Selective cation exchange in the core region of Cu2-xSe/Cu2-xS core/shell nanocrystals.

We studied cation exchange (CE) in core/shell Cu2-xSe/Cu2-xS nanorods with two cations, Ag(+) and Hg(2+), which are known to induce rapid exchange within metal chalcogenide nanocrystals (NCs) at room temperature. At the initial stage of the reaction, the guest ions diffused through the Cu2-xS shell and reached the Cu2-xSe core, replacing first Cu(+) ions within the latter region. These experiments prove that CE in copper chalcogenide NCs is facilitated by the high diffusivity of guest cations in the lattice, such that they can probe the whole host structure and identify the preferred regions where to initiate the exchange. For both guest ions, CE is thermodynamically driven as it aims for the formation of the chalcogen phase characterized by the lower solubility under the specific reaction conditions.

Nanocrystal film patterning by inhibiting cation exchange via electron-beam or X-ray lithography.

In this Letter we report patterning of colloidal nanocrystal films that combines direct e-beam (electron beam) writing with cation exchange. The e-beam irradiation causes cross-linking of the ligand molecules present at the nanocrystal surface, and the cross-linked molecules act as a mask for further processing. Consequently, in the following step of cation exchange, which is performed by directly dipping the substrate in a solution containing the new cations, the regions that have not been exposed to the electron beam are chemically transformed, while the exposed ones remain unchanged. This selective protection allows the design of patterns that are formed by chemically different nanocrystals, yet in a homogeneous nanocrystal film. Spatially resolved compositional analysis by energy-dispersive X-ray spectroscopy (EDS) corroborates that the selective exchange occurs only in the nonirradiated regions. We demonstrate the utility of this lithography approach by fabricating conductive wires and luminescent patterns in CdSe/CdS nanocrystal films by converting nonirradiated regions to Cu2-xSe/Cu2-xS. Furthermore, we show that X-ray irradiation too can lead to protection from cation exchange.

Self-assembly of octapod-shaped colloidal nanocrystals into a hexagonal ballerina network embedded in a thin polymer film.

Nanoparticles with unconventional shapes may exhibit different types of assembly architectures that depend critically on the environmental conditions under which they are formed. Here, we demonstrate how the presence of polymer (polymethyl methacrylate, PMMA) molecules in a solution, in which CdSe(core)/CdS(pods) octapods are initially dispersed, affects the octapod-polymer organization upon solvent evaporation. We show that a fast drop-drying process can induce a remarkable two-dimensional (2D) self-assembly of octapods at the polymer/air interface. In the resulting structure, each octapod is oriented like a "ballerina", that is, only one pod sticks out of the polymer film and is perpendicular to the polymer-air interface, while the opposite pod (with respect to the octapod's center) is fully immersed in the film and points toward the substrate, like a ballerina performing a grand battement. In some areas, a hexagonal-like pattern is formed by the ballerinas in which the six nonvertical pods, which are all embedded in the film, maintain a pod-pod parallel configuration with respect to neighboring particles. We hypothesize that the mechanism responsible for such a self-assembly is based on a fast adsorption of the octapods from bulk solution to the droplet/air interface during the early stages of solvent evaporation. At this interface, the octapods maintain enough rotational freedom to organize mutually in a pod-pod parallel configuration between neighboring octapods. As the solvent evaporates, the octapods form a ballerina-rich octapod-polymer composite in which the octapods are in close contact with the substrate. Finally, we found that the resulting octapod-polymer composite is less hydrophilic than the polymer-only film.

Hollow and concave nanoparticles via preferential oxidation of the core in colloidal core/shell nanocrystals.

Hollow and concave nanocrystals find applications in many fields, and their fabrication can follow different possible mechanisms. We report a new route to these nanostructures that exploits the oxidation of Cu(2-x)Se/Cu(2-x)S core/shell nanocrystals with various etchants. Even though the Cu(2-x)Se core is encased in a thick Cu(2-x)S shell, the initial effect of oxidation is the creation of a void in the core. This is rationalized in terms of diffusion of Cu(+) ions and electrons from the core to the shell (and from there to the solution). Differently from the classical Kirkendall effect, which entails an imbalance between in-diffusion and out-diffusion of two different species across an interface, the present mechanism can be considered as a limiting case of such effect and is triggered by the stronger tendency of Cu(2-x)Se over Cu(2-x)S toward oxidation and by fast Cu(+) diffusion in copper chalcogenides. As the oxidation progresses, expansion of the inner void erodes the entire Cu(2-x)Se core, accompanied by etching and partial collapse of the shell, yielding Cu(2-x)S(y)Se(1-y) concave particles.

Copper sulfide nanocrystals with tunable composition by reduction of covellite nanocrystals with Cu+ ions.

Platelet-shaped copper sulfide nanocrystals (NCs) with tunable Cu stoichiometry were prepared from Cu-rich covellite (Cu1.1S) nanoplates through their reaction with a Cu(I) complex ([Cu(CH3CN)4]PF6) at room temperature. Starting from a common sample, by this approach it is possible to access a range of compositions in these NCs, varying from Cu1.1S up to Cu2S, each characterized by a different optical response: from the metallic covellite, with a high density of free carriers and strong localized surface plasmon resonance (LSPR), up to Cu2S NCs with no LSPR. In all these NCs the valency of Cu in the lattice stays always close to +1, while the average -1 valency of S in covellite gradually evolves to -2 with increasing Cu content; i.e., sulfur is progressively reduced. The addition of copper to the starting covellite NCs is similar to the intercalation of metal species in layered transition metal dichalcogenides (TMDCs); i.e., the chalcogen-chalcogen bonds holding the layers are progressively broken to make room for the intercalated metals, while their overall anion sublattice does not change much. However, differently from the TMDCs, the intercalation in covellite NCs is sustained by a change in the redox state of the anion framework. Furthermore, the amount of Cu incorporated in the NCs upon reaction is associated with the formation of an equimolar amount of Cu(II) species in solution. Therefore, the reaction scheme can be written as: Cu1.1S + 2γCu(I) → Cu1.1+γS + γCu(II).

Hierarchical self-assembly of suspended branched colloidal nanocrystals into superlattice structures.

Self-assembly of molecular units into complex and functional superstructures is ubiquitous in biology. The number of superstructures realized by self-assembly of man-made nanoscale units is also growing. However, assemblies of colloidal inorganic nanocrystals are still at an elementary level, not only because of the simplicity of the shape of the nanocrystal building blocks and their interactions, but also because of the poor control over these parameters in the fabrication of more elaborate nanocrystals. Here, we show how monodisperse colloidal octapod-shaped nanocrystals self-assemble, in a suitable solution environment, on two sequential levels. First, linear chains of interlocked octapods are formed, and subsequently the chains spontaneously self-assemble into three-dimensional superstructures. Remarkably, all the instructions for the hierarchical self-assembly are encoded in the octapod shape. The mechanical strength of these superstructures is improved by welding the constituent nanocrystals together.

Plasmon dynamics in colloidal Cu2-xSe nanocrystals.

The optical response of metallic nanostructures after intense excitation with femtosecond-laser pulses has recently attracted increasing attention: such response is dominated by ultrafast electron-phonon coupling and offers the possibility to achieve optical modulation with unprecedented terahertz bandwidth. In addition to noble metal nanoparticles, efforts have been made in recent years to synthesize heavily doped semiconductor nanocrystals so as to achieve a plasmonic behavior with spectrally tunable features. In this work, we studied the dynamics of the localized plasmon resonance exhibited by colloidal Cu(2-x)Se nanocrystals of 13 nm in diameter and with x around 0.15, upon excitation by ultrafast laser pulses via pump-probe experiments in the near-infrared, with ∼200 fs resolution time. The experimental results were interpreted according to the two-temperature model and revealed the existence of strong nonlinearities in the plasmonic absorption due to the much lower carrier density of Cu(2-x)Se compared to noble metals, which led to ultrafast control of the probe signal with modulation depth exceeding 40% in transmission.

Reversible tunability of the near-infrared valence band plasmon resonance in Cu(2-x)Se nanocrystals.

We demonstrate that colloidal Cu(2-x)Se nanocrystals exhibit a well-defined infrared absorption band due to the excitation of positive charge carrier oscillations (i.e., a valence band plasmon mode), which can be tuned reversibly in width and position by varying the copper stoichiometry. The value of x could be incrementally varied from 0 (no plasmon absorption, then a broad peak at 1700 nm) to 0.4 (narrow plasmon band at 1100 nm) by oxidizing Cu(2)Se nanocrystals (upon exposure either to oxygen or to a Ce(IV) complex), and it could be incrementally restored back to zero by the addition of a Cu(I) complex. The experimentally observed plasmonic behavior is in good agreement with calculations based on the electrostatic approximation.

Steady-state photoinduced absorption of CdSe/CdS octapod shaped nanocrystals.

Colloidal branched nanocrystals have been attracting increasing attention due to evidence of an interesting relationship between their complex shape and charge carrier dynamics. Herein, continuous wave photoinduced absorption (CW PIA) measurements of CdSe/CdS octapod-shaped nanocrystals are reported. CW PIA spectra show strong bleaching due to the one-dimensional (1D) CdS pod states (480 nm) and the zero-dimensional (0D) CdSe core states (690 nm). The agreement with previously reported ultrafast pump-probe experiments indicates that this strong bleaching signal may be assigned to state filling. Additional bleaching features at 520 and 560 nm are characterized by a longer lifetime and are thus ascribed to defect states, localized at the pod-core interface of the octapod, showing that some of the initially photogenerated carriers get quickly trapped into these long-lived defect states. However, we remark that a relevant part of electrons remain untrapped: this opens up the opportunity to exploit octapod shaped nanocrystals in photovoltaics applications, as electron acceptor materials, considering that several efficient hole extracting materials are already available for the realization of a composite bulk heterojunction.

Octapod-shaped colloidal nanocrystals of cadmium chalcogenides via "one-pot" cation exchange and seeded growth.

The growth behavior of cadmium chalcogenides (CdE = CdS, CdSe, and CdTe) on sphalerite Cu(2-x)Se nanocrystals (size range 10-15 nm) is studied. Due to the capability of Cu(2-x)Se to undergo a fast and quantitative cation exchange reaction in the presence of excessive Cd(2+) ions, no Cu(2-x)Se/CdE heterostructures are obtained and instead branched CdSe/CdE nanocrystals are built which consist of a sphalerite CdSe core and wurtzite CdE arms. While CdTe growth yields multiarmed structures with overall tetrahedral symmetry, CdS and CdSe arm growth leads to octapod-shaped nanocrystals. These results differ significantly from literature findings about the growth of CdE on sphalerite CdSe particles, which until now had always yielded tetrapod-shaped nanocrystals.

Phosphine-free synthesis of p-type copper(I) selenide nanocrystals in hot coordinating solvents.

We report a phosphine-free synthesis of p-type copper(I) selenide nanocrystals by a colloidal approach in a mixture of oleylamine and 1-octadecene. The nanocrystals had a cuboctahedral shape and cubic berzelianite phase. Films of these nonstoichiometric copper-deficient Cu(2-x)Se nanocrystals were highly conductive and showed high absorption coefficient in the near-infrared region. These nanocrystals could be used as hole-injection layers in optoelectronic devices.

Reconfigurable Printed Liquids.

Liquids lack the spatial order required for advanced functionality. Interfacial assemblies of colloids, however, can be used to shape liquids into complex, 3D objects, simultaneously forming 2D layers with novel magnetic, plasmonic, or structural properties. Fully exploiting all-liquid systems that are structured by their interfaces would create a new class of biomimetic, reconfigurable, and responsive materials. Here, printed constructs of water in oil are presented. Both form and function are given to the system by the assembly and jamming of nanoparticle surfactants, formed from the interfacial interaction of nanoparticles and amphiphilic polymers that bear complementary functional groups. These yield dissipative constructs that exhibit a compartmentalized response to chemical cues. Potential applications include biphasic reaction vessels, liquid electronics, novel media for the encapsulation of cells and active matter, and dynamic constructs that both alter, and are altered by, their external environment.

Cold field emission dominated photoconductivity in ordered three-dimensional assemblies of octapod-shaped CdSe/CdS nanocrystals.

Semiconductor nanocrystals, especially their ordered assemblies, are promising materials for various applications. In this paper, we investigate the photoconductive behavior of sub-micron size, ordered three-dimensional (3D) assemblies of octapod-shaped CdSe/CdS nanocrystals that are contacted by overlay electron-beam lithography. The regular structure of the assemblies leads to photocurrent-voltage curves that can be described by the cold field electron emission model. Mapping of the photoconductivity versus excitation wavelength and bias voltage allows the extraction of the band gap and identification of the photoactive region in the voltage and spectral domain. These results have important implications for the understanding of photoconductive transport in similar systems.

Compression stiffness of porous nanostructures from self-assembly of branched nanocrystals.

The novelty and potential of self-assembled superstructures reside not only in the more commonly investigated optical, magnetic and charge transport properties, but also in their mechanical behaviour, which is strictly dependent on their structural morphology. We report here nanocompression tests on highly porous, geometrically interlocked superstructures fabricated by self-assembly of colloidal CdSe/CdS octapod shaped nanocrystals. We show that, despite being formed via weak van der Waals forces, these superstructures present an elastic response similar to that of porous materials and indeed were found to be modelled fittingly by classical open-cell models. The simple model based on the relative density of the superstructures holds also when the chemical composition of the superstructures is modified by processes such as cation exchange of Cd(2+) with Cu(+) and oxygen plasma treatment.

Influence of chloride ions on the synthesis of colloidal branched CdSe/CdS nanocrystals by seeded growth.

We studied the influence of chloride ions (Cl(-)), introduced as CdCl(2), on the seeded growth synthesis of colloidal branched CdSe(core)/CdS(pods) nanocrystals. This is carried out by growing wurtzite CdS pods on top of preformed octahedral sphalerite CdSe seeds. When no CdCl(2) is added, the synthesis of multipods has a low reproducibility, and the side nucleation of CdS nanorods is often observed. At a suitable concentration of CdCl(2), octapods are formed and they are stable in solution during the synthesis. Our experiments indicate that Cl(-) ions introduced in the reaction reduce the availability of Cd(2+) ions in solution, most likely via formation of strong complexes with both Cd and the various surfactants. This prevents homogeneous nucleation of CdS nanocrystals, so that the heterogeneous nucleation of CdS pods on top of the CdSe seeds is the preferred process. Once such optimal concentration of CdCl(2) is set for a stable growth of octapods, the pod lengths can be tuned by varying the relative ratios of the various alkyl phosphonic acids used. Furthermore, at higher concentrations of CdCl(2) added, octapods are initially formed, but many of them evolve into tetrapods over time. This transformation points to an additional role of Cl species in regulating the growth rate and stability of various crystal facets of the CdS pods.

Cation exchange reactions in colloidal branched nanocrystals.

Octapod-shaped colloidal nanocrystals composed of a central "core" region of cubic sphalerite CdSe and pods of hexagonal wurtzite CdS are subject to a cation exchange reaction in which Cd(2+) ions are progressively exchanged by Cu(+) ions. The reaction starts from the tip regions of the CdS pods and proceeds toward the center of the nanocrystals. It preserves both the shape and the anionic lattices of the heterostructures. During the exchange, the hexagonal wurtzite CdS pods are converted gradually into pods of hexagonal Cu(2)S chalcocite. Therefore, the partial cation exchange reactions lead to the formation of a ternary nanostructure, consisting of an octapod in which the central core is still CdSe, while the pods have a segmented CdS/Cu(2)S composition. When the cation exchange reaches the core, the cubic sphalerite CdSe core is converted into a core of cubic Cu(2-x)Se berzelianite phase. Therefore fully exchanged octapods are composed of a core of Cu(2-x)Se and eight pods of Cu(2)S. All these structures are stable, and the epitaxial interfaces between the various domains are characterized by low lattice mismatch. The Cu(2-x)Se(core)/Cu(2)S(pods) octapod represents another example of a nanostructure in which branching is achieved by proper organization of cubic and hexagonal domains in a single nanocrystal.

Spatially resolved photoconductivity of thin films formed by colloidal octapod-shaped CdSe/CdS nanocrystals.

We studied the optical absorption and photoconductive properties of thin films consisting of core-shell octapod-shaped nanocrystals, which consisted of CdS pods that branch out from a CdSe core. The current-voltage characteristics were measured at room and cryogenic temperatures and agreed well with a phenomenological exponential fitting model, from which we could extract the sheet resistance and the average voltage barrier for the charge tunneling between the octapods. The temperature dependence of the photocurrent showed temperature activated behavior above 220 K and a non-Arrhenius exponential (T/T(0))(n) dispersion below 220 K. Furthermore, we mapped the photocurrent generation within the octapod film via scanning photocurrent microscopy, which revealed photocurrent enhancement near micron-size voids and spatial shifts of the photocurrent maxima with bias voltage.