Realizing optical magnetism from dielectric metamaterials.

We demonstrate, for the first time, an all-dielectric metamaterial composite in the midinfrared based on micron-sized, high-index tellurium dielectric resonators. Dielectric resonators are desirable compared to conventional metallodielectric metamaterials at optical frequencies as they are largely angular invariant, free of Ohmic loss, and easily integrated into three-dimensional volumes. Measurements and simulation provide evidence of optical magnetism, which could be used for infrared magnetic mirrors, hard or soft surfaces, and subwavelength cavities.

Nano-lithographically fabricated titanium dioxide based visible frequency three dimensional gap photonic crystal.

Photonic crystals (PC) have emerged as important types of structures for light manipulation. Ultimate control of light is possible by creating PCs with a complete three dimensional (3D) gap [1, 2]. This has proven to be a considerable challenge in the visible and ultraviolet frequencies mainly due to complications in integrating transparent, high refractive index (n) materials with fabrication techniques to create ~ 100nm features with long range translational order. In this letter, we demonstrate a nano-lithography approach based on a multilevel electron beam direct write and physical vapor deposition, to fabricate four-layer titania woodpile PCs that potentially exhibit complete 3D gap at visible wavelengths. We achieved a short wavelength bandedge of 525nm with a 300nm lattice constant PC. Due to the nanoscale precision and capability for defect control, the nanolithography approach represents an important step toward novel visible photonic devices for lighting, lasers, sensing and biophotonics.

Pressure compression of CdSe nanoparticles into luminescent nanowires.

Oriented attachment (OA) of synthetic nanocrystals is emerging as an effective means of fabricating low-dimensional nanoscale materials. However, OA relies on energetically favorable nanocrystal facets to grow nanostructured materials. Consequently, nanostructures synthesized through OA are generally limited to a specific crystal facet in their final morphology. We report our discovery that high-pressure compression can induce consolidation of spherical CdSe nanocrystal arrays, leading to unexpected one-dimensional semiconductor nanowires that do not exhibit the typical crystal facet. In particular, in situ high-pressure synchrotron x-ray scattering, optical spectroscopy, and high-resolution transmission electron microscopy characterizations indicate that by manipulating the coupling between nanocrystals through external pressure, a reversible change in nanocrystal assemblies and properties can be achieved at modest pressure. When pressure is increased above a threshold, these nanocrystals begin to contact one another and consolidate, irreversibly forming one-dimensional luminescent nanowires. High-fidelity molecular dynamics (MD) methods were used to calculate surface energies and simulate compression and coalescence mechanisms of CdSe nanocrystals. The MD results provide new insight into nanowire assembly dynamics and phase stability of nanocrystalline structures.

Poly(N-isopropylacrylamide) surfactant-functionalized responsive silver nanoparticles and superlattices.

Metal nanoparticles exhibit unique optical characteristics in visible spectra produced by local surface plasmon resonance (SPR) for a wide range of optical and electronic applications. We report the synthesis of poly(N-isopropylacrylamide) surfactant (PNIPAM-C18)-functionalized metal nanoparticles and ordered superlattice arrays through an interfacial self-assembly process. The method is simple and reliable without using complex chemistry. The PNIPAM-C18-functionalized metal nanoparticles and ordered superlattices exhibit responsive behavior modulated by external temperature and relative humidity (RH). In situ grazing-incidence small-angle X-ray scattering studies confirmed that the superlattice structure of PNIPAM-C18 surfactant-functionalized nanoparticle arrays shrink and spring back reversibly based on external thermal and RH conditions, which allow flexible manipulation of interparticle spacing for tunable SPR. PNIPAM-C18 surfactants play a key role in accomplishing this responsive property. The ease of fabrication of the responsive nanostructure facilitates investigation of nanoparticle coupling that depends on interparticle separation for potential applications in chemical and biological sensors as well as energy storage devices.

Stress-induced phase transformation and optical coupling of silver nanoparticle superlattices into mechanically stable nanowires.

One-dimensional silver materials display unique optical and electrical properties with promise as functional blocks for a new generation of nanoelectronics. To date, synthetic approaches and property engineering of silver nanowires have primarily focused on chemical methods. Here we report a simple physical method of metal nanowire synthesis, based on stress-induced phase transformation and sintering of spherical Ag nanoparticle superlattices. Two phase transformations of nanoparticles under stress have been observed at distinct length scales. First, the lattice dimensions of silver nanoparticle superlattices may be reversibly manipulated between 0-8 GPa compressive stresses to enable systematic and reversible changes in mesoscale optical coupling between silver nanoparticles. Second, stresses greater than 8 GPa induced an atomic lattice phase transformation, which induced sintering of silver nanoparticles into micron-length scale nanowires. The nanowire synthesis mechanism displays a dependence on both nanoparticle crystal surface orientation and presence of particular grain boundaries to enable nanoparticle consolidation into nanowires.

Fast lithium-ion conducting thin-film electrolytes integrated directly on flexible substrates for high-power solid-state batteries.

By utilizing an equilibrium processing strategy that enables co-firing of oxides and base metals, a means to integrate the lithium-stable fast lithium-ion conductor lanthanum lithium tantalate directly with a thin copper foil current collector appropriate for a solid-state battery is presented. This resulting thin-film electrolyte possesses a room temperature lithium-ion conductivity of 1.5 × 10(-5) S cm(-1) , which has the potential to increase the power of a solid-state battery over current state of the art.

Systematic analysis of micromixers to minimize biofouling on reverse osmosis membranes.

Micromixers, UV-curable epoxy traces printed on the surface of a reverse osmosis membrane, were tested on a cross-flow system to determine their success at reducing biofouling. Biofouling was quantified by measuring the rate of permeate flux decline and the median bacteria concentration on the surface of the membrane (as determined by fluorescence intensity counts due to nucleic acid stains as measured by hyperspectral imaging). The micromixers do not appear to significantly increase the pressure needed to maintain the same initial permeate flux and salt rejection. Chevrons helped prevent biofouling of the membranes in comparison with blank membranes. The chevron design controlled where the bacteria adhered to the membrane surface. However, blank membranes with spacers had a lower rate of permeate flux decline than the membranes with chevrons despite having greater bacteria concentrations on their surfaces. With better optimization of the micromixer design, the micromixers could be used to control where the bacteria will adhere to the surface and create a more biofouling resistant membrane that will help to drive down the cost of water treatment.

Synthesis and characterization of a family of structurally characterized dysprosium alkoxides for improved fatigue-resistance characteristics of PDyZT thin films.

Using either an ammoniacal route, the reaction between DyCl3, Na0, and HOR in liquid ammonia, or preferentially reacting Dy(N(SiMe3)2)3 with HOR in a solvent, we isolated a family of dysprosium alkoxides as [Dy(mu-ONep)2(ONep)]4 (1), (ONep)2Dy[(mu3-ONep)(mu-ONep)Dy(ONep)(THF)]2(mu-ONep) (2), (ONep)2Dy[(mu3-ONep)(mu-ONep)Dy(ONep)(py)]2(mu-ONep) (3), [Dy3(mu3-OBut)2(mu-OBut3(OBut)4(HOBut)2] (4), [Dy3(mu3-OBut)2(mu-OBut)3(OBut)4(THF)2] (5), [Dy3(mu3-OBut)2(mu-OBut)3(OBut)4(py)2] (6), (DMP)Dy(mu-DMP)4[Dy(DMP)2(NH3)]2 (7), [Dy(eta6-DMP)(DMP)2]2 (8), Dy(DMP)3(THF)3 (9), Dy(DMP)3(py)3 (10), Dy(DIP)3(NH3)2 (11), [Dy(eta6-DIP)(DIP)2]2 (12), Dy(DIP)3(THF)2 (13), Dy(DIP)3(py)3 (14), Dy(DBP)3(NH3) (15), Dy(DBP)3 (16), Dy(DBP)3(THF) (17), Dy(DBP)3(py)2 (18), [Dy(mu-TPS)(TPS2]2 (19), Dy(TPS)3(THF)3 (20), and Dy(TPS)3(py)3 (21), where ONep = OCH2CMe3, OBut) = OCMe3, DMP = OC6H3(Me)(2)-2,6, DIP = OC6H3(CHMe2)(2)-2,6, DBP = OC6H3(CMe3)(2)-2,6, TPS = OSi(C6H5)3, tol = toluene, THF = tetrahydrofuran, and py = pyridine. We were not able to obtain X-ray quality crystals of compounds 2, 8, and 9. The structures observed and data collected for the Dy compounds are consistent with those reported for its other congeners. A number of these precursors were used as Dy dopants in Pb(Zr0.3Ti0.7)O3 (PZT 30/70) thin films, with compound 12 yielding the highest-quality films. The resulting Pb0.94Dy0.04(Zr0.3Ti0.7)O3 [PDyZT (4/30/70)] had similar properties to PZT (30/70), but showed substantial resistance to polarization reversal fatigue.