We deploy optical microscopy with and without an applied magnetic field to characterize the three-dimensional morphology and measure the line tension of twist disclinations in twisted nematic liquid crystal (LC) sample cells. Twist disclinations are generated by quenching the LC, 5CB (4-cyano-4'-pentylbiphenyl), into the nematic phase; 5CB is confined between substrates with in-plane anchoring directions perpendicular to one another. The disclinations form loops separating domains of opposite twist handedness.
View Article and Find Full Text PDFWe study the director configurations of nematic liquid crystal (NLC) droplets with homeotropic anchoring in a magnetic field and report observation of a magnetic-field-driven transition from a deformed radial to an axial-with-defect configuration. Magnetic-field-induced transitions in NLC droplets differ fundamentally from the traditional planar Freedericksz transition due to the spherical droplet geometry and resulting topological defect. This transition has been studied theoretically, but the director configurations and mechanism of defect evolution in an applied magnetic field have yet to be observed experimentally.
View Article and Find Full Text PDFA top-down lithographic patterning and deposition process is reported for producing nanoparticles (NPs) with well-defined sizes, shapes, and compositions that are often not accessible by wet-chemical synthetic methods. These NPs are ligated and harvested from the substrate surface to prepare colloidal NP dispersions. Using a template-assisted assembly technique, fabricated NPs are driven by capillary forces to assemble into size- and shape-engineered templates and organize into open or close-packed multi-NP structures or NP metamolecules.
View Article and Find Full Text PDFWe 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.
View Article and Find Full Text PDFWe 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.
View Article and Find Full Text PDFTopology 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 MnSn exhibits many exotic physical properties such as a large spontaneous Hall effect and has recently attracted intense interest.
View Article and Find Full Text PDFWe investigated Xe binding in a previously reported paramagnetic metal-organic tetrahedral capsule, [CoL], where L = 4,4'-bis[(2-pyridinylmethylene)amino][1,1'-biphenyl]-2,2'-disulfonate. The Xe-inclusion complex, [XeCoL], was confirmed by H NMR spectroscopy to be the dominant species in aqueous solution saturated with Xe gas. The measured Xe dissociation rate in [XeCoL], = 4.
View Article and Find Full Text PDFWe report a family of two-dimensional hybrid perovskites (2DHPs) based on phenethylammonium lead iodide ((PEA)PbI) 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 () 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.
View Article and Find Full Text PDFThe properties of van der Waals (vdW) materials often vary dramatically with the atomic stacking order between layers, but this order can be difficult to control. Trilayer graphene (TLG) stacks in either a semimetallic ABA or a semiconducting ABC configuration with a gate-tunable band gap, but the latter has only been produced by exfoliation. Here we present a chemical vapor deposition approach to TLG growth that yields greatly enhanced fraction and size of ABC domains.
View Article and Find Full Text PDFThe 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) phase in order to reduce the usage of precious metal, enhance the ORR performance, and improve catalyst stability. In this work, monodisperse Pt-Co nanocrystals (NCs) with well-defined size (4-5 nm) and cobalt composition (25-75 at%) were synthesized via colloidal synthesis.
View Article and Find Full Text PDFLarge-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'-WTe, 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.
View Article and Find Full Text PDFBirefringence 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.
View Article and Find Full Text PDFThe 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.
View Article and Find Full Text PDFWe 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.
View Article and Find Full Text PDFNext-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.
View Article and Find Full Text PDFQuantum 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 temperatures <75 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.
View Article and Find Full Text PDFGrowth 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 ].
View Article and Find Full Text PDFA 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.
View Article and Find Full Text PDFWith 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.
View Article and Find Full Text PDFWe 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.
View Article and Find Full Text PDFA 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.
View Article and Find Full Text PDFWe 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 Mössbauer spectroscopy. Two sets of oxides are studied: (a) as-synthesized magnetite-rich and (b) aged maghemite nanocrystals.
View Article and Find Full Text PDFWe 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.
View Article and Find Full Text PDFWe use subpicosecond time-resolved photoluminescence measurements to study the nature of photoluminescence in graphene oxide and reduced graphene oxide. Our data indicate that, in contrast to prior suggestions, the photoluminescence spectra of graphene oxide and reduced graphene oxide are inhomogeneously broadened. We observe substantial energy redistribution and relaxation among the emitting states within the first few picoseconds, leading to a progressive red shift of the emission spectrum.
View Article and Find Full Text PDFSelf-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.
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