Tuning and Locking the Localized Surface Plasmon Resonances of CuS (Covellite) Nanocrystals by an Amorphous CuPdxS Shell

[Image: see text] We demonstrate the stabilization of the localized surface plasmon resonance (LSPR) in a semiconductor-based core–shell heterostructure made of a plasmonic CuS core embedded in an amorphous-like alloyed CuPd(x)S shell. This heterostructure is prepared by reacting the as-synthesized CuS nanocrystals (NCs) with Pd(2+) cations at room temperature in the presence of an electron donor (ascorbic acid). The reaction starts from the surface of the CuS NCs and proceeds toward the center, causing reorganization of the initial lattice and amorphization of the covellite structure. According to density functional calculations, Pd atoms are preferentially accommodated between the bilayer formed by the S–S covalent bonds, which are therefore broken, and this can be understood as the first step leading to amorphization of the particles upon insertion of the Pd(2+) ions. The position and intensity in near-infrared LSPRs can be tuned by altering the thickness of the shell and are in agreement with the theoretical optical simulation based on the Mie–Gans theory and Drude model. Compared to the starting CuS NCs, the amorphous CuPd(x)S shell in the core–shell nanoparticles makes their plasmonic response less sensitive to a harsh oxidation environment (generated, for example, by the presence of I(2))

Raman spectroscopy and strain mapping in individual Ge-SixGe1-x core-shell nanowires

Core-shell Ge-SixGe1-x nanowires (NWs) are expected to contain large strain fields due to the lattice-mismatch at the core/shell interface. Here we report the measurement of core strain in a NW heterostructure using Raman spectroscopy. We compare the Raman spectra, and the frequency of the Ge-Ge mode measured in individual Ge-Si0.5Ge0.5 core-shell, and bare Ge NWs. We find that the Ge-Ge mode frequency is diameter-independent in GeNWs with a value similar to that of bulk Ge, 300.5 cm-1. On the other hand, Ge-Si0.5Ge0.5 core-shell nanowires reveal a strain-induced blue shift of the Ge-Ge mode, dependent on the relative core and shell thicknesses. Using lattice dynamical theory we determine the strain in the Ge core, and show that the results are in good agreement with values calculated using a continuum elasticity model.Comment: 9 pages, 5 figure

Pushing indium phosphide quantum dot emission deeper into the near infrared

Cadmium-free near infrared (NIR) emitting quantum dots (QDs) have significant potential for multiplexed tissue-depth imaging applications in the first optical tissue window (i.e., 650 – 900 nm). Indium phosphide (InP) chemistry provides one of the more promising cadmium-free options for biomedical imaging, but the full tunability of this material has not yet been achieved. Specifically, InP QD emission has been tuned from 480 – 730 nm in previous literature reports, but examples of samples emitting from 730 nm to the InP bulk bandgap limit of 925 nm are lacking. We hypothesize that by generating inverted structures comprising ZnSe/InP/ZnS in a core/shell/shell heterostructure, optical emission from the InP shell can be tuned by changing the InP shell thickness, including pushing deeper into the NIR than current InP QDs. Colloidal synthesis methods including hot injection precipitation of the ZnSe core and a modified successive ion layer adsorption and reaction (SILAR) method for stepwise shell deposition were used to promote growth of core/shell/shell materials with varying thicknesses of the InP shell. By controlling the number of injections of indium and phosphorous precursor material, the emission peak was tuned from 515 nm to 845 nm (2.41 – 1.47 eV) with consistent full width half maximum (FWHM) values of the emission peak ~0.32 eV. To confer water solubility, the nanoparticles were encapsulated in PEGylated phospholipid micelles, and multiplexing of NIR-emitting InP QDs was demonstrated using an IVIS imaging system. These materials show potential for multiplexed imaging of targeted QD contrast agents in the first optical tissue window

Surface plasmon and photonic mode propagation in gold nanotubes with varying wall thickness

Gold nanotube arrays are synthesized with a range of wall thicknesses (15 to >140 nm) and inner diameters of ∼200 nm using a hard-template method. A red spectral shift (>0.39 eV) with decreasing wall thickness is observed in dark-field spectra of nanotube arrays and single nanowire/nanotube heterostructures. Finite-difference-time-domain simulations show that nanotubes in this size regime support propagating surface plasmon modes as well as surface plasmon ring resonances at visible wavelengths (the latter is observed only for excitation directions normal to the nanotube long axis with transverse polarization). The energy of the surface plasmon modes decreases with decreasing wall thickness and is attributed to an increase in mode coupling between propagating modes in the nanotube core and outer surface and the circumference dependence of ring resonances. Surface plasmon mode propagation lengths for thicker-walled tubes increase by a factor of ∼2 at longer wavelengths (>700 nm), where ohmic losses in the metal are low, but thinner-walled tubes (30 nm) exhibit a more significant increase in surface plasmon propagation length (by a factor of more than four) at longer wavelengths. Additionally, nanotubes in this size regime support a photonic mode in their core, which does not change in energy with changing wall thickness. However, photonic mode propagation length is found to decrease for optically thin walls. Finally, correlations are made between the experimentally observed changes in dark-field spectra and the changes in surface plasmon mode properties observed in simulations for the various gold nanotube wall thicknesses and excitation conditions

Interfacial confinement in core-shell nanowires due to high dielectric mismatch

We theoretically investigate the role of the dielectric mismatch between materials on the energy levels and recombination energies of a core-shell nanowire. Our results demonstrate that when the dielectric constant of the core material is lower than that of the shell material, the self-image potential pushes the charge carriers towards the core-shell interface, in such a way that the ideal confinement model is no longer suitable. The effects of this interfacial confinement on the electronic properties of such wires, as well as on its response to applied magnetic fields, are discussed.Comment: 4 pages, 3 figures and 1 material Supplementary; Applied Physics Letters 201

Gold-free GaAs/GaAsSb heterostructure nanowires grown on silicon

Growth of GaAs/GaAsSb heterostructurenanowires on silicon without the need for gold seed particles is presented. A high vertical yield of GaAsnanowires is first obtained, and then GaAsₓSb₁ˍₓ segments are successfully grown axially in these nanowires. GaAsSb can also be integrated as a shell around the GaAs core. Finally, two GaAsSb segments are grown inside a GaAsnanowire and passivated using an AlₓGa₁ˍₓAs shell. It is found that no stacking faults or twin planes occur in the GaAsSb segments.Part of this work was funded by the Swedish Foundation for Strategic Research SSF, the Swedish Research Council VR, and the Knut and Alice Wallenberg Foundation

The inter-sublevel optical properties of a spherical quantum dot-quantum well with and without a donor impurity

In this study, we have investigated the inter-sublevel optical properties of a core/shell/well/shell spherical quantum dot with the form of quantum dot-quantum well heterostructure. In order to determine the energy eigenvalues and corresponding wave functions, the Schr\"{o}dinger equation has been solved full numerically by using shooting method in the effective mass approximation for a finite confining potential. The inter-sublevel optical absorption and the oscillator strength between ground ($1s$) and excited ($1p$) states have been examined based on the computed energies and wave functions. Also, the effect of a hydrogenic donor impurity, located at the center of the multi-shell spherical quantum dot (MSQD), has been researched for different core radii ($R_1$), shell thicknesses ($T_s$) and well widths ($T_w$) in certain potential. It is observed that the oscillator strengths and the absorption coefficients are strongly depend on the core radii and layer thicknesses of the MSQD.Comment: 24 pages, 13 figure