Synthesis and Characterization of Magnetoplasmonic Air-Stable Au@FeCo.

The synthesis of FeCo alloys as highly magnetic nanoparticles has been valuable, as far as applications for magnetic nanoparticles are concerned. However, recently, a field of magnetoplasmonics in which magnetic nanoparticles such as the FeCo alloys doped with plasmonic materials such as Au and Ag to create a hybrid nanostructure with both properties has emerged. These magnetoplasmonic metamaterials have greatly enhanced the limit of detection of analytes in spectroscopic methods, as well as providing a more widely applicable nanoparticle to broaden the use of FeCo alloys even further. Herein, we discuss the synthesis of high-yield and fairly monodisperse spherical FeCo and Au-doped FeCo (Au@FeCo) with varying compositions of Au synthesized via the thermal decomposition of iron pentacarbonyl (Fe(CO)5) and dicobalt octacarbonyl (Co2(CO)8), followed by the addition of Au atoms using triphenylphosphine gold(I) chloride ((Ph3P)AuCl) via both coprecipitation and by delayed addition methods. The products were separated using a hand-held magnet, and then characterized via ultraviolet-visible light (UV-vis), scanning electron microscopy coupled with energy-dispersive X-ray analysis (SEM-EDX), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), flame atomic absorption spectrometry (F-AAS), and magnetization measurements. Optical studies revealed a plasmonic peak at 550 nm in the Au@FeCo nanoparticles that had a gold content (%Au) of >2% (by weight), determined using F-AAS. Colocation of the Fe, Co, and Au were demonstrated through EDX analysis. Location of the Au atoms in the core were seen through high-resolution bright-field imaging. To understand the use of these nanoparticles for potential application in therapeutics and/or electronics, resistance measurements were performed to assess power loss as a function of frequency. We also achieved magnetization values as high as 150 emu/g and as low as 50 emu/g for gold-loaded samples based on %Au by weight. This paves the way to continue to develop magneto-plasmonic structures chemically using these synthesis strategies.

Observation of Coexisting Weak Localization and Superconducting Fluctuations in Strained Sn1-xInxTe Thin Films.

Topological superconductors have attracted tremendous excitement as they are predicted to host Majorana zero modes that can be utilized for topological quantum computing. Candidate topological superconductor Sn1-xInxTe thin films (0 < x < 0.3) grown by molecular beam epitaxy and strained in the (111) plane are shown to host quantum interference effects in the conductivity coexisting with superconducting fluctuations above the critical temperature Tc. An analysis of the normal state magnetoresistance reveals these effects. A crossover from weak antilocalization to localization is consistently observed in superconducting samples, indicating that superconductivity originates dominantly from charge carriers occupying trivial states that may be strongly spin-orbit split. A large enhancement of the conductivity is observed above Tc, indicating the presence of superconducting fluctuations. Our results motivate a re-examination of the debated pairing symmetry of this material when subjected to quantum confinement and lattice strain.

Large-Area Periodic Arrays of Atomically Flat Single-Crystal Gold Nanotriangles Formed Directly on Substrate Surfaces.

The advancement of nanoenabled wafer-based devices requires the establishment of core competencies related to the deterministic positioning of nanometric building blocks over large areas. Within this realm, plasmonic single-crystal gold nanotriangles represent one of the most attractive nanoscale components but where the formation of addressable arrays at scale has heretofore proven impracticable. Herein, a benchtop process is presented for the formation of large-area periodic arrays of gold nanotriangles. The devised growth pathway sees the formation of an array of defect-laden seeds using lithographic and vapor-phase assembly processes followed by their placement in a growth solution promoting planar growth and threefold symmetric side-faceting. The nanotriangles formed in this high-yield synthesis distinguish themselves in that they are epitaxially aligned with the underlying substrate, grown to thicknesses that are not readily obtainable in colloidal syntheses, and present atomically flat pristine surfaces exhibiting gold atoms with a close-packed structure. As such, they express crisp and unambiguous plasmonic modes and form photoactive surfaces with highly tunable and readily modeled plasmon resonances. The devised methods, hence, advance the integration of single-crystal gold nanotriangles into device platforms and provide an overall fabrication strategy that is adaptable to other nanomaterials.

Molybdenum Carbamate Nanosheets as a New Class of Potential Phase Change Materials.

We report for the first time the synthesis of large, free-standing, Mo2O2(µ-S)2(Et2dtc)2 (MoDTC) nanosheets (NSs), which exhibit an electron-beam induced crystalline-to-amorphous phase transition. Both electron beam ionization and femtosecond (fs) optical excitation induce the phase transition, which is size-, morphology-, and composition-preserving. Resulting NSs are the largest, free-standing regularly shaped two-dimensional amorphous nanostructures made to date. More importantly, amorphization is accompanied by dramatic changes to the NS electrical and optical response wherein resulting amorphous species exhibit room-temperature conductivities 5 orders of magnitude larger than those of their crystalline counterparts. This enhancement likely stems from the amorphization-induced formation of sulfur vacancy-related defects and is supported by temperature-dependent transport measurements, which reveal efficient variable range hopping. MoDTC NSs represent one instance of a broader class of transition metal carbamates likely having applications because of their intriguing electrical properties as well as demonstrated ability to toggle metal oxidation states.

Silica nanoparticle remodeling under mild conditions: versatile one step conversion of mesoporous to hollow nanoparticles with simultaneous payload loading.

A binary mixture of mesoporous silica nanoparticles plus organic polyammonium additive (dye or drug) is cleanly converted upon mild heating into hollow nanoparticles. The remodeled nanoparticle shell is an organized nanoscale assembly of globular additive/silica subunits and cancer cell assays show that a loaded drug additive is bioavailable.

Universal Size-Dependent Stokes Shifts in Lead Halide Perovskite Nanocrystals.

Size-dependent photoluminescence Stokes shifts (ΔEs) universally exist in CsPbX3 (X = Cl-, Br-, or I-) perovskite nanocrystals (NCs). ΔEs values, which range from ∼15 to 100 meV for NCs with average edge lengths (l) from approximately 13 to 3 nm, are halide-dependent such that ΔEs(CsPbI3) > ΔEs(CsPbBr3) ≳ ΔEs(CsPbCl3). Observed size-dependent Stokes shifts are not artifacts of ensemble size distributions as demonstrated through measurements of single CsPbBr3 NC Stokes shifts (⟨ΔEs⟩ = 42 ± 5 meV), which are in near quantitative agreement with associated ensemble (l = 6.8 ± 0.8 nm) ΔEs values (ΔEs ≈ 50 meV). Transient differential absorption measurements additionally illustrate no significant spectral dynamics on the picosecond time scale that would contribute to ΔEs. This excludes polaron formation as being responsible for ΔEs. Altogether, the results point to an origin for ΔEs, intrinsic to the size-dependent electronic properties of individual perovskite NCs.

Synthesis of Ultrathin and Thickness-Controlled Cu2-xSe Nanosheets via Cation Exchange.

We demonstrate the use of cation exchange to synthesize ultrathin and thickness-controlled Cu2-xSe nanosheets (NSs) beginning with CdSe NSs. In this manner, extremely thin (i.e., 1.6 nm thickness) Cu2-xSe NSs, beyond which can be made directly, have been obtained. Furthermore, they represent the thinnest NSs produced via cation exchange. Notably, the exchange reaction preserves the starting morphology of the CdSe sheets and also retains their cubic crystal structure. The resulting nonstoichiometric and cubic Cu2-xSe NSs are stable and do not exhibit any signs of Cu or Se oxidation after exposure to air for 2 weeks. Resulting NSs also show the existence of a localized surface plasmon resonance in the infrared due to the presence of copper vacancies. Efforts to isolate intermediates during the cation exchange reaction show that it occurs via a mechanism where entire sheets are rapidly converted into the final product once the exchange reaction commences, precluding the isolation of alloyed species.

Nanowire-functionalized cotton textiles.

We show the general functionalization of cotton fabrics using solution-synthesized CdSe and CdTe nanowires (NWs). Conformal coatings onto individual cotton fibers have been achieved through various physical and chemical approaches. Some involve the electrostatic attraction of NWs to cotton charged positively with a Van de Graaff generator or via 2,3-epoxypropyltrimethylammonium chloride treatments. Resulting NW-functionalized textiles consist of dense, conformal coatings and have been characterized for their UV-visible absorption as well as Raman activity. We demonstrate potential uses of these functionalized textiles through two proof-of-concept applications. The first entails barcoding cotton using the unique Raman signature of the NWs. We also demonstrate the surface-enhancement of their Raman signatures using codeposited Au. A second demonstration takes advantage of the photoconductive nature of semiconductor NWs to create cotton-based photodetectors. Apart from these illustrations, NW-functionalized cotton textiles may possess other uses in the realm of medical, anticounterfeiting, and photocatalytic applications.