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We find evidence for the formation and relaxation of large exciton polarons in 2D organic-inorganic hybrid perovskites. Using ps-scale time-resolved photoluminescence within the phenethylammonium lead iodide family of compounds, we identify a red shifting of emission that we associate with exciton polaron formation time scales of 3-10 ps. Atomic substitutions of the phenethylammonium cation allow local control over the structure of the inorganic lattice, and we show that the structural differences among materials strongly influence the exciton polaron relaxation process, revealing a polaron binding energy that grows larger (up to 15 meV) in more strongly distorted compounds.

We investigated Xe binding in a previously reported paramagnetic metal–organic tetrahedral capsule, [Co4L6]4–, where L2– = 4,4′-bis[(2-pyridinylmethylene)amino][1,1′-biphenyl]-2,2′-disulfonate. The...

We report a family of two-dimensional hybrid perovskites (2DHPs) based on phenethylammonium lead iodide ((PEA)$_2$PbI$_4$) that show complex structure in their low-temperature excitonic absorption and photoluminescence (PL) spectra as well as hot exciton PL. We replace the 2-position (ortho) H on the phenyl group of the PEA cation with F, Cl, or Br to systematically increase the cation's cross-sectional area and mass and study changes in the excitonic structure. These single atom substitutions substantially change the observable number of and spacing between discrete resonances in the excitonic absorption and PL spectra and drastically increase the amount of hot exciton PL that violates Kasha's rule by over an order of magnitude. To fit the progressively larger cations, the inorganic framework distorts and is strained, reducing the Pb-I-Pb bond angles and increasing the 2DHP band gap. Correlation between the 2DHP structure and steady-state and time-resolved spectra suggests the complex structure of resonances arises from one or two manifolds of states, depending on the 2DHP Pb-I-Pb bond angle (as)symmetry, and the resonances within a manifold are regularly spaced with an energy separation that decreases as the mass of the cation increases. The uniform separation between resonances and the dynamics that show excitons can only relax to the next-lowest state are consistent with a vibronic progression caused by a vibrational mode on the cation. These results demonstrate that simple changes to the structure of the cation can be used to tailor the properties and dynamics of the confined excitons without directly modifying the inorganic framework., Comment: 39 pages

We present a novel technique for generating beams of light carrying orbital angular momentum (OAM) that increases mode purity and decreases singularity splitting by orders of magnitude. This technique also works to control and mitigate beam divergence within propagation distances less than the Rayleigh length. Additionally, we analyze a tunable parameter of this technique that can change the ratio of beam purity to power to fit desired specifications. Beam generation via this technique is achievable using only phase-modulating optical elements, which reduces experimental complexity and beam energy loss., 9 pages, 7 figures, submitted to Optics Express 18 August 2022

The development of a suitable catalyst for the oxygen reduction reaction (ORR), the cathode reaction of proton exchange membrane fuel cells (PEMFC), is necessary to push this technology toward widespread adoption. There have been substantial efforts to utilize bimetallic Pt-M alloys that adopt the ordered face-centered tetragonal (L1

Evolution of Kondo effect in Weyl semimetal Mn3Sn leads to extraordinary terahertz and DC transport properties., Topology and strong electron correlations are crucial ingredients in emerging quantum materials, yet their intersection in experimental systems has been relatively limited to date. Strongly correlated Weyl semimetals, particularly when magnetism is incorporated, offer a unique and fertile platform to explore emergent phenomena in novel topological matter and topological spintronics. The antiferromagnetic Weyl semimetal Mn3Sn exhibits many exotic physical properties such as a large spontaneous Hall effect and has recently attracted intense interest. In this work, we report synthesis of epitaxial Mn3+xSn1−x films with greatly extended compositional range in comparison with that of bulk samples. As Sn atoms are replaced by magnetic Mn atoms, the Kondo effect, which is a celebrated example of strong correlations, emerges, develops coherence, and induces a hybridization energy gap. The magnetic doping and gap opening lead to rich extraordinary properties, as exemplified by the prominent DC Hall effects and resonance-enhanced terahertz Faraday rotation.

The topological kagome metal CoSn hosts orbital-selective Dirac bands and very flat bands near the Fermi energy that lead to a range of exotic phenomena, such as fractional quantum Hall states. In this work, we report the synthesis of high-quality epitaxial (0001) CoSn films by magnetron sputtering. Comprehensive structural characterizations demonstrate high crystalline quality with low disorder, sharp interfaces, and a smooth surface. Complementary magnetic and transport properties show a paramagnetic, metallic ground state as seen in bulk. Our work creates a synthetic foundation to investigate and utilize rich topological physics in CoSn thin films and heterostructures.

The topological kagome magnet (TKM) Fe3Sn2 exhibits unusual topological properties, flat electronic bands, and chiral spin textures, making it an exquisite materials platform to explore the interplay between topological band structure, strong electron correlations, and magnetism. Here we report the first synthesis of high-quality epitaxial (0001) Fe3Sn2 films with large intrinsic anomalous Hall effect close to that measured in bulk single crystals. In addition, we measured a large, anisotropic anomalous Nernst coefficient Syx of 1.26 {\mu}V/K, roughly 2-5x greater than that of common ferromagnets, suggesting the presence of Berry curvature sources near the Fermi level in this system. Crucially, the realization of high-quality Fe3Sn2 films opens the door to explore emergent interfacial physics and create novel spintronic devices based on TKMs by interfacing Fe3Sn2 with other quantum materials and by nanostructure patterning., Comment: accepted by Physical Review Materials

Topology and strong electron correlations are crucial ingredients in emerging quantum materials, yet their intersection in experimental systems has been relatively limited to date. Strongly correlated Weyl semimetals, particularly when magnetism is incorporated, offer a unique and fertile platform to explore emergent phenomena in novel topological matter and topological spintronics. The antiferromagnetic Weyl semimetal Mn3Sn exhibits many exotic physical properties such as a large spontaneous Hall effect and has recently attracted intense interest. In this work, we report synthesis of epitaxial Mn3+x Sn1-x films with greatly extended compositional range in comparison with that of bulk samples. As Sn atoms are replaced by magnetic Mn atoms, the Kondo effect, which is a celebrated example of strong correlations, emerges, develops coherence, and induces a hybridization energy gap. The magnetic doping and gap opening lead to rich extraordinary properties, as exemplified by the prominent DC Hall effects and resonance-enhanced terahertz Faraday rotation.

Next-generation 'smart' nanoparticle systems should be precisely engineered in size, shape and composition to introduce multiple functionalities, unattainable from a single material. Bottom-up chemical methods are prized for the synthesis of crystalline nanoparticles, that is, nanocrystals, with size- and shape-dependent physical properties, but they are less successful in achieving multifunctionality. Top-down lithographic methods can produce multifunctional nanoparticles with precise size and shape control, yet this becomes increasingly difficult at sizes of ∼10 nm. Here, we report the fabrication of multifunctional, smart nanoparticle systems by combining top-down fabrication and bottom-up self-assembly methods. Particularly, we template nanorods from a mixture of superparamagnetic Zn

Quantum and dielectric confinement effects in Ruddlesden-Popper 2D hybrid perovskites create excitons with a binding energy exceeding 150 meV. We exploit the large exciton binding energy to study exciton and carrier dynamics as well as electron-phonon coupling (EPC) in hybrid perovskites using absorption and photoluminescence (PL) spectroscopies. At temperatures75 K, we resolve splitting of the excitonic absorption and PL into multiple regularly spaced resonances every 40-46 meV, consistent with EPC to phonons located on the organic cation. We also resolve resonances with a 14 meV spacing, in accord with coupling to phonons with mixed organic and inorganic character. These assignments are supported by density-functional theory calculations. Hot exciton PL and time-resolved PL measurements show that vibrational relaxation occurs on a picosecond time scale competitive with that for PL. At temperatures75 K, excitonic absorption and PL exhibit homogeneous broadening. While absorption remains homogeneous, PL becomes inhomogeneous at temperatures75K, which we speculate is caused by the formation and subsequent dynamics of a polaronic exciton.

Growth of transition metal dichalcogenide (TMD) monolayers is of interest due to their unique electrical and optical properties. Films in the 2H and 1T phases have been widely studied but monolayers of some 1T'-TMDs are predicted to be large-gap quantum spin Hall insulators, suitable for innovative transistor structures that can be switched via a topological phase transition rather than conventional carrier depletion [ Qian et al. Science 2014 , 346 , 1344 - 1347 ]. Here we detail a reproducible method for chemical vapor deposition of monolayer, single-crystal flakes of 1T'-MoTe2. Atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy confirm the composition and structure of MoTe2 flakes. Variable temperature magnetotransport shows weak antilocalization at low temperatures, an effect seen in topological insulators and evidence of strong spin-orbit coupling. Our approach provides a pathway to systematic investigation of monolayer, single-crystal 1T'-MoTe2 and implementation in next-generation nanoelectronic devices.

Large-area growth of monolayer films of the transition metal dichalcogenides is of the utmost importance in this rapidly advancing research area. The mechanical exfoliation method offers high quality monolayer material but it is a problematic approach when applied to materials that are not air stable. One important example is 1T’-WTe2, which in multilayer form is reported to possess a large non saturating magnetoresistance, pressure induced superconductivity, and a weak antilocalization effect, but electrical data for the monolayer is yet to be reported due to its rapid degradation in air. Here we report a reliable and reproducible large-area growth process for obtaining many monolayer 1T’-WTe2 flakes. We confirmed the composition and structure of monolayer 1T’-WTe2 flakes using x-ray photoelectron spectroscopy, energy-dispersive x-ray spectroscopy, atomic force microscopy, Raman spectroscopy and aberration corrected transmission electron microscopy. We studied the time dependent degradation of monolayer 1T’-WTe2 under ambient conditions, and we used first-principles calculations to identify reaction with oxygen as the degradation mechanism. Finally we investigated the electrical properties of monolayer 1T’-WTe2 and found metallic conduction at low temperature along with a weak antilocalization effect that is evidence for strong spin–orbit coupling.

Spinel ferrite nanocrystals (NCs) have shown great promise for a wide variety of electromagnetic and medical applications. In this work, the AC magnetic properties of nonstoichiometric manganese and cobalt ferrites (MxFe3–xO4, M = Mn, Co) NCs are systematically studied as a function of composition. Samples of very similar average size and shape, but different Mn to Fe and Co to Fe ratios are prepared to study the effect of composition. Conventional syntheses are combined with a size-selective precipitation method using oleic acid as an antisolvent yielding nearly monodisperse samples. DC and AC magnetic measurements shows that introducing Co to the ferrite crystal increases the blocking temperatures and magnetic anisotropies of the nanocrystals with corresponding shifts in AC magnetic susceptibilities, while manganese ferrites are relatively insensitive to the variation in compositions as size and shape dominate over crystal anisotropy. The systematic AC-magnetic characterizations of superparamagnetic Mnx...

With an ultrafast time-resolved photoluminescence system utilizing a Kerr gate, the time-resolved photoluminescence of core and shell constituents within CdSe/CdS dot-in-rod heterostructures is studied as a function of heterostructure size. Measurements performed at low excitation fluence generating, on average, less than one exciton per nanorod, reveal photoluminescence from direct recombination of carriers in the CdS heterostructure rod with lifetime generally increasing from 0.4 ps to 1.3 ps as the rod length increases. Decay of the CdS rod photoluminescence is accompanied by an increase in emission from the CdSe core on comparable time scales, also trending towards larger values as the rod length increases. The observed kinetics can be explained without invoking a non-radiative trapping mechanism. We also present alloying as a mechanism for enhancing electron confinement and reducing fluorescence lifetime at nanosecond time scales.

A safe, scalable method for producing highly conductive aligned films of single-walled carbon nanotubes (SWNTs) from water suspensions is presented. While microfluidic assembly of SWNTs has received significant attention, achieving desirable SWNT dispersion and morphology in fluids without an insulating surfactant or toxic superacid is challenging. We present a method that uniquely produces a noncorrosive ink that can be directly applied to a device in situ, which is different from previous fabrication techniques. Functionalized SWNTs (f-SWNTs) are dispersed in an aqueous urea solution to leverage binding between the amine group of urea and the carboxylic acid group of f-SWNTs and obtain urea-SWNT. Compared with SWNTs dispersed using conventional methods (e.g., superacid and surfactants), the dispersed urea-SWNT aggregates have a higher aspect ratio with a rodlike morphology as measured by light scattering. The Mayer rod technique is used to prepare urea-SWNT, highly aligned films (two-dimensional nematic order parameter of 0.6, 5 μm spot size, via polarized Raman) with resistance values as low as 15-1700 Ω/sq in a transmittance range of 2-80% at 550 nm. These values compete with the best literature values for conductivity of SWNT-enabled thin films. The findings offer promising opportunities for industrial applications relying on highly conductive thin SWNT films.

A low temperature, aqueous synthesis of polyhedral iron oxide nanoparticles (IONPs) is presented. The modification of the co-precipitation hydrolysis method with Triton X surfactants results in the formation of crystalline polyhedral particles. The particles are herein termed iron oxide “nanobricks” (IONBs) as the variety of particles made are all variations on a simple “brick-like” rhombohedral shape as evaluated by TEM. These IONBs can be easily coated with hydrophilic silane ligands, allowing them to be dispersed in aqueous media. The dispersed particles are investigated for potential applications as hyperthermia and T2 MRI contrast agents. The results demonstrate that the IONBs perform better than comparable spherical IONPs in both applications, and show r2 values amongst the highest for iron oxide based materials reported in the literature.

The collective magnetic properties of nanoparticle (NP) solid films are greatly affected by inter-particle dipole–dipole interactions and therefore the proximity of the neighboring particles. In this study, a series of dendritic ligands (generations 0 to 3, G0–G3) have been designed and used to cover the surface of magnetic NPs to control the spacings between the NP components in single lattices. The dendrons of different generations introduced here were based on the 2,2-bis(hydroxymethyl)propionic acid (Bis-MPA) scaffold and equipped with an appropriate surface binding group at one end and several fatty acid segments at the other extremity. The surface of the NPs was then modified by partial ligand exchange between the primary stabilizing surfactants and the new dendritic wedges. It was shown that this strategy permitted very precise tuning of inter-particle spacings in the range of 2.9–5.0 nm. As expected, the increase in the inter-particle spacings reduced the dipole–dipole interactions between magnetic NPs and therefore allowed changes in their magnetic permeability. The dendron size and inter-particle distance dependence was studied to reveal the dendritic effect and identify the optimal geometry and generation.

Birefringence in stable glasses produced by physical vapor deposition often implies molecular alignment similar to liquid crystals. As such, it remains unclear whether these glasses share the same energy landscape as liquid-quenched glasses that have been aged for millions of years. Here, we produce stable glasses of 9-(3,5-di(naphthalen-1-yl)phenyl)anthracene molecules that retain three-dimensional shapes and do not preferentially align in a specific direction. Using a combination of angle- and polarization-dependent photoluminescence and ellipsometry experiments, we show that these stable glasses possess a predominantly isotropic molecular orientation while being optically birefringent. The intrinsic birefringence strongly correlates with increased density, showing that molecular ordering is not required to produce stable glasses or optical birefringence, and provides important insights into the process of stable glass formation via surface-mediated equilibration. To our knowledge, such novel amorphous packing has never been reported in the past.

We explore the evolution of plasmonic modes in two-dimensional nanocrystal oligomer "metamolecules" as the number of nanocrystals is systematically varied. Precise, hexagonally ordered Au nanocrystal oligomers with 1-31 members are assembled via capillary forces into polygonal topographic templates defined using electron-beam lithography. The visible and near-infrared scattering response of individual oligomers is measured by spatially resolved, polarized darkfield scattering spectroscopy. The response is highly sensitive to in-plane versus out-of-plane incident polarization, and we observe an exponentially saturating red shift in plasmon resonance wavelength as the number of nanocrystals per oligomer increases, in agreement with theoretical predictions. Simulations further elucidate the modes supported by the oligomers, including electric dipole and magnetic dipole resonances and their Fano interference. The single-oligomer sensitivity of our measurements also reveals the role of positional disorder in determining the wavelength and character of the plasmonic response. The progression of oligomer metamolecule structures studied here advances our understanding of fundamental plasmonic interactions in the transition regime between few-member plasmonic clusters and extended two-dimensional arrays.

We study gate-controlled, low-temperature resistance and magnetotransport in indium-doped CdSe quantum dot field effect transistors. We show that using the gate to accumulate electrons in the quantum dot channel increases the "localization product" (localization length times dielectric constant) describing transport at the Fermi level, as expected for Fermi level changes near a mobility edge. Our measurements suggest that the localization length increases to significantly greater than the quantum dot diameter.

Self-assembly of multicomponent nanocrystal superlattices provides a modular approach to the design of metamaterials by choosing constituent nanocrystal building blocks with desired physical properties and engineering the interparticle coupling. In this work, we report the self-assembly of binary nanocrystal superlattices composed of magnetically hard CoFe2O4 nanocrystals and magnetically soft Fe3O4 nanocrystals. Both NaZn13- and MgZn2-type CoFe2O4–Fe3O4 binary nanocrystal superlattices have been formed by the liquid–air interfacial assembly approach. Exchange coupling is achieved in both types of binary superlattices after thermal annealing under vacuum at 400 °C. The exchange-coupled CoFe2O4–Fe3O4 binary nanocrystal superlattices show single-phase magnetization switching behavior and magnetoresistance switching behavior below 200 K. The NaZn13-type CoFe2O4–Fe3O4 binary nanocrystal superlattices annealed at 500 °C even exhibit bistable magnetoresistance switching behavior at room temperature constituting...

We calculate the orbital magnetic anisotropy (Δχ) of semiconducting single-walled carbon nanotubes at different carrier densities using a nearest-neighbor tight-binding model. Kataura plots of Δχ exhibit 2n + m family groupings and chiral index dependence at all carrier densities which are consistent with the trigonal warping effect. The diameter dependence of Δχ varies strongly with carrier density. We fit our data with a symmetry-restricted model to obtain approximate analytic expressions for Δχ as a function of nanotube chirality and carrier density. Our results illustrate the important role of doping on the magnetic properties of carbon nanotubes. Experimental studies of Δχ should take these effects into account for accurate interpretation of their results.

We report the growth of NaCl-type binary nanocrystal (NC) superlattice membranes by coassembly of FePt and MnO NCs at the liquid-air interface. The constituent FePt NCs were converted into the hard magnetic L1(0) phase by thermal annealing at 650 °C without degradation of the long-range NC ordering. In contrast, both FePt-only NC superlattices and FePt-MnO disordered NC mixtures showed substantial FePt sintering under the same annealing conditions. Our results demonstrate that the incorporation of FePt NCs into binary superlattices can solve the problems of FePt sintering during conversion to the L1(0) phase, opening a new route to the fabrication of ordered ferromagnetic NC arrays on a desired substrate for high-density data storage applications.

The manipulation of radiative properties of light emitters coupled with surface plasmons is important for engineering new nanoscale optoelectronic devices, including lasers, detectors and single photon emitters. However, so far the radiative rates of excited states in semiconductors and molecular systems have been enhanced only moderately, typically by a factor of 10-50, producing emission mostly from thermalized excitons. Here, we show the generation of dominant hot-exciton emission, that is, luminescence from non-thermalized excitons that are enhanced by the highly concentrated electromagnetic fields supported by the resonant whispering-gallery plasmonic nanocavities of CdS-SiO(2)-Ag core-shell nanowire devices. By tuning the plasmonic cavity size to match the whispering-gallery resonances, an almost complete transition from thermalized exciton to hot-exciton emission can be achieved, which reflects exceptionally high radiative rate enhancement of10(3) and sub-picosecond lifetimes. Core-shell plasmonic nanowires are an ideal test bed for studying and controlling strong plasmon-exciton interaction at the nanoscale and opens new avenues for applications in ultrafast nanophotonic devices.

Uranium compounds supported by redox-active α-diimine ligands, which have methyl groups on the ligand backbone and bulky mesityl substituents on the nitrogen atoms {(Mes)DAB(Me) = [ArN═C(Me)C(Me)═NAr], where Ar = 2,4,6-trimethylphenyl (Mes)}, are reported. The addition of 2 equiv of (Mes)DAB(Me), 3 equiv of KC(8), and 1 equiv of UI(3)(THF)(4) produced the bis(ligand) species ((Mes)DAB(Me))(2)U(THF) (1). The metallocene derivative, Cp(2)U((Mes)DAB(Me)) (2), was generated by the addition of an equimolar ratio of (Mes)DAB(Me) and KC(8) to Cp(3)U. The bond lengths in the molecular structure of both species confirm that the α-diimine ligands have been doubly reduced to form ene-diamide ligands. Characterization by electronic absorption spectroscopy shows weak, sharp transitions in the near-IR region of the spectrum and, in combination with the crystallographic data, is consistent with the formulation that tetravalent uranium ions are present and supported by ene-diamide ligands. This interpretation was verified by U L(III)-edge X-ray absorption near-edge structure (XANES) spectroscopy and by variable-temperature magnetic measurements. The magnetic data are consistent with singlet ground states at low temperature and variable-temperature dependencies that would be expected for uranium(IV) species. However, both complexes exhibit low magnetic moments at room temperature, with values of 1.91 and 1.79 μ(B) for 1 and 2, respectively. Iodomethane was used to test the reactivity of 1 and 2 for multielectron transfer. While 2 showed no reactivity with CH(3)I, the addition of 2 equiv of iodomethane to 1 resulted in the formation of a uranium(IV) monoiodide species, ((Mes)DAB(Me))((Mes)DAB(Me2))UI {3; (Mes)DAB(Me2) = [ArN═C(Me)C(Me(2))NAr]}, which was characterized by single-crystal X-ray diffraction and U M(4)- and M(5)-edge XANES. Confirmation of the structure was also attained by deuterium labeling studies, which showed that a methyl group was added to the ene-diamide ligand carbon backbone.

The ability to engineer surface properties of nanocrystals (NCs) is important for various applications, as many of the physical and chemical properties of nanoscale materials are strongly affected by the surface chemistry. Here, we report a facile ligand-exchange approach, which enables sequential surface functionalization and phase transfer of colloidal NCs while preserving the NC size and shape. Nitrosonium tetrafluoroborate (NOBF4) is used to replace the original organic ligands attached to the NC surface, stabilizing the NCs in various polar, hydrophilic media such as N,N-dimethylformamide for years, with no observed aggregation or precipitation. This approach is applicable to various NCs (metal oxides, metals, semiconductors, and dielectrics) of different sizes and shapes. The hydrophilic NCs obtained can subsequently be further functionalized using a variety of capping molecules, imparting different surface functionalization to NCs depending on the molecules employed. Our work provides a versatile ligand-exchange strategy for NC surface functionalization and represents an important step toward controllably engineering the surface properties of NCs.

We describe the temperature-dependent characterization of resistive switching behavior in bulk silver nanowire−polystyrene composites between 10 and 300 K. We propose that the resistive switching behavior is caused by the electroformation of silver filaments between adjacent nanowire clusters, resulting in an extension of the electrical percolation network in the on state. This process is reversible above 200 K, and irreversible below 100 K. The switching fields are shown to depend strongly on sample composition (i.e., proximity to the electrical percolation threshold), as well as measurement temperature.

Co-assembly of two types of nanocrystals (NCs) into binary NC superlattices (BNSLs) provides a solution-based, inexpensive way to create novel metamaterials with rationally designed properties. The fundamental challenge is to probe and understand the nature and extent of complex interparticle interactions present in BNSLs, which can lead to collective properties that differ from their dispersed constituents or phase-separated counterparts. Here, we report the growth and magnetic characterization of large-area (∼1 cm(2)) BNSL membranes self-assembled from distinct magnetic NCs at the liquid-air interface. The resulting BNSL membranes exhibit a single-phase-like magnetization alignment process, which is not observed in the phase-separated NC mixtures having the same stoichiometry. This single-phase-like magnetic behavior is attributed to the collective interparticle dipolar interactions between two NC components in BNSLs, corroborated by calculation of the random dipolar fields as well as Monte Carlo simulation. The collective magnetic properties are demonstrated in magnetic BNSL membranes having different structures (stoichiometry) and different NC combinations.

Traditionally, bulk nanocomposites of electrically conducting particles and insulating polymers have been categorized as either insulating or conducting when the nanoparticle concentration is below or above the percolation threshold, respectively. Meanwhile, thin-film polymer nanocomposites can exhibit resistive switching behavior appropriate for digital memory applications. Here, we present the first report of reversible resistive switching in bulk, glassy polymer nanocomposites. At compositions close to the electrical percolation threshold measured at low voltage, silver nanowire-polystyrene nanocomposites demonstrate reversible resistive switching with increasing voltage at room temperature. Nanocomposites with compositions outside of this range exhibit either irreversible switching, or no switching at all. We propose that resistive switching in these materials is the result of the field-induced formation of silver filaments that bridge adjacent nanowire clusters, extending the percolation network and decreasing the sample’s bulk resistivity. These findings break from the usual dichotomy of insulating or conducting properties in polymer nanocomposites and could inspire new devices that capitalize on this responsive behavior in these versatile materials.

The design and preparation of isotropic silver nanowire-polystyrene composites is described, in which the nanowires have fi nite L/D ( < 35) and narrow L/D distribution. These model composites allow the L/D dependence of the electrical percolation threshold, φ c , to be isolated for fi nite- L/D particles. Experimental φ c values decrease with increasing L/D , as predicted qualitatively by analytical percolation models. However, quantitative agreement between experimental data and both soft-core and core–shell analytical models is not achieved, because both models are strictly accurate only in the infi nite- L/D limit. To address this analytical limitation, a soft-core simulation method to calculate φ c and network conductivity for cylinders with fi nite L/D are developed. Our simulated φ c results agree strongly with our experimental data, suggesting i) that the infi nite-aspect-ratio assumption cannot safely be made for experimental networks of particles with L/D < 35 and ii) in predicting φ c , the soft-core model makes a less signifi cant assumption than the infi nite- L/D models do. The demonstrated capability of the simulations to predict φ c in the fi nite- L/D regime will allow researchers to optimize the electrical properties of polymer nanocomposites of fiL/D particles.

Aerogels are ultralight, highly porous materials typicallyfabricated by subjecting a wet-gel precursor to critical-point-drying (CPD) or lyophilization (freeze-drying) in order toremove background liquid without collapsing the network.Microscopically, aerogels are composed of tenuous networksof clustered nanoparticles, and the materials often haveunique properties, including very high strength-to-weight andsurface-area-to-volume ratios. To date most aerogels are fab-ricated from silica

A low temperature, aqueous synthesis of polyhedral iron oxide nanoparticles (IONPs) is presented. The modification of the co-precipitation hydrolysis method with Triton X surfactants results in the formation of crystalline polyhedral particles. The particles are herein termed iron oxide “nanobricks” (IONBs) as the variety of particles made are all variations on a simple “brick-like” rhombohedral shape as evaluated by TEM. These IONBs can be easily coated with hydrophilic silane ligands, allowing them to be dispersed in aqueous media. The dispersed particles are investigated for potential applications as hyperthermia and T2 MRI contrast agents. The results demonstrate that the IONBs perform better than comparable spherical IONPs in both applications, and show r2 values amongst the highest for iron oxide based materials reported in the literature.

Photoluminescence (PL) identifies spectroscopic signatures of intertube transfer of optically pumped carriers in single-walled carbon nanotube (SWNT) ensembles. Resonant photoexcitation of large band gap SWNTs produces strong PL from smaller band gap SWNTs. Magnetic alignment measurements associate the energy-transfer PL peaks with the formation of SWNT bundles, suggesting that efficient coupling results from physical contact.

We use time-integrated and time-resolved photoluminescence and absorption to characterize the low-temperature optical properties of CdSe quantum dot solids after exchanging native aliphatic ligands for thiocyanate and subsequent thermal annealing. In contrast to trends established at room temperature, our data show that at low temperature the band-edge absorptive bleach is dominated by 1S3/2h hole occupation in the quantum dot interior. We find that our ligand treatments, which bring enhanced interparticle coupling, lead to faster surface state electron trapping, a greater proportion of surface-related photoluminescence, and decreased band-edge photoluminescence lifetimes.

Large-area growth of monolayer films of the transition metal dichalcogenides is of the utmost importance in this rapidly advancing research area. The mechanical exfoliation method offers high quality monolayer material but it is a problematic approach when applied to materials that are not air stable. One important example is 1T'-WTe2, which in multilayer form is reported to possess a large non saturating magnetoresistance, pressure induced superconductivity, and a weak antilocalization effect, but electrical data for the monolayer is yet to be reported due to its rapid degradation in air. Here we report a reliable and reproducible large-area growth process for obtaining many monolayer 1T'-WTe2 flakes. We confirmed the composition and structure of monolayer 1T'-WTe2 flakes using x-ray photoelectron spectroscopy, energy-dispersive x-ray spectroscopy, atomic force microscopy, Raman spectroscopy and aberration corrected transmission electron microscopy. We studied the time dependent degradation of monolayer 1T'-WTe2 under ambient conditions, and we used first-principles calculations to identify reaction with oxygen as the degradation mechanism. Finally we investigated the electrical properties of monolayer 1T'-WTe2 and found metallic conduction at low temperature along with a weak antilocalization effect that is evidence for strong spin-orbit coupling.

The syntheses of tri- and tetravalent uranium complexes of the Ar(F)(3)TPA(3-) ligand [Ar(F) = 3,5-bis(trifluoromethyl)phenyl; TPA = tris(pyrrolyl-α-methylamine)] are described. Interligand noncovalent interactions between arene groups within the complexes are detected both in the solid state and in solution.

The conproportionation reaction between the dimeric diimidouranium(V) species [U(N(t)Bu)(2)(I)((t)Bu(2)bpy)](2) ((t)Bu(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridyl) and UI(3)(THF)(4) in the presence of additional (t)Bu(2)bpy yields U(N(t)Bu)(I)(2)((t)Bu(2)bpy)(THF)(2) (2), an unprecedented example of a monoimidouranium(IV) dihalide complex. The general synthesis of this family of uranium(IV) derivatives can be achieved more readily by adding 2 equiv of MN(H)R (M = Li, K; R = (t)Bu, 2,6-(i)PrC(6)H(3), 2-(t)BuC(6)H(4)) to UX(4) in the presence of coordinating Lewis bases to give complexes with the general formula U(NR)(X)(2)(L)(n) (X = Cl, I; L = (t)Bu(2)bpy, n = 1; L = THF, n = 2). The complexes were characterized by (1)H NMR spectroscopy and single-crystal X-ray diffraction analysis of compounds 2 and {U[N(2,6-(i)PrC(6)H(3))](Cl)(2)(THF)(2)}(2) (4). (The X-ray structures of 5 and 6 are reported in the Supporting Information.)

We investigate the size- and composition-dependent ac magnetic permeability of superparamagnetic iron oxide nanocrystals for radio frequency (RF) applications. The nanocrystals are obtained through high-temperature decomposition synthesis, and their stoichiometry is determined by Mossbauer spectroscopy. Two sets of oxides are studied: (a) as-synthesized magnetite-rich and (b) aged maghemite nanocrystals. All nanocrystalline samples are confirmed to be in the superparamagnetic state at room temperature by SQUID magnetometry. Through the one-turn inductor method, the ac magnetic properties of the nanocrystalline oxides are characterized. In magnetite-rich iron oxide nanocrystals, size-dependent magnetic permeability is not observed, while maghemite iron oxide nanocrystals show clear size dependence. The inductance, resistance, and quality factor of hand-wound inductors with a superparamagnetic composite core are measured. The superparamagnetic nanocrystals are successfully embedded into hand-wound inductors to function as inductor cores.

2- and 4-probe dark conductivity (DC) data obtained for thin-film and solid-state samples of undoped PZnn oligomers show that the measured DCs for these species span an impressively wide range. Sterically unencumbered PZnn oligomers enable augmented interchain electronic coupling in the solid state and provide electronically functional thin films via direct spin-casting.

Self-assembly of multicomponent nanocrystal superlattices provides a modular approach to the design of metamaterials by choosing constituent nanocrystal building blocks with desired physical properties and engineering the interparticle coupling. In this work, we report the self-assembly of binary nanocrystal superlattices composed of magnetically hard CoFe₂O₄ nanocrystals and magnetically soft Fe₃O₄ nanocrystals. Both NaZn₁₃- and MgZn₂-type CoFe₂O₄--Fe₃O₄ binary nanocrystal superlattices have been formed by the liquid-air interfacial assembly approach. Exchange coupling is achieved in both types of binary superlattices after thermal annealing under vacuum at 400 °C. The exchange-coupled CoFe₂O₄--Fe₃O₄ binary nanocrystal superlattices show single-phase magnetization switching behavior and magnetoresistance switching behavior below 200 K. The NaZn₁₃-type CoFe₂O₄--Fe₃O₄ binary nanocrystal superlattices annealed at 500 °C even exhibit bistable magnetoresistance switching behavior at room temperature constituting a simple nonvolatile memory function.

We investigate the ac magnetic behavior of solution processable, non-stoichiometric zinc ferrite nanocrystals with a series of sizes and zinc concentrations. Nearly monodisperse ZnxFe3−xO4 nanocrystals (x = 0–0.25) with an average size ranging from 7.4 nm to 13.8 nm are synthesized by using a solvothermal method. All the nanocrystals are in a superparamagnetic state at 300 K, which is confirmed by Superconductive Quantum Interference Device magnetometry. Due to the doping of non-magnetic Zn2+ into A site of ferrite, the saturation magnetization of nanocrystals increases as the size and Zn concentration increases. The ac magnetic permeability measurements at radio frequencies reveal that the real part of the magnetic permeability of similarly sized ferrite nanocrystals can be enhanced by almost twofold as the Zn2+ doping level increases from 0 to 0.25. The integration of 12.3 nm Zn0.25Fe2.75O4 nanocrystals into a toroidal inductor and a solenoid inductor prepared via a simple solution cast process yields a...

Pentavalent uranium complexes of the formula U(V)X(2)[N(SiMe(3))(2)](3) (X = F(-), Cl(-), Br(-), N(3)(-), NCS(-)) are accessible from the oxidation of U(III)[N(SiMe(3))(2)](3) through two sequential, one-electron oxidation reactions (halides) and substitution through salt metathesis (pseudohalides). Uranium(v) mixed-halides are also synthesized by successive one-electron oxidation reactions.

We report how to control the self-assembly of magnetic nanoparticles and a prototypical amphiphilic block-copolymer composed of poly(acrylic acid) and polystyrene (PAA-b-PS). Three distinct structures were obtained by controlling the solvent-nanoparticle and polymer-nanoparticle interactions: (1) polymersomes densely packed with nanoparticles (magneto-polymersomes), (2) core-shell type polymer assemblies where nanoparticles are radially arranged at the interface between the polymer core and the shell (magneto-core shell), and (3) polymer micelles where nanoparticles are homogeneously incorporated (magneto-micelles). Importantly, we show that the incorporation of nanoparticles drastically affects the self-assembly structure of block-copolymers by modifying the relative volume ratio between the hydrophobic block and the hydrophilic block. As a consequence, the self-assembly of micelle-forming block-copolymers typically produces magneto-polymersomes instead of magneto-micelles. On the other hand, vesicle-forming polymers tend to form magneto-micelles due to the solubilization of nanoparticles in polymer assemblies. The nanoparticle-polymer interaction also controls the nanoparticle arrangement in the polymer matrix. In N,N-dimethylformamide (DMF) where PS is not well-solvated, nanoparticles segregate from PS and form unique radial assemblies. In tetrahydrofuran (THF), which is a good solvent for both nanoparticles and PS, nanoparticles are homogeneously distributed in the polymer matrix. Furthermore, we demonstrated that the morphology of nanoparticle-encapsulating polymer assemblies significantly affects their magnetic relaxation properties, emphasizing the importance of the self-assembly structure and nanoparticle arrangement as well as the size of the assemblies.

The spontaneous organization of multicomponent micrometre-sized colloids or nanocrystals into superlattices is of scientific importance for understanding the assembly process on the nanometre scale and is of great interest for bottom-up fabrication of functional devices. In particular, co-assembly of two types of nanocrystal into binary nanocrystal superlattices (BNSLs) has recently attracted significant attention, as this provides a low-cost, programmable way to design metamaterials with precisely controlled properties that arise from the organization and interactions of the constituent nanocrystal components. Although challenging, the ability to grow and manipulate large-scale BNSLs is critical for extensive exploration of this new class of material. Here we report a general method of growing centimetre-scale, uniform membranes of BNSLs that can readily be transferred to arbitrary substrates. Our method is based on the liquid-air interfacial assembly of multicomponent nanocrystals and circumvents the limitations associated with the current assembly strategies, allowing integration of BNSLs on any substrate for the fabrication of nanocrystal-based devices. We demonstrate the construction of magnetoresistive devices by incorporating large-area (1.5 mm x 2.5 mm) BNSL membranes; their magnetotransport measurements clearly show that device magnetoresistance is dependent on the structure (stoichiometry) of the BNSLs. The ability to transfer BNSLs also allows the construction of free-standing membranes and other complex architectures that have not been accessible previously.

We study structural symmetries of two-dimensional (2D) photonic crystals with anisotropic unit cells, including square- and rectangular-lattices with orientationally modulated elliptic motifs, a compound structure consisting of circles with 6-fold rotational symmetry and elliptical lines with 2-fold symmetry, and a rectangular lattice of aligned ovals, which are created through elastic deformation of an elastomeric membrane with circular pores. We then investigate the photonic bandgap (PBG) properties of the corresponding 2D Si posts, and their tolerance to the structural deviation. We find that in the compound structure the overall PBGs are dominated by the sublattice with a higher symmetry, while the total symmetry is determined by the one with a lower symmetry.