Mapping Charge Distribution in Single PbS Core - CdS Arm Nano-Multipod Heterostructures by Off-Axis Electron Holography.

We synthesized PbS core-CdS arm nanomultipod heterostructures (NMHs) that exhibit PbS{111}/CdS{0002} epitaxial relations. The PbS-CdS interface is chemically sharp as determined by aberration corrected transmission electron microscopy (TEM) and compared to density functional theory (DFT) calculations. Ensemble fluorescence measurements show quenching of the optical signal from the CdS arms indicating charge separation due to the heterojunction with PbS. A finite-element three-dimensional (3D) calculation of the Poisson equation shows a type-I heterojunction, which would prevent recombination in the CdS arm after optical excitation. To examine charge redistribution, we used off-axis electron holography (OAEH) in the TEM to map the electrostatic potential across an individual heterojunction. Indeed, a built-in potential of 500 mV is estimated across the junction, though as opposed to the thermal equilibrium calculations significant accumulation of positive charge at the CdS side of the interface is detected. We conclude that the NMH multipod geometry prevents efficient removal of generated charge carriers by the high energy electrons of the TEM. Simulations of generated electron-hole pairs in the insulated CdS arm of the NMH indeed show charge accumulation in agreement with the experimental measurements. Thus, we show that OAEH can be used as a complementary methodology to ensemble measurements by mapping the charge distribution in single NMHs with complex geometries.

Surface plasmon resonance in surfactant coated copper sulfide nanoparticles: Role of the structure of the capping agent.

HYPOTHESIS: The optical properties of as-synthesized CuS nanoparticles are affected by shape, size and morphology and exhibit increased optical absorbance in the infrared range due to localized surface plasmon resonance (LSPR), which is also affected by these parameters. An additional parameter which affects the LSPR-related absorbance is crystallinity of the surfactant coating. EXPERIMENTS: CuS nanoparticles with varying morphologies were synthesized using a single source, single surfactant/solvent route. Thereafter, the particles were heat treated at temperatures varying from 130 °C to 230 °C with and without protective environment. Prior to and following the treatments, the particles were characterized using various techniques. Additionally, temperature resolved structural study and thermal analysis of the surfactant coating were performed. FINDINGS: We confirm that the previously reported effects of particle dimensions and chemical composition on LSPR apply for the synthesized particles. Moreover, we report an additional, previously unreported effect, connecting the crystal structure of the nanoparticle surfactant coating to LSPR. This in turn allows control over LSPR peak position by varying the degree of crystallinity of the capping surfactant layer. Thermal study of the surfactant coating showed gradual structural transition and high dependence of phase transformation on atmospheric environment during treatment.

New nanocrystalline materials: a previously unknown simple cubic phase in the SnS binary system.

We report a new phase in the binary SnS system, obtained as highly symmetric nanotetrahedra. Due to the nanoscale size and minute amounts of these particles in the synthesis yield, the structure was exclusively solved using electron diffraction methods. The atomic model of the new phase (a = 11.7 Å, P2(1)3) was deduced and found to be associated with the rocksalt-type structure. Kramers-Kronig analysis predicted different optical and electronic properties for the new phase, as compared to α-SnS.

Time, illumination and solvent dependent stability of cadmium sulfide nanoparticle suspensions.

HYPOTHESIS: The optical properties of cadmium sulfide (CdS) nanoparticles in suspension are affected by morphology and suspending solvent. Time dependent stability of these properties is solvent dependent and is affected by illumination conditions under which the suspension is stored. Moreover, minute amounts of dissolved oxygen are sufficient in order to facilitate photodegradation. EXPERIMENTS: CdS nanoparticles were synthesized with various shapes using a single precursor, single surfactant route. Thereafter, their optical properties were measured from chloroform and toluene suspensions following periods of up to 4 months, under illumination conditions, which included dark storage, visible light and UV irradiation. FINDINGS: The changes in optical properties, best shown by the photoluminescence (PL), reveal an intricate behavior, which is dependent upon both the chemical environment and illumination conditions. This is mainly manifested in two ways: the first is an initial intensification of the PL, while later on gradual degradation of the particles and their optical activity are observed. Moreover, a distinct variation of surface state emission was demonstrated for each solvent. Additionally, a solvent dependent variation of the final photodegraded state was observed. Based on these observations, we describe the photodegradation route for CdS nanoparticles in chloroform suspensions.

Directed coassembly of oriented PbS nanoparticles and monocrystalline sheets of alkylamine surfactant.

We demonstrate control over the orientation of PbS nanoparticles by way of directed assembly, which in turn affects the crystal structure of alkylamine surfactants such as octadecylamine (ODA, C(18)H(37)NH(2)) and hexadecylamine (HDA, C(16)H(33)NH(2)). This directed assembly method results in the arrangement of PbS nanoparticles with a well-defined epitaxial orientation on lamellar alkylamine sheets, which undertake a new crystal structure to accommodate these relations. Understanding these surfactant-nanoparticle inter-relations is very instrumental in understanding surfactant-assisted nanoparticle synthesis and assembly.

Hierarchical superstructure of alkylamine-coated ZnS nanoparticle assemblies.

We describe methodology for producing highly uniform, ordered and reproducible superstructures of surfactant-coated ZnS nanorod and nanowire assemblies, and propose a predictive multiscale "packing model" for superstructure formation based on electron microscopy and powder X-ray diffraction data on the superstructure, as well as on individual components of the nanostructured system. The studied nanoparticles showed a hierarchical structure starting from the individual faceted ZnS inorganic cores, onto which the crystalline surfactant molecules are adsorbed, to the superstructure of the nanoparticle arrays. Our results point out the critical role of the surfactant headgroup and polarity in nanoparticle assembly, and demonstrate the relationship between the molecular structure of the surfactant and the resulting superstructure of the nanoparticle assemblies.