Water-Soluble Lead Sulfide Nanoparticles: Direct Synthesis and Ligand Exchange Routes.

Colloidal semiconductor nanoparticles (NPs) represent an emergent state of matter with unique properties, bridging bulk materials and molecular structures. Their distinct physical attributes, such as bandgap and photoluminescence, are intricately tied to their size and morphology. Ligand passivation plays a crucial role in shaping NPs and determining their physical properties. Ligand exchange (LE) offers a versatile approach to tailoring NP properties, often guided by Pearson's Hard-Soft Acid-Base theory. Lead sulfide (PbS), a semiconductor of considerable interest, exhibits size-dependent tunable bandgaps from the infrared to the visible range. Here, we present two methods for synthesizing water-soluble, polyvinylpyrrolidone (PVP)-coated PbS NPs. The first involves direct synthesis in an aqueous solution while utilizing PVP as the surfactant for the formation of nano-cubes with a crystal coherence length of ~30 nm, while the second involves LE from octadecylamine-coated PbS truncated nano-cubes to PVP-coated PbS NPs with a crystal coherence length of ~15 nm. Multiple characterization techniques, including X-ray diffraction, transmission electron microscopy, Fourier-transform infrared spectroscopy, and thermal gravimetric analysis, confirmed the results of the synthesis and allowed us to monitor the ligand exchange process. Our findings demonstrate efficient and environmentally friendly approaches for synthesizing PVP-coated PbS NPs.

Entrapment of metastable nanocrystals by polyoxometalates.

Entirely inorganic polyoxometalate cluster-anion ligands are herein used to entrap and impart heat resistance to metastable metal-oxide based NCs. This is demonstrated by trapping 6-line ferrihydrite NCs that form as intermediates in the spontaneous conversion of ß-FeOOH to hematite (α-Fe2O3). The results suggest that polyoxometalate ligation may prove to be a general method for stabilizing metastable phases as the cores of entirely inorganic macro-anion like complexes.

MXene-Based Ceramic Nanocomposites Enabled by Pressure-Assisted Sintering.

As MXenes become increasingly widespread, approaches to utilize this versatile class of 2D materials are sought. Recently, there has been growing interest in incorporating MXenes into metal or ceramic matrices to create advanced nanocomposites. This study presents a facile approach of mixing MXene with ceramic particles followed by pressure-assisted sintering to produce bulk MXene/ceramic nanocomposites. The effect of MXene addition on the densification behavior and properties of nanocomposites was explored through the Ti3C2Tz/alumina model system. We discovered that the presence of MXene altered the densification behavior and significantly enhanced the densification rate at low temperatures. In-depth microstructural characterization showed a homogeneous distribution of Ti3C2Tz MXene at the alumina grain boundaries. The Ti3C2Tz/alumina nanocomposites exhibited electrical conductivity but reduced hardness. We also demonstrated that using multilayered Ti3C2Tz as a precursor can produce composites with plate-like TiCx morphology. This work provides a conceptual approach for utilizing the diversity and versatility of MXenes in creating tunable advanced nanocomposites.

The Non-Classical Crystallization Mechanism of a Composite Biogenic Guanine Crystal.

Spectacular colors and visual phenomena in animals are produced by light interference from highly reflective guanine crystals. Little is known about how organisms regulate crystal morphology to tune the optics of these systems. By following guanine crystal formation in developing spiders, a crystallization mechanism is elucidated. Guanine crystallization is a "non-classical," multistep process involving a progressive ordering of states. Crystallization begins with nucleation of partially ordered nanogranules from a disordered precursor phase. Growth proceeds by orientated attachment of the nanogranules into platelets which coalesce into single crystals, via progressive relaxation of structural defects. Despite their prismatic morphology, the platelet texture is retained in the final crystals, which are composites of crystal lamellae and interlamellar sheets. Interactions between the macromolecular sheets and the planar face of guanine appear to direct nucleation, favoring platelet formation. These findings provide insights on how organisms control the morphology and optical properties of molecular crystals.

Sample preparation induced phase transitions in solution deposited copper selenide thin films.

Thin films of CuSe were deposited onto GaAs substrate. XRD showed that the as-deposited films were of the Klockmannite (CuSe - P63/mmc 194) phase with lattice parameters a 0 = b 0 = 0.3939 nm, c 0 = 1.7250 nm; however, electron diffraction in the TEM surprisingly indicated the ß-Cu2-x Se phase (Cu1.95Se - R3̄m 166) with lattice parameters a 0 = b 0 = 0.412 nm, c 0 = 2.045 nm. The discrepancy originated from the specimen preparation method, where the energy of the focused ion beam resulted in loss of selenium which drives a phase transition to ß-Cu2-x Se in this system. The same phase transition was observed also upon thermal treatment in vacuum, as well as when the 200 keV electron beam was focused on a powder sample in the TEM. The initial phase can be controlled to some extent by changing the composition of the reactants in solution, resulting in thin films of the cubic α-Cu2-x Se (Cu1.95Se - Fm3̄m) phase co-existing together with the ß-Cu2-x Se phase.

Alloying copper and palladium nanoparticles by pulsed laser irradiation of colloids suspended in ethanol.

Nanoparticles (NPs) of copper, palladium and Cu0.8Pd0.2 alloy have been prepared by pulsed laser ablation/irradiation in ethanol, by the second harmonic of a pulsed Nd : YAG laser (532 nm, ∼5 ns, 10 Hz). The monometallic NPs were synthesized by laser ablation of pure bulk targets immersed in ethanol and the alloyed ones by laser irradiation of stirred mixtures of suspended monometallic colloids. The suspensions were irradiated through two distinctive configurations, including lateral collimated and top focused beams that reached the corresponding fluences for NPs vaporization and for extensive plasma formation. The generated NPs were characterized by ultraviolet-visible absorption spectrometry, low and high-resolution transmission electron microscopy, energy-dispersive spectroscopy and selected area electron diffraction. The first fluence regime afforded the synthesis of alloyed NPs in the few nm diameter range, where alloying was somewhat disturbed by agglomeration, while the second led to larger size NPs and faster alloying, due to laser scattering by the plasma. These findings were supported and interpreted by the particle heating-melting-evaporation model. The approach developed here, assisted by the model and the various characterization methods, proved to control the alloying process and the size distribution of the NPs and to give the best indication for its progress.

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.

Nanostructure synthesis at the solid-water interface: spontaneous assembly and chemical transformations of tellurium nanorods.

Bottom-up synthesis offers novel routes to obtain nanostructures for nanotechnology applications. Most self-assembly processes are carried out in three dimensions (i.e. solutions); however, the large majority of nanostructure-based devices function in two dimensions (i.e. on surfaces). Accordingly, an essential and often cumbersome step in bottom-up applications involves harvesting and transferring the synthesized nanostructures from the solution onto target surfaces. We demonstrate a simple strategy for the synthesis and chemical transformation of tellurium nanorods, which is carried out directly at the solid-solution interface. The technique involves binding the nanorod precursors onto amine-functionalized surfaces, followed by in situ crystallization/oxidation. We show that the surface-anchored tellurium nanorods can be further transformed in situ into Ag2Te, Cu2Te, and SERS-active Au-Te nanorods. This new approach offers a way to construct functional nanostructures directly on surfaces.

Transparent, conductive gold nanowire networks assembled from soluble Au thiocyanate.

Extremely long gold nanowires spontaneously assemble in a water-dimethylsulfoxide (DMSO) solution of Au(SCN)4(-). The Au nanowires were crystalline, exhibited a very high aspect ratio, and, importantly, were produced without co-addition of reducing agents. Transparent conductive films were formed by surface deposition of the nanowires and plasma treatment.

Nanometer size effects in nucleation, growth and characterization of templated CdS nanocrystal assemblies.

We report on the oriented nucleation of CdS nanocrystals on well-defined polydiacetylene Langmuir film templates. Nucleation on the red phase of polydiacetylene resulted in ordered linear arrays of CdS nanocrystals that are aligned with respect to the template. High resolution transmission electron microscopy showed crystalline particles of ~5 to 8 nm size. Selected area electron diffraction micrographs showed spot patterns which are attributed to the well-defined orientations of both polymorphs: the cubic zinc blende and the hexagonal wurtzite polymorphs of CdS. We present a unique growth mechanism where oriented nucleation of CdS on the polydiacetylene template initially takes place in the zinc blende phase. Beyond a certain size threshold, growth proceeds in the more stable wurtzite phase. This transformation keeps the stacking direction of the close packed planes, while altering only their stacking sequence. Notably, size-confinement effects were observed in electron diffraction patterns from the wurtzite phase. These effects originated from off-axis planes that do not fulfill the Bragg conditions, yet their elongated Bragg rods intersect with the Ewald sphere, giving rise to unexpected reflections.

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.