Unusual Defect Chemistry of Thorium Doping of PbS.

The unusual defect chemistry of thorium doping in the PbS system was investigated computationally to answer several open questions arising from the experimental observations. These include finding Th in a +4 oxidation state in contrast to Pb, attracting more than two oxygen atoms on average per thorium and affecting the growth morphology of PbS and its electronic properties. We find Th to be energetically stable at the lead lattice position in PbS and to attract 2-3 oxygens, including in the adjacent interstitial position, which binds strongly to Th.

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.

Versatile Patterning of Liquid Metal via Multiphase 3D Printing.

This paper presents a scalable and straightforward technique for the immediate patterning of liquid metal/polymer composites via multiphase 3D printing. Capitalizing on the polymer's capacity to confine liquid metal (LM) into diverse patterns. The interplay between distinctive fluidic properties of liquid metal and its self-passivating oxide layer within an oxidative environment ensures a resilient interface with the polymer matrix.

Nanoparticle Assembly: From Self-Organization to Controlled Micropatterning for Enhanced Functionalities.

Nanoparticles form long-range micropatterns via self-assembly or directed self-assembly with superior mechanical, electrical, optical, magnetic, chemical, and other functional properties for broad applications, such as structural supports, thermal exchangers, optoelectronics, microelectronics, and robotics. The precisely defined particle assembly at the nanoscale with simultaneously scalable patterning at the microscale is indispensable for enabling functionality and improving the performance of devices. This article provides a comprehensive review of nanoparticle assembly formed primarily via the balance of forces at the nanoscale (e.

Real-time monitoring of phase transitions in π-SnS nanoparticles.

While the new cubic phase of tin monosulfide, π-SnS, shows potential for various applications, not much work was focused on the phase transitions, thermal stability, and thermal properties of π-SnS. In this work, we addressed these issues using temperature-resolved X-ray diffraction combined with thermo-gravimetric differential scanning calorimetry and thermo-gravimetric infrared spectroscopy. The cubic π-SnS phase nanoparticles capped with polyvinylpyrrolidone were proven stable for 12 hours at 400 °C, pointing out the possible utilization of this new cubic phase at elevated temperatures.

Electrical and Optical Properties of γ-SnSe: A New Ultra-narrow Band Gap Material.

We describe the unusual properties of γ-SnSe, a new orthorhombic binary phase in the tin monoselenide system. This phase exhibits an ultranarrow band gap under standard pressure and temperature conditions, leading to high conductivity under ambient conditions. Density functional calculations identified the similarity and difference between the new γ-SnSe phase and the conventional α-SnSe based on the electron localization function.

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 - 6/ 194) phase with lattice parameters = = 0.3939 nm, = 1.

'Beneficial impurities' in colloidal synthesis of surfactant coated inorganic nanoparticles.

Colloidal synthesis of nanoparticles (NP) has advanced tremendously over the past 25 years, with an increasing number of research papers introducing nanomaterials with a variety of compositions, shapes, sizes, and phases. Although much progress has been achieved, commonly used synthetic procedures often fail to reproduce results, and the fine details of the syntheses are often disregarded. Reproducibility issues in synthesis can be ascribed to the effects of impurities, trace amounts of chemical moieties which significantly affect the reaction products.

The role of CdS doping in improving SWIR photovoltaic and photoconductive responses in solution grown CdS/PbS heterojunctions.

Low cost short wavelength infrared (SWIR) photovoltaic (PV) detectors and solar cells are of very great interest, yet the main production technology today is based on costly epitaxial growth of InGaAs layers. In this study, layers of p-type, quantum confined (QC) PbS nano-domains (NDs) structure that were engineered to absorb SWIR light at 1550 nm (Eg = 0.8 eV) were fabricated from solution using the chemical bath deposition (CBD) technique.

Stability of cubic tin sulphide nanocrystals: role of ammonium chloride surfactant headgroups.

New semiconducting metastable cubic phases have been recently discovered in the tin monosulfide and monoselenide systems. Surface energy calculations and experimental studies indicate that this cubic π-phase is stabilized by specific ligand adsorption on the surface. In this work, it is shown experimentally that the synthesis carried out using mixtures of oleylamine and oleylammonium chloride (OACl) surfactants results in the cubic phase, transforming the growth from orthorhombic to cubic nanoparticles with increasing OACl concentration up to a limiting point.

Beneficial Impurities and Phase Control in Colloidal Synthesis of Tin Monoselenide.

The effect of impurities in colloidal synthesis of SnSe in oleylamine surfactant was investigated. Specifically, it was found that impurities such as water, hydrochloric acid, and carbon dioxide stabilize the recently discovered cubic phase of tin monoselenide, π-SnSe. We describe the reaction that releases HCl to the reaction medium through reaction of SnCl with moisture and its subsequent reaction with oleylamine, transforming it from neutral to charged surfactant.

Electric Response of CuS Nanoparticle Lubricant Additives: The Effect of Crystalline and Amorphous Octadecylamine Surfactant Capping Layers.

Octadecylamine-coated CuS nanoparticles were designed and confirmed to play an important role in their electric response and boundary lubrication in the ester lubricant. For the case of CuS nanoparticles coated with crystalline surfactant, the surface potential is 18.47 ± 0.

π-Phase Tin and Germanium Monochalcogenide Semiconductors: An Emerging Materials System.

Cubic π-phase monochalcogenides (MX, M = Sn, Ge; X = S, Se) are an emerging new class of materials that has recently been discovered. Here, their thermodynamic stability, progress in synthetic routes, properties, and prospective applications are reviewed. The thermodynamic stability is demonstrated through density functional theory total energy and phonon spectra calculations, which show that the π-phase polytype is stable across the monochalcogenide family.

A New Solid Solution Approach for the Study of Self-Irradiating Damage in non-Radioactive Materials.

A new method to produce a model system for the study of radiation damage in non-radioactive materials is presented. The method is based on homogenously dissolving minute amounts of Th ions in thin films in a controllable manner using a small volume chemical bath deposition technique. This approach is demonstrated for PbS films.

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.

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.

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.

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.

A bottom-up approach toward fabrication of ultrathin PbS sheets.

Two-dimensional (2D) sheets are currently in the spotlight of nanotechnology owing to high-performance device fabrication possibilities. Building a free-standing quantum sheet with controlled morphology is challenging when large planar geometry and ultranarrow thickness are simultaneously concerned. Coalescence of nanowires into large single-crystalline sheet is a promising approach leading to large, molecularly thick 2D sheets with controlled planar morphology.

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.

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.

Origin of the contact angle hysteresis of water on chemisorbed and physisorbed self-assembled monolayers.

Self-assembled monolayers (SAMs) are known to form on a variety of substrates either via chemisorption (i.e., through chemical interactions such as a covalent bond) or physisorption (i.

Effect of metal cations on polydiacetylene Langmuir films.

Polydiacetylene (PDA) Langmuir films (LFs) are a unique class of materials that couple a highly aligned conjugated backbone with tailorable pendant side groups and terminal functionalities. The films exhibit chromatic transitions from monomer to blue polymer and finally to a red phase that can be activated optically, thermally, chemically, and mechanically. The properties of PDA LFs are strongly affected by the presence of metal cations in the aqueous subphase of the film due to their interaction with the carboxylic head groups of the polymer.