Christopher A. Barrett

Spontaneous room temperature elongation of CdS and Ag2S nanorods via oriented attachment.

Spontaneous elongation from nanorod to nanowire in the presence of an amine is reported for nanocrystals of cadmium sulfide and silver sulfide (cation exchanged from CdS). Elongation occurs instantaneously where the final aspect ratio is a controllable multiple of the original nanorod length. Transmission electron microscopy (TEM) analysis reveals the influential factors on the attachment process are the concentration of amine, duration and temperature of the reaction. The elongated nanorods are further characterized by X-ray diffraction (XRD), photoluminescence (PL), ultraviolet-visible spectroscopy (UV-vis) and X-ray photoelectron spectroscopy (XPS). A mechanism of oriented attachment is evidenced by the doubling in length of asymmetrically gold tipped CdS nanorods with the corresponding absence of elongation in symmetrically tipped nanorods.

Controlled semiconductor nanorod assembly from solution: influence of concentration, charge and solvent nature

Spontaneous supercrystal organisation of semiconductor nanorods (CdS and CdSe) of different aspect ratios into ordered superstructures was obtained by controlled evaporation of a nanorod solution. The rods either align into two dimensional close packed perpendicular arrays or into one dimensional rail tracks depending on the total interaction energy between the rods in solution. A detailed study has identified critical factors that affect this interaction energy such as nanorod concentration, surface charge, dipole moment and solvent nature (polarity and volatility), thereby allowing a general approach to control the nature of nanorod assembly (1D or 2D). Molecular dynamics (MD) of small charged nanorods showed that opposite dipolar alignment (antiferromagnetic) was the preferred rod orientation during self-assembly.

Size controlled gold tip growth onto II–VI nanorods

Gold tip size and multiplicity are controlled in hybrid gold–semiconductor nanorods (CdS–Au, CdSe–Au and CdTe–Au) in fast reaction times of less than 2 minutes by optimising precursor type, concentration and temperature. Controllable gold tips up to as large as 40 nm on a rod diameter of 7 nm are reported with the tip size shown to be directly related to the redox potentials of the dangling atoms on the nanorod and the gold chloride precursors (mono- or trivalent). The preference for symmetric (both ends) over asymmetric (single end) is achieved by simply elevating the reaction temperature to 80 °C without changing the reaction time. TEM and XRD analyses were preformed to verify both the gold nanoparticle size and crystallinity of the hybrid nanostructures. Increased quenching of nanorod emission is observed as the size of the gold tip increases suggesting optimisation of charge transfer between the semiconductor and the metal.

Nanoscience of an Ancient Pigment

We describe monolayer nanosheets of calcium copper tetrasilicate, CaCuSi(4)O(10), which have strong near-IR luminescence and are amenable to solution processing methods. The facile exfoliation of bulk CaCuSi(4)O(10) into nanosheets is especially surprising in view of the long history of this material as the colored component of Egyptian blue, a well-known pigment from ancient times.

Metal surface nucleated supercritical fluid–solid–solid growth of Si and Ge/SiOx core–shell nanowires

High yields of both single-crystalline Si and Ge/SiOx core–shell nanowires were nucleated and grown in metal reactor cells under high-pressure supercritical fluid conditions, without the addition of catalyst particle seeds or a porous template. Nanowire growth was only achieved when the fluid medium of supercritical CO2 and the organometallic precursors were used in conjunction with a coordinating solvent, trioctylphosphine. The diameter and length of the nanowires are found to be in the ranges of 30 to 60 nm and 1 to 10 µm, respectively. The correlation of nanowire growth with the eutectic binary phase diagrams of the semiconductor–metal and the presence of metal impurities at the base of the synthesized nanowires suggest a supercritical fluid–solid–solid growth mechanism occurring from the reaction cell walls. The nanowires are characterized by transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy. The electrical characteristics for individually picked nanowires are also investigated by means of mechanical nanoprobing.

The evolution of pseudo-spherical silicon nanocrystals to tetrahedra, mediated by phosphonic acid surfactants

Silicon nanocrystals were synthesized at high temperatures and high pressures by the thermolysis of diphenylsilane using a combination of supercritical carbon dioxide and phosphonic acid surfactants. Size and shape evolution from pseudo-spherical silicon nanocrystals to well-faceted tetrahedral-shaped silicon crystals with edge lengths in the range of 30-400 nm were observed with sequentially decreasing surfactant chain lengths. The silicon nanocrystals were characterized by transmission electron microscopy (TEM), energy-dispersive x-ray spectroscopy (EDX), x-ray diffraction (XRD), photoluminescence (PL), scanning electron microscopy (SEM) and Raman scattering spectroscopy.

Complete synthesis of germanium nanocrystal encrusted carbon colloids in supercritical CO2 and their superhydrophobic properties

Colloidal carbon spheres were synthesized by the carbonization of squalane, a nonvolatile hydrocarbon solvent, in supercritical carbon dioxide. Precise pressure modulation of the fluid medium led to size controlled growth of carbon spheres ranging from 300 to 1500 nm in diameter. This unique synthetic approach of carbonizing a hydrocarbon suspension in supercritical fluid is found to suppress any particle aggregation, resulting in excellent sphere monodispersity. Core-shell hybrid structures of C-Ge were subsequently formed by inducing the growth of 10-40 nm sized germanium nanocrystals from the spheres in a hierarchical bottom-up approach. Extensive characterization of the spheres and nanocrystals was conducted using transmission and scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman, and thermogravametric analysis. Assemblies of nanocrystal modified carbon colloids impart outstanding superhydrophobic properties due to the combined nano- and microstructuring of the particle arrays.

Direct Functionalization of an Acid-Terminated Nanodiamond with Azide: Enabling Access to 4-Substituted-1,2,3-Triazole-Functionalized Particles

Azides on the periphery of nanodiamond materials (ND) are of great utility because they have been shown to undergo Cu-catalyzed and Cu-free cycloaddition reactions with structurally diverse alkynes, affording particles tailored for applications in biology and materials science. However, current methods employed to access ND featuring azide groups typically require either harsh pretreatment procedures or multiple synthesis steps and use surface linking groups that may be susceptible to undesirable cleavage. Here we demonstrate an alternative single-step approach to producing linker-free, azide-functionalized ND. Our method was applied to low-cost, detonation-derived ND powders where surface carbonyl groups undergo silver-mediated decarboxylation and radical substitution with azide. ND with directly grafted azide groups were then treated with a variety of aliphatic, aromatic, and fluorescent alkynes to afford 1-(ND)-4-substituted-1,2,3-triazole materials under standard copper-catalyzed cycloaddition conditions. Surface modification steps were verified by characteristic infrared absorptions and elemental analyses. High loadings of triazole surface groups (up to 0.85 mmol g-1) were obtained as determined from thermogravimetric analysis. The azidation procedure disclosed is envisioned to become a valuable initial transformation in numerous future applications of ND.