C. The sublimation process induced by annealing is structurally and chemically anisotropic and takes place through the preferential dismantling of the prismatic 011-0 type planes, and through the preferential sublimation of Te or Se., Comment: 23 pages, 5 figures, May 27, 2016 Letter pubs.acs.org/NanoLett Nano Letters, May 27, 2016

Cu2-xTe nanocubes were used as starting seeds to access metal telluride nanocrystals by cation exchanges at room temperature. The coordination number of the entering cations was found to play an important role in dictating the reaction pathways. The exchanges with tetrahedrally coordinated cations (i.e. with coordination number 4), such as Cd2+ or Hg2+, yielded monocrystalline CdTe or HgTe nanocrystals with Cu2-xTe/CdTe or Cu2-xTe/HgTe Janus-like heterostructures as intermediates. The formation of Janus-like architectures was attributed to the high diffusion rate of the relatively small tetrahedrally coordinated cations, which could rapidly diffuse in the Cu2-xTe NCs and nucleate the CdTe (or HgTe) phase in a preferred region of the host structure. Also, with both Cd2+ and Hg2+ ions the exchange led to wurtzite CdTe and HgTe phases rather than the more stable zinc-blende ones, indicating that the anion framework of the starting Cu2- xTe particles could be more easily deformed to match the anion framework of the metastable wurtzite structures. As hexagonal HgTe had never been reported to date, this represents another case of metastable new phases that can only be accessed by cation exchange. On the other hand, the exchanges involving octahedrally coordinated ions (i.e. with coordination number 6), such as Pb2+ or Sn2+, yielded rock-salt polycrystalline PbTe or SnTe nanocrystals with Cu2-xTe@PbTe or Cu2-xTe@SnTe core@shell architectures at the early stages of the exchange process. In this case, the octahedrally coordinated ions are probably too large to diffuse easily through the Cu2-xTe structure: their limited diffusion rate restricts their initial reaction to the surface of the nanocrystals, where cation exchange is initiated unselectively, leading to core@shell architectures., Comment: 11 pages, 7 figures in J. Am. Chem. Soc, 13 May 2016